CN109863431A - Phase difference film, its manufacturing method, polarizing film and display device - Google Patents

Phase difference film, its manufacturing method, polarizing film and display device Download PDF

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Publication number
CN109863431A
CN109863431A CN201780065876.6A CN201780065876A CN109863431A CN 109863431 A CN109863431 A CN 109863431A CN 201780065876 A CN201780065876 A CN 201780065876A CN 109863431 A CN109863431 A CN 109863431A
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China
Prior art keywords
phase difference
layer
inorganic particulate
difference film
thermoplastic resin
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CN201780065876.6A
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CN109863431B (en
Inventor
浅田毅
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Zeon Corp
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Nippon Zeon Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Abstract

A kind of phase difference film, include the layer A containing thermoplastic resin A and inorganic particulate I, the NZ coefficient of 540nm is more than 0.1 and less than 1.0, postpone Re in the face of 540nm to be more than 50nm and be less than 300nm, above-mentioned thermoplastic resin A is the resin with negative intrinsic birefringence value, above-mentioned inorganic particulate I is the inorganic particulate of plate, the mean radius of the board direction of above-mentioned inorganic particulate I is 10nm or more and 60nm hereinafter, the content ratio of the above-mentioned inorganic particulate I in above-mentioned layer A is 5 weight % or more and 20 weight % or less.

Description

Phase difference film, its manufacturing method, polarizing film and display device
Technical field
The present invention relates to phase difference film, its manufacturing method, polarizing film and display devices.
Background technique
As the method for the viewing angle compensation in plane conversion (IPS) formula liquid crystal display device, proposes and use a piece of NZ The method for the wave plate of diaxiality λ/2 that coefficient is about 0.5.
The manufacturing method of phase difference film as coefficient < 10 < NZ, it is known that be bonded shrinkage film in the face of resin film and formed Laminated body controls the method (patent document 1) of the refractive index of the thickness direction of resin film using the convergent force of shrinkage film.
In addition, the method as the other viewing angle compensation in IPS formula liquid crystal display device, it is also proposed that combine negative The method of C plate and negative A plate.
As being combined with the phase difference film of negative C plate and negative A plate, it is known that the phase of inorganic layered compounds will have been used Poor film and the uniaxial orientation phase difference film by having the thermoplastic resin of negative refractive anisotrop to be formed are combined Compensation with phase difference film (patent document 2).
Existing technical literature
Patent document
Patent document 1: No. 2818983 bulletins of Japanese Patent No. (corresponding other countries' bulletin: U.S. Patent No. 5245456 Number specification)；
Patent document 2: No. 3206132 bulletins of Japanese Patent No..
Summary of the invention
Problems to be solved by the invention
It is above-mentioned to be about using a piece of NZ coefficient like that from the viewpoint of number of components to be advisable less in order to compensate for visual angle The method of 0.5 wave plate of diaxiality λ/2 is more excellent than the method for combining multi-disc optical film.
However, realizing that the method for the characteristic of coefficient < 10 < NZ is limited by a piece of phase difference film.System as phase difference film Method is made, by general this means of stretched thermoplastic resin, that is, allows to obtain the phase of coefficient >=1 NZ or coefficient≤0 NZ Potential difference film, it is also difficult to obtain the phase difference film of coefficient < 10 < NZ.
Resin film is not only needed in order to manufacture phase difference film according to the technology of patent document 1, it is also necessary to which shrinkage film glues Connect multiple materials such as agent, therefore the producing rate variance of phase difference film, high production cost.
According to the technology of patent document 2, not only component count quantitative change is more, but also in addition to the extrusion operation of thermoplastic resin, drawing Stretch the painting process that inorganic layered compounds are needed further exist for except process, therefore the producing rate variance of phase difference film, production cost It is high.
It is therefore desirable to phase excellent in terms of productivity and production cost, with the performance for being suitable for viewing angle compensation Poor film.
The solution to the problem
The present inventor has made intensive studies to solve the above-mentioned problems, as a result, it has been found that, by the inclusion of defined thermoplastic Property Resin A and regulated proportion inorganic particulate I, delay Re and NZ coefficient is the phase difference film of defined range in face, so as to It enough solves the above problems, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of phase difference film, comprising the layer A containing thermoplastic resin A and inorganic particulate I,
The NZ coefficient of 540nm is more than 0.1 and less than 1.0,
Postponing Re in the face of 540nm is more than 50nm and less than 300nm,
Above-mentioned thermoplastic resin A is the resin with negative intrinsic birefringence value,
Above-mentioned inorganic particulate I is the inorganic particulate of plate,
The mean radius of the board direction of above-mentioned inorganic particulate I be 10nm or more and 60nm hereinafter,
The content ratio of above-mentioned inorganic particulate I in above-mentioned layer A is 5 weight % or more and 20 weight % or less.
[2] phase difference film according to [1], wherein above-mentioned thermoplastic resin A includes polymer, above-mentioned polymer packet Containing styrene units and selected from one or more of maleic anhydride units, methacrylic acid unit and maleimide amine unit list Member.
[3] phase difference film according to [1] or [2], wherein further include a layer B, above-mentioned layer B contains thermoplastic resin Rouge B is as principal component, and 50% energy of rupture is 1.0 × 10-2J or more.
[4] phase difference film according to [3], wherein the glass transition temperature Tg A (DEG C) of above-mentioned thermoplastic resin A Meet the relationship of TgA > TgB with the glass transition temperature Tg B (DEG C) of above-mentioned thermoplastic resin B.
[5] phase difference film according to [3] or [4], wherein postponing Re (B) in the face of the 540nm of above-mentioned layer B is 0nm More than and less than 10nm, the absolute value of the delay Rth (B) of the thickness direction of 540nm is 0nm more than and less than 10nm.
[6] a kind of manufacturing method of phase difference film,
Above-mentioned phase difference film includes the layer A containing thermoplastic resin A and inorganic particulate I,
The NZ coefficient of the above-mentioned phase difference film of 540nm is more than 0.1 and less than 1.0,
Postponing Re in the face of the above-mentioned phase difference film of 540nm is more than 50nm and less than 300nm,
Above-mentioned thermoplastic resin A is the resin with negative intrinsic birefringence value,
Above-mentioned inorganic particulate I is the inorganic particulate of plate,
The content ratio of above-mentioned inorganic particulate I in above-mentioned layer A is 5 weight % or more and 20 weight % or less.
The mean radius of the board direction of above-mentioned inorganic particulate I be 10nm or more and 60nm hereinafter,
The above method includes following processes:
The process for obtaining the stretching cephacoria comprising layer a, above-mentioned layer a contain above-mentioned thermoplastic resin A and above-mentioned inorganic particulate I, and the content ratio of above-mentioned inorganic particulate I be 5 weight % or more and 20 weight % hereinafter, and
The process for stretching above-mentioned stretching cephacoria along at least one direction.
[7] manufacturing method of the phase difference film according to [6], wherein above-mentioned phase difference film further includes a layer B, institute It states a layer B and contains thermoplastic resin B as principal component, and 50% energy of rupture is 1.0 × 10-2J or more,
Above-mentioned stretching cephacoria further includes the layer b containing above-mentioned thermoplastic resin B.
[8] a kind of polarizing film includes phase difference film described in wantonly 1 in the polarizer and [1]~[5].
[9] a kind of display device includes polarizing film described in [8].
Invention effect
According to the present invention it is possible to provide in terms of the productivity and production cost it is excellent, with being suitable for viewing angle compensation The phase difference film of performance.
Specific embodiment
Hereinafter, showing embodiment to the present invention and example object is described in detail.But the present invention is not limited to Embodiment and example object as shown below, the range of the range and its same range that do not depart from request of the invention can be with It arbitrarily changes and implements.
In the following description, the film of " strip " refers to the film of the length relative to wide at least 5 times or more, preferably has There are 10 times or the length more than it, specifically refers to the film that can be rolled into roll and the length of keeping or the degree transported. Length is not particularly limited relative to the upper limit of the ratio of width, such as can be set as 100000 times or less.
In the following description, unless otherwise specified, postponing Re in the face of film is to be indicated by Re=(nx-ny) × d Value.In addition, the delay Rth of the thickness direction of film is unless otherwise specified, to pass through Rth={ (nx+xy)/2-nz } × d The value of expression.In addition, NZ coefficient is unless otherwise specified, for the value indicated by (nx-nz)/(nx-ny).Here, nx table Show the refractive index that the direction of largest refractive index is provided in the direction (direction in face) of the thickness direction perpendicular to film.Ny is indicated upper State the refractive index in the direction that the direction direction Zhong Yunx is orthogonal in face.The refractive index of nz expression thickness direction.The thickness of d expression film. Unless otherwise specified, measurement wavelength is 540nm.
In the following description, unless otherwise specified, intrinsic birefringence value is in the refractive index ratio of draw direction and its Positive value is set as in the case that the refractive index in orthogonal direction is big, draw direction refractive index than orthogonal to that direction folding Penetrate rate it is small in the case where be set as negative value.Intrinsic birefringence value can be distributed according to the dielectric constant of material to be calculated.
In the following description, " (methyl) alkyl acrylate " includes " alkyl acrylate ", " methacrylate Ester " and their combination, " (methyl) acrylate " include " acrylate ", " methacrylate " and their combination.
In the following description, the direction " parallel " " vertical " of element and " orthogonal " unless otherwise specified, not It damages in the range of effect of the invention, also may include the error for example in the range of ± 5 °.
In the following description, the length direction of the film of strip is usually flat with the flow direction of the film in manufacturing line Row.Inclined direction refers to neither width direction is also not the direction of length direction.
In the following description, unless otherwise specified, " polarizing film ", " 1/2 wave plate " and " quarter wave plate " not only includes Upright and outspoken component also may include the such component with pliability of film of such as resin.
In the following description, unless otherwise specified, bonding agent refers not only to the bonding agent of narrow sense (irradiation energy is penetrated After line or after heat treatment, 23 DEG C of storage shear modulus is the bonding agent of 1MPa~500MPa), it also include 23 DEG C of shearing Storage modulus is less than the adhesive of 1MPa.
In the following description, unless otherwise specified, the slow axis of film indicates the slow axis in the face of the film.
[summaries of 1. phase difference films]
Phase difference film of the invention includes the layer A containing thermoplastic resin A and inorganic particulate I.Layer A is preferably single layer knot Structure.
[2. thermoplastic resin A]
Thermoplastic resin A is the thermoplastic resin with negative intrinsic birefringence value.With negative intrinsic birefringence value Thermoplastic resin includes the polymer with negative intrinsic birefringence value.
As long as thermoplastic resin A is not limited especially then comprising having the resin of the polymer of negative intrinsic birefringence value It is fixed, such as resin (the also referred to as polyphenyl containing the polymer comprising styrene units or styrene derivative unit can be enumerated Vinyl)；Polyacrylonitrile resin；Plexiglass；Comprising being selected from styrene, styrene derivative, propylene The resin of the multiple copolymer of the monomer of nitrile and methyl methacrylate；With the combination of these resins.It, can as styrene resin It enumerates the resin for example containing the polymer being made of styrene units or styrene derivative unit and contains comprising benzene second The resin of the polymer of alkene unit or styrene derivative and other monomers unit.
As styrene derivative unit, such as ring-alkylated styrenes unit, halogenated styrenes unit, alkoxy benzene can be enumerated Ethylene unit.
It, can as the other monomers unit that the polymer comprising styrene units or styrene derivative unit may include Enumerate acrylonitrile unit, maleic anhydride units, (methyl) methyl acrylate units, (methyl) acrylic acid units, maleimide Unit and butadiene unit.
Thermoplastic resin A is more excellent from the easness of phase difference shown this viewpoint preferably polystyrene resin It is selected as the polystyrene resin comprising following polymer, which includes styrene units or styrene derivative unit, with And a kind or more selected from maleic anhydride units, methacrylic acid unit and maleimide amine unit, from this high viewpoint of heat resistance It sets out, further preferably includes the polystyrene resin of following polymer, which includes styrene units or styrene Derivative unit and maleic anhydride units.
Thermoplastic resin A particularly preferably includes the polystyrene resin of following polymer, which includes styrene Unit and selected from one or more of maleic anhydride, methacrylic acid unit and maleic amide unit unit, is most preferably wrapped Polystyrene resin containing following polymer, the polymer include styrene units and maleic anhydride units.
The ratio with the polymer of negative birefringence value in thermoplastic resin A is preferably 50 weight % or more, more excellent It is selected as 60 weight % or more, particularly preferably 70 weight % or more.The polymerization with negative birefringence value in thermoplastic resin A The upper limit of the ratio of object is 100 weight %.
Thermoplastic resin A can be independent a kind, or combination of more than two kinds.
The glass transition temperature Tg A of thermoplastic resin A is not particularly limited, and preferably 120 DEG C or more, more preferably 125 DEG C or more, further preferably 130 DEG C or more, preferably 160 DEG C hereinafter, more preferably 155 DEG C hereinafter, further preferably It is 150 DEG C or less.
Thermoplastic resin A of the invention may include any other than having the polymer of negative intrinsic birefringence value Ingredient.
As the arbitrary ingredient that thermoplastic resin A may include, such as antioxidant can be enumerated；Light stabilizer；Wax；At Core agent；Fluorescent whitening agent；Ultraviolet absorbing agent；Colorant；Fire retardant；Flame retardant；Antistatic agent；Plasticizer；Near infrared ray Absorbent；Lubricant；Filler etc..It, can also be in addition, the arbitrary ingredient that may include of thermoplastic resin A can be independent a kind For the combination of more than two kinds of arbitrary ratio.
[3. inorganic particulate I]
Inorganic particulate I is the inorganic particulate of plate.In the present specification, for inorganic particulate, " plate " refers to plate face side To radius relative to a thickness of 10 times or more.Radius is not particularly limited relative to the upper limit of the ratio of thickness, can be set as example Such as 100 times or less.The mean radius of the board direction of inorganic particulate I be 10nm or more and 60nm hereinafter,
[constituent material of 3.1. inorganic particulate I]
Inorganic particulate I can be the particle of the inorganic matter of plate, be also possible to the inorganic matter and organic compound of plate Compound.
As the inorganic matter for constituting inorganic particulate I, clay mineral for example with layer structure can be enumerated, it is further specific For, clay mineral (such as hectorite, montmorillonite and the bentonite of such as terre verte race can be enumerated；These substituent；These Derivative) and its mixture.From the viewpoint of obtaining the excellent phase difference film of the transparency, the inorganic of inorganic particulate I is constituted Object is preferably or mixtures thereof the clay mineral of terre verte race.
The inorganic matter for constituting inorganic particulate I can be synthetic, be also possible to natural products, since impurity is few and saturating Bright property is excellent, therefore preferred synthetic, more preferable synthetic li-montmorillonite.
In the case where the compound of inorganic matter and organic compound that inorganic particulate I is plate, as the inorganic grain of composition The organic compound of sub- I can enumerate the compound that can be for example reacted with the oxygen atom of clay mineral or hydroxyl, comprising can With the ionic compound for the ion that the exchangeable cation with the crystallization interlayer for being present in clay mineral swaps, it is specific and Speech, can enumerate such as quaternary ammonium compound.
In the case where inorganic matter is clay mineral, carrying out compound organic compound with inorganic matter is preferably quaternary ammonium compounds Object, more preferably comprising by alkyl and/or benzyl instead of the compound of ammonium ion (such as include two (octadecane of dimethyl Base) ammonium ion compound, the compound comprising dimethyl benzyl octadecyl ammonium ion, include tricaprylmethyl ammonium ion Compound) or the compound of the ammonium ion comprising being replaced by the substituent group of long-chain (such as include methyl diethyl polyoxypropylene The compound of (such as degree of polymerization 25) ammonium ion).
Quaternary ammonium compound can be according to solvent (such as the aromatic hydrocarbons such as benzene,toluene,xylene for dispersing inorganic particulate I； The ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK)；The lower alcohols such as methanol, ethyl alcohol, propyl alcohol；Carbon tetrachloride, chloroform, methylene chloride, two The halogenated hydrocarbons such as chloroethanes) and it is suitable for selection.
Make inorganic matter and quaternary ammonium compound carry out it is compound and in the case where as inorganic particulate I, quaternary ammonium compound is usual It is imported into inorganic matter in the form of quaternary ammonium ion, forms the compound of inorganic matter and quaternary ammonium ion.
In the case where inorganic particulate I is the compound of inorganic matter and organic compound, inorganic matter and organic compound are manufactured The method of the compound of object is not particularly limited, and can be manufactured by well known method.It can enumerate for example in decentralized medium In, the organic compounds such as the inorganic matters such as clay mineral and quaternary ammonium compound are contacted, will be present in the inorganic matters such as clay mineral Crystallize the method that the cation such as the exchangeable cation of interlayer and the quaternary ammonium ion of composition organic compound swaps.
Specifically, can enumerate is dispersed in water clay mineral (such as synthetic li-montmorillonite), organic compound is added (such as the quaternary ammonium compounds such as dimethyl two (octadecyl) ammonium chloride), the method being stirred.Reaction time can be set to example Such as 2 hours.Reaction temperature can be set to such as room temperature.After the reaction, compound and water as decentralized medium can be passed through Such as filtering is separated, and is next cleaned using decentralized medium, thus removes byproduct salt from compound.
Sun in the case where inorganic particulate I is the compound of clay mineral and quaternary ammonium compound, relative to clay mineral Ion exchange capacity preferably uses quaternary ammonium compound with 0.5~1.5 times of equivalent, more preferably uses quaternary ammonium compounds with 1.0 equivalents Object.
For inorganic particulate I, the dispersibility due to dispersibility in a solvent and in resin is excellent, preferably plate Inorganic matter and organic compound compound, the more preferably compound of clay mineral and quaternary ammonium compound, further preferably For the compound of hectorite and quaternary ammonium compound.
As inorganic particulate I, commercially available product can be used.Hectorite (the KUNIMINE that organises can be used for example INDUSTRIES corporation " SUMECTON-SAN ").
[mean radius of 3.2. inorganic particulate I]
The mean radius of the board direction of inorganic particulate I can be measured by following methods.
After dispersing solvent (such as toluene) for inorganic particulate I, drips in substrate surface, evaporate solvent, by sweeping Retouch remaining nothing on the surface of type electron microscope (such as Japan Electronics " JSM-7200F ", 150000 times of multiplying power) observation substrate Machine particle, the inorganic particulate arbitrarily selected for 200 calculate the area A of plate face, according to 200 obtained inorganic particulates Plate face area, pass through lower formula (I) calculate 200 inorganic particulates board direction radius r.
[mathematical expression 1]
Using the average value of the radius r of the board direction of 200 inorganic particulates of calculating as the board direction of inorganic particulate Mean radius R.
For inorganic particulate I of the invention, the mean radius of board direction is 10nm or more, preferably 15nm with On.Thus it enables that NZ coefficient is more than 0 and less than 1.0.
For inorganic particulate I of the invention, the mean radius of board direction be 60nm hereinafter, preferably 50nm with Under, more preferably 40nm or less.Thus it enables that the haze value of phase difference film is low.
[content ratio of the inorganic particulate I in 3.3. layers of A]
Inorganic particulate I is 5 weight % or more, preferably 7 weight % or more in the content ratio in layer A.Thus it enables that NZ coefficient is more than 0.1 and less than 1.0.
Inorganic particulate I is 20 weight % hereinafter, preferably 15 weight % or less in the content ratio in layer A.Thus, it is possible to The mechanical strength of retaining layer A.
[thickness of 3.4. layers of A]
Layer A thickness can be suitable for setting, preferably 10 μm or more, more preferably 20 μm or more, preferably 100 μm with Under, more preferably 80 μm or less.
[any ingredient of 3.5. layers of A]
Layer A can also include arbitrary ingredient other than thermoplastic resin A and inorganic particulate I.As arbitrarily at Point, such as surfactant can be enumerated.
[4. arbitrary layer]
Phase difference film of the invention can also have arbitrary layer other than layer A.
As arbitrary layer, it can enumerate and contain thermoplastic resin B as principal component and 50% energy of rupture is 1.0 × 10-2J with On layer B.
[physical property of 4.1. layers of B]
For layer B, 50% energy of rupture is 1.0 × 10-2J or more, preferably 1.5 × 10-2J or more, more preferably 2.0×10-2J or more.Only there is compared to phase difference film the case where layer A as a result, can be improved the mechanical strength of phase difference film. 50% energy of rupture is the bigger the better.Therefore the upper limit of 50% energy of rupture is not particularly limited, and can be set to such as 10 × 10-2J or less.
50% energy of rupture can be measured according to JIS-K7124-1 (staircase method).As measurement device, punching can be used Hit exerciser (such as ASKA COMPANY system " S gauge ").
Delay Re (B) is preferably less than 10nm, more preferably 5nm hereinafter, further preferably in the face of the 540nm of layer B 2nm or less.Thereby, it is possible to reduce layer B to the influence of the optical characteristics bring of phase difference film.Postpone Re in the face of the 540nm of layer B It (B) is usually 0nm or more.
The absolute value of the delay Rth (B) of the thickness direction of the 540nm of layer B is preferably less than 10nm, more preferably 5nm with Under, further preferably 2nm or less.Thereby, it is possible to reduce layer B to the influence of the optical characteristics bring of phase difference film.Layer B's The absolute value of the delay Rth (B) of the thickness direction of 540nm is usually 0nm or more.
[4.2. thermoplastic resin B]
Layer B includes thermoplastic resin B.As thermoplastic resin B, as long as can make 50% energy of rupture 1.0 of layer B × 10-2The resin of J or more is not particularly limited, and can enumerate such as acrylic resin.
Acrylic resin is the resin containing the polymer comprising (methyl) acrylate unit.
As the alkyl acrylate for constituting acrylate unit, such as methyl acrylate, propylene can be enumerated Acetoacetic ester, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, propylene Tert-butyl acrylate, the just own ester of acrylic acid, cyclohexyl acrylate, n-octyl, acrylic acid-2-ethyl caproite, the acrylic acid positive last of the ten Heavenly stems Ester, acrylic acid n-dodecane base ester.
As the alkyl acrylate for constituting alkylmethacrylate unit, such as methyl methacrylate can be enumerated Ester, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, metering system The secondary butyl ester of sour isobutyl ester, methacrylic acid, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, The positive last of the ten Heavenly stems ester of methacrylic acid -2- ethylhexyl, methacrylic acid, methacrylic acid n-dodecane base ester.
(methyl) acrylate unit can have the arbitrary substituent group such as hydroxyl, halogen atom.Have as composition The ester of (methyl) acrylic ester unit of these substituent groups can enumerate such as 2-Hydroxy ethyl acrylate, acrylic acid -2- hydroxyl Propyl ester, acrylic acid -4- hydroxybutyl, methacrylic acid -2- hydroxy methacrylate, methacrylic acid -2- hydroxy propyl ester, metering system Acid -4- hydroxybutyl, methacrylic acid -3- chlorine-2-hydroxyl propyl ester, glycidyl methacrylate.
Acrylic resin can be the resin containing the homopolymer being made of a kind of (methyl) acrylate unit, It can be the resin containing the copolymer comprising two or more (methyl) acrylate unit.In addition, acrylic resin can be with It is to contain (methyl) alkyl acrylate and can be with the resin of the copolymer of the monomer of (methyl) alkyl acrylate copolymer.
(methyl) acrylic acid alkyl in the polymer comprising (methyl) acrylate unit in acrylic resin The content ratio of ester units is preferably 50 weight % or more, more preferably 60 weight % or more, further preferably 70 weight % More than.
It can be not particularly limited with the monomer of (methyl) alkyl acrylate copolymer, such as fumaric acid diformazan can be enumerated Ester, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate etc. are in addition to (methyl) acrylic acid alkyl α other than ester, β-ethylenically unsaturated carboxylic acids ester；Acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, richness The α, β-ethylenically unsaturated carboxylic acids such as horse acid mono ethyl ester, fumaric acid list N-butyl, maleic anhydride, itaconic anhydride；Styrene, Alpha-Methyl The alkenyl aromas races such as styrene, methyl α-methylstyrene, vinyltoluene, divinylbenzene；1,3- butadiene, 2- methyl- 1,3- butadiene, 1,3- pentadiene, 2,3- dimethyl -1,3- butadiene, the chloro- 1,3- butadiene of 2-, cyclopentadiene equiconjugate two Alkene；The non-conjugated dienes such as 1,4- hexadiene, dicyclopentadiene, ethylidene norbornene；Acrylonitrile, methacrylonitrile, α-chlorine third The cyanidings alkene such as alkene nitrile, α-ethyl acrylonitrile；Acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N- hydroxymethyl, methyl Acrylamide, N, the unsaturated carboxylic acids amide such as N- dimethylacrylamide；The carboxylic acids unsaturation alcohol ester such as vinylacetate；Ethylene, The alkene such as propylene, butylene, amylene.These monomers can be used alone or two or more is applied in combination.It can be with (methyl) third The monomer of olefin(e) acid Arrcostab copolymerization is preferably selected from one or more of alkenyl aroma race and α, β-ethylenically unsaturated carboxylic acids, more excellent It is selected as a kind or more selected from styrene, maleic anhydride and methacrylic acid.
In the polymer comprising (methyl) acrylate unit in acrylic resin can be with (methyl) propylene The content ratio of the unit of acid alkyl ester copolymerization is preferably 50 weight % hereinafter, more preferably 40 weight % are hereinafter, further excellent It is selected as 30 weight % or less.
As including (methyl) alkyl acrylate and can be with the copolymerization of the monomer of (methyl) alkyl acrylate copolymer Object can specifically be enumerated for example comprising methyl methacrylate/acrylic acid methyl esters/butyl acrylate/styrol copolymer Resin, the resin comprising methyl methacrylate/acrylic acid methyl terpolymer include methyl methacrylate/styrene/propylene The resin of butyl acrylate copolymer, comprising methyl methacrylate/methacrylic acid/styrol copolymer resin, include methyl Methyl acrylate/phenylethylene/maleic anhydride copolymer resin.
Thermoplastic resin B is preferably acrylic resin, further preferably includes the polymerization of alkylmethacrylate unit The resin (alkyl methacrylate resin) of object, the further preferably resin of the polymer comprising methyl methacrylate (polymethyl methacrylate resin).
The ratio of the polymer comprising (methyl) acrylate unit in thermoplastic resin B is preferably 80 weight % More than, more preferably 90 weight % or more, particularly preferably 95 weight % or more.
Thermoplastic resin B can be independent a kind, or combination of more than two kinds.
Thermoplastic resin B may include the arbitrary ingredient other than polymer.
As the arbitrary ingredient that thermoplastic resin B may include, it can enumerate and be removed as what thermoplastic resin A may include Arbitrary ingredient and exemplary ingredient other than polymer.In addition, the arbitrary ingredient that thermoplastic resin B may include can be Independent a kind, or the combination of more than two kinds of arbitrary ratio.
The glass transition temperature Tg B of thermoplastic resin B is not particularly limited, and preferably 90 DEG C or more, more preferable 100 DEG C More than, preferably 120 DEG C hereinafter, more preferably 115 DEG C hereinafter, further preferably 110 DEG C or less.
The glass transition temperature of the glass transition temperature Tg A (DEG C) and thermoplastic resin B of preferred thermoplastic resin A TgB (DEG C) meets the relationship of TgA > TgB.It will include as a result, the layer A of thermoplastic resin A and comprising the layer B of thermoplastic resin B When carrying out while stretching, it is able to maintain the anisotropy of layer A and the anisotropy of reduction layer B.
The difference (TgA-TgB) (DEG C) of TgA and TgB is preferably 10 DEG C or more, and more preferably 15 DEG C or more, further preferably 20 DEG C or more, preferably 40 DEG C are hereinafter, more preferably 35 DEG C or less.By the way that the difference (TgA-TgB) of TgA and TgB is set as above-mentioned Range, so as to the range that do not overbate in stretching process in thermoplastic resin B, the anisotropy of retaining layer A simultaneously subtracts The anisotropy of weak layer B.
Differential scanning calorimeter (such as Seiko Instruments can be used in glass transition temperature Tg A and TgB Inc. " DSC-6100 " is made), it is measured with the condition of 10 DEG C sample size 10mg, heating rate/min.
Layer B contains thermoplastic resin B as principal component.
Principal component refers to, in layer B containing in ingredient, contains the maximum ingredient of weight ratio.
Thermoplastic resin B is preferably 50 weight % or more in the content ratio in layer B, more preferably 70 weight % or more, Further preferably 90 weight % or more.The upper limit of the content ratio of thermoplastic resin B in layer B is 100 weight %.
Layer B may include the arbitrary ingredient other than thermoplastic resin B.
[thickness of 4.3. layers of B]
Layer B thickness can be suitable for setting, preferably 10 μm or more, more preferably 15 μm or more, preferably 70 μm hereinafter, More preferably 50 μm or less.
[physical property of 5. phase difference films]
For phase difference film of the invention, the NZ coefficient of 540nm is more than 0.1 and less than 1.0.
For phase difference film of the invention, the NZ coefficient of 540nm is preferably 0.2 or more, and more preferably 0.25 or more, Preferably 0.9 hereinafter, more preferably 0.8 hereinafter, further preferably 0.75 or less.Thus, it is possible to well by phase difference film Viewing angle compensation for liquid crystal display device.
Postpone Re for phase difference film of the invention, in the face of 540nm to be more than 50nm and be less than 300nm.
Postponing Re in the face of the 540nm of phase difference film of the present invention is preferably 100nm or more, and more preferably 120nm or more is excellent 290nm is selected as hereinafter, more preferably 280nm or less.
Postpone Re in the face of phase difference film of the invention, delay Rth and the NZ coefficient of thickness direction can be surveyed by delay Determine device to be measured.As delay measurement device, such as great Zhong Electronics Co., Ltd system " RE-200 " can be used, Axometrics Co. Ltd. system " AxoScan ".
Postpone in the face of above-mentioned layer B Re (B) and thickness direction delay Rth (B) can also in the face of phase difference film Postpone Re, the delay Rth of thickness direction is carried out similarly measurement.
The mist degree of phase difference film of the invention be preferably 1% hereinafter, more preferably 0.5% hereinafter, further preferably 0.3% or less.Mist degree is the smaller the better, and usually 0% or more.
Mist degree can be measured according to JIS-K-7136.As measurement device, haze meter (such as Japan's electricity can be used Color Industrial Co., Ltd system " NDH-4000 ").
The thickness of phase difference film of the invention can be set appropriately depending on the application, be not particularly limited, preferably 10 μ M or more, more preferably 15 μm or more, further preferably 20 μm or more, preferably 70 μm hereinafter, more preferably 60 μm hereinafter, Further preferably 50 μm or less.
[manufacturing methods of 6. phase difference films]
The method for manufacturing phase difference film of the invention is not particularly limited, can be for example, by the side comprising following processes Method is preferably manufactured by the inclusion of the method for following processes to be manufactured.Phase difference film of the invention can pass through drawing It stretches this simple method to be manufactured, therefore can have high production rate, inhibit production cost.
(i) process for obtaining the stretching cephacoria comprising layer a, this layer of a contain thermoplastic resin A and inorganic particulate I, and above-mentioned The content ratio of inorganic particulate I is 5 weight % or more and 20 weight % or less；
(ii) stretching process of above-mentioned stretching cephacoria is stretched along at least one direction.
In process (i), the method for obtaining stretching cephacoria is not limited, and can enumerate such as solution casting method, extrusion molding The resin formings method such as method.
Stretching cephacoria preferably further includes the layer b containing thermoplastic resin B.
Before the stretching in the case where layer composition of the film other than layer a also comprising layer b, with (a/ layer b of layer), as obtaining The method for stretching cephacoria can be the film b that manufacture first includes layer b, pass through the methods of solution casting method forming layer a on film b And the method for stretching cephacoria is obtained, it is also possible to the material of layer a and layer b being coextruded the method for obtaining stretching cephacoria.Altogether Squeezing out can be implemented for example, by the extruder of the branch manifold die head with 2 stratotypes.
In process (ii), above-mentioned stretching cephacoria is stretched along at least one direction.
In process (ii), the draft temperature for stretching cephacoria is preferably the (TgA (glass transition temperature of thermoplastic resin rouge A Degree) -10 DEG C) more than, more preferably more than (TgA-5 DEG C), preferably (TgA+30 DEG C) hereinafter, more preferably (TgA+20 DEG C) with Under.
Stretching ratio can be suitable for selecting, preferably 1.2 times or more, more preferably 1.3 times or more, further preferably 1.4 times or more, preferably 4 times hereinafter, more preferably 3 times hereinafter, further preferably 2.5 times or less.In addition, along two with In the case that upper direction stretches, above-mentioned stretching ratio means stretching ratio in all directions.
In process (ii), stretched film is stretched along at least one direction, can also along more than two directions into Row stretches.As the direction for stretching stretched film, such as width direction, length direction and inclined direction can be enumerated.On edge Width direction and length direction in the case that both direction stretches these stretching cephacorias, such as along film are stretched.
It, can be by all directions in the case where being stretched stretched film along more than two directions in process (ii) Be stretching in different temperatures progress, also can be set to different stretching ratios and carry out.
[7. polarizing film]
Phase difference film of the invention can combine with the polarizer and polarizing film is made.
As the polarizer, can be used such as to the hydrophily for being suitable for polyvinyl alcohol, part dimethoxym ethane polyvinyl alcohol The film of polymer according to suitable sequence and mode implement using the dichroic substances such as iodine, dichroism fuel dyeing processing and Stretch processing, and then the film for the processing that implement crosslinking Treatment etc. suitable as needed.
Phase difference film of the invention is bonded with the polarizer by using suitable bonding agent, so as to manufacture tool The polarizing film for thering is the layer of (phase difference film/adhesive layer/polarizer) to constitute.Polarizing film can further include such as protective film layer Etc. arbitrary layer.
Phase difference film of the invention can be with 1 be combined with the polarizer and manufactures polarizing film, can also be with 2 or more and the polarizer It combines and manufactures polarizing film.Therefore, polarizing film may include multiple phase difference films of the invention.
[8. display device]
Phase difference film of the invention and the polarizing film comprising the polarizer can be with liquid crystal display elements and organic electroluminescent The combination of the image-displaying members such as display element, is made display device.As combined image-displaying member, such as liquid crystal can be enumerated Display element (liquid crystal display element of the arbitrary mode such as plane conversion (IPS) mode) and organic electroluminescent device.
[purposes of 9. phase difference films]
Phase difference film of the invention can be used as such as 1/2 wave plate, quarter wave plate, furthermore can be used as liquid crystal The reflection suppression of the viewing angle compensation of showing device, display device with and use well.
Embodiment
The present invention is specifically described hereinafter, showing embodiment.But the present invention is not limited by embodiment below, In the range of the range and its same range that do not depart from request of the invention, implementation can be arbitrarily changed.
In the following description, " % " and " part " of expression amount, is unless otherwise specified weight basis.Operation below Unless otherwise specified, it is carried out in normal temperature and pressure atmosphere.In addition, postponing the delay Rth and NZ system of Re, thickness direction in face Number indicates the measured value of wavelength 540nm.
[evaluation method]
The evaluation method of assessment item in the present embodiment is illustrated.
(mean radius of the board direction of inorganic particulate)
Toluene is added to inorganic particulate, 60 minutes ultrasonications is carried out and prepares the toluene dispersion liquid of inorganic particulate. Obtained dispersion liquid is dripped on the surface of mica substrate, makes toluene from the dispersion liquid evaporation dripped.It is aobvious by scanning electron Micro mirror (Japan Electronics system " JSM-7200F ", 150000 times of multiplying power) observation remains in the inorganic particulate on the surface of mica substrate, To 200 inorganic particulates arbitrarily selected, the area A of plate face is calculated respectively.According to the plate face of 200 obtained inorganic particulates Area calculates the radius r of the board direction of 200 inorganic particulates by above-mentioned formula (I).
Using the average value of the radius r of the board direction of 200 inorganic particulates of calculating as the board direction of inorganic particulate Mean radius R (nm).
(postponing Re in face)
To the film as evaluation object, surveyed using delay measurement device (great Zhong Electronics Co., Ltd system " RE-200 ") It is fixed.To postponing in the position finding face of the interval 5cm arranged on the same straight line of width direction, will similarly measure along length Direction (production line flow direction) interval 1m it is repeated 5 times.Using the average value of obtained measured value as postponing Re in the face of film.
(the delay Rth of thickness direction)
To the film as evaluation object, surveyed using delay measurement device (great Zhong Electronics Co., Ltd system " RE-200 ") It is fixed.Delay to the position finding thickness direction of the interval 5cm arranged on the same straight line of width direction, will similarly measure It is repeated 5 times to (production line flow direction) interval 1m along its length.Using the average value of obtained measured value as the thickness of film The delay Rth in direction.
(NZ coefficient)
It is right using delay measurement device (Axometrics Co. Ltd. system " AxoScan ") to the film as evaluation object The position finding NZ coefficient of the interval 5cm arranged on the same straight line of width direction will be measured similarly (raw along its length Producing line flow direction) interval 1m it is repeated 5 times.Using the average value of obtained measured value as the NZ coefficient of film.
(mist degree)
Film is determined according to JIS-K-7136 using haze meter (Nippon Denshoku Industries Co., Ltd.'s system " NDH-4000 ") Monolithic mist degree.
(50% energy of rupture)
Using impact tester (ASKA COMPANY system " S gauge "), surveyed according to JIS-K7124-1 (staircase method) It is fixed.
(glass transition temperature)
Using differential scanning calorimeter (Seiko Instruments Inc. system " DSC-6100 "), pass through sample size 10mg, 10 DEG C/min of heating rate condition determine glass transition temperature.
[embodiment 1]
(preparation of coating)
As thermoplastic resin A, styrene-maleic anhydride copolymer (NovaChemicals corporation is used " DylarkD332 ", 135 DEG C of glass transition temperature).
As inorganic particulate, the hectorite that organises (KUNIMINE INDUSTRIES corporation " SUMECTON- is used SAN ", plate, mean radius R=35 (nm), the compound of inorganic matter and organic compound).
To 10 parts of toluene, the inorganic particulate of 0.4 part of addition, stirring at normal temperature after ten minutes, is implemented at 30 minutes ultrasonic waves Reason.Then, the particle for adding 3.6 parts of thermoplastic resin A, further implements 120 minutes ultrasonications, obtains coating A1. In the whole components (inorganic particulate and thermoplastic resin A) of removing solvent (toluene) in coating A1 shared by thermoplastic resin A Ratio is 10 weight %.
(unstretching film A)
Coating A1 is cast (casting) on steel band, after removing toluene by drying oven, both ends is trimmed and obtains width 600mm, 100 μm of thickness of unstretching film A.The content ratio of inorganic particulate in unstretching film A is 10 weight %.
(manufacture of phase difference film: stretching process)
Continuously to spoke stretching-machine supply unstretching film A is expanded, by 150 DEG C of draft temperature, 2.0 times of stretching ratio along width Direction carries out stretch processing, obtains horizontal stretched film.Obtained horizontal stretched film is further supplied to vertical stretching device, stretching is passed through 140 DEG C of temperature, 1.5 times of stretching ratio and along its length (flow direction) carry out stretch process, obtained have table 1 shown in The phase difference film 1 of characteristic.Phase difference film 1 is equivalent to the layer A comprising inorganic particulate and thermoplastic resin A.Nothing in phase difference film 1 The content ratio (i.e. the content ratio of inorganic particulate in layer A) of machine particle is 10 weight %.
(manufacture of polarizing film and display device)
Remove the axis of homology be in width direction strip polarizer coiling body (Sanritz corporation " HLC2-5618S ", 180 μm of thickness) unilateral protective film, be bonded in the mode that the slow axis of phase difference film 1 is parallel with the axis of homology of the polarizer. Polarizing film is cut into from the coiling body.
Side is recognized in the display device of commercially available IPS liquid crystal display panel (LG chemistry system) with the polarizing film replacement configuration being cut into Polarizing film, assembled in such a way that the phase difference film side of above-mentioned polarizing film is configured in liquid crystal cell side.Pass through under light outside The display characteristic for the display device that visual confirmation obtains, as a result compared with before replacement, throughout it is comprehensive be very good aobvious Show characteristic.
[embodiment 2]
By following sequences, obtained with shown in table 1 specifically as the phase difference film of stacked film 2.
(production of film B)
As thermoplastic resin B, acrylic resin (Sumitomo Chemical Co's system " Sumipex HT55X ", glass have been used 105 DEG C of glass transition temperature).Thermoplastic resin B investment is had to the extruder of the diameter 60mm of T die head, will be melted at 270 DEG C Resin from T die head squeeze out casting drum on, made the film B of width 700mm, 50 μm of thickness of strip.The 50% of film B destroys It can be 6.0 × 10-2(J).Postponing Re in the face of the 540nm of film B is 0.5nm, and the absolute value of the delay Rth of thickness direction is 0.5nm。
(non-stretched stacked film)
The coating A1 prepared by embodiment 1 is cast (casting) on film B, after removing toluene by drying oven, trimming Both ends and the unstretching film B for obtaining width 600mm, 80 μm of thickness.
(manufacture of phase difference film)
The non-stretched stacked film B continuously supplied to expansion spoke stretching-machine, passes through 150 DEG C of draft temperature, stretching ratio 2.0 Stretch processing is carried out in the width direction again, obtains horizontal stretching stacked film.By obtained horizontal stretching stacked film further to vertical drawing Unit feeding is stretched, stretch process is carried out along its length (flow direction) by 135 DEG C of draft temperature, 1.5 times of stretching ratio, The phase difference film 2 as stacked film with characteristic shown in table 1 is obtained.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 2 instead of phase difference film 1 Piece and assemble the display device 2 of the polarizing film.Have rated the display characteristic of display device 2 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be very good display characteristic.
[embodiment 3]
(preparation of particle A)
Device (Hitachi's corporation) is concentrated and dried with 270 DEG C of temperature, pressure 1kPa or less from passing through using cylinder type Coating A1 prepared by embodiment 1 removes toluene as solvent, from the die head of the extruder for being connected directly between concentrate drying device with Molten condition is extruded as strand, cuts off after cooling, obtains particle A.
(manufacture of phase difference film)
By particle A and as the acrylic resin (Sumitomo Chemical Co system " Sumipex of thermoplastic resin B HT55X ", 105 DEG C of glass transition temperature) particle be supplied respectively to the extruder of screw rod radius 40mm and 20mm, from 2 stratotypes Branch manifold die head is squeezed out upper to cooling drum and is cooled down, and has obtained 80 μm of thickness (comprising inorganic particulate and thermoplastic resin A A:50 μm of layer, B:30 μm of the layer comprising thermoplastic resin B), the stacking unstretching film C of width 600mm.Include inorganic particulate and heat The layer A of the layer of plastic resin A and thickness as the layer B comprising thermoplastic resin B are adjusted by the revolving speed of extruder.Even Continue the non-stretched stacked film C supplied to expansion spoke stretching-machine, by 150 DEG C of draft temperature, 2.0 times of stretching ratio along width Direction carries out stretch processing, obtains horizontal stretching stacked film.Obtained horizontal stretching stacked film is further supplied to vertical stretching device, Stretch process is carried out along its length (flow direction) by 135 DEG C of draft temperature, 1.5 times of stretching ratio, is had The phase difference film 3 as stacked film of characteristic shown in table 1.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 3 instead of phase difference film 1 Piece and assemble the display device 3 of the polarizing film.Have rated the display characteristic of display device 3 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be very good display characteristic.
[embodiment 4]
(manufacture of phase difference film)
The water of 1000mL is dispersed by the synthesis lithium montmorillonite (BYK corporation " Laponite ") of 20g, is added to it 20g Dimethyl two (octadecyl) ammonium chloride, 2 hours are reacted at room temperature while stirring and obtains reaction product.Next, Reaction product is filtered, washes with water and removes byproduct salt, dry, pulverize, obtained organically-modified hectorite.It obtains Organically-modified hectorite be inorganic matter and organic matter compound.
As inorganic particulate, instead of the hectorite that organises (KUNIMINE INDUSTRIES corporation " SUMECTON- SAN ") above-mentioned organically-modified hectorite (plate, mean radius R=20 (nm)) is used, in addition to this, and described in embodiment 1 The preparation of coating A1 be carried out similarly, be prepared for coating A2.Instead of coating A1 use coating A2, by stretching condition such as table 1 that Sample changes, and in addition to this, is performed in the same manner as in Example 2, and has obtained phase difference film 4.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 4 instead of phase difference film 1 Piece and assemble the display device 4 of the polarizing film.Have rated the display characteristic of display device 4 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be very good display characteristic.
[embodiment 5]
(manufacture of phase difference film)
By the weight ratio of inorganic particulate and thermoplastic resin A in coating become 15: 85 in a manner of adjust inorganic particulate and The additive amount of thermoplastic resin A, in addition to this, the preparation with coating A1 are carried out similarly, and are prepared for coating A3.Instead of coating A1 Using coating A3, stretching condition is changed as was the case with table 1, in addition to this, is performed in the same manner as in Example 2, has obtained phase Potential difference film 5.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 5 instead of phase difference film 1 Piece and assemble the display device 5 of the polarizing film.Have rated the display characteristic of display device 5 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be very good display characteristic.
[embodiment 6]
(manufacture of phase difference film)
As thermoplastic resin A, instead of styrene-maleic anhydride copolymer (NovaChemicals corporation " DylarkD332 "), using polystyrene (PS Japan Co. Ltd. system " HF77 ", 100 DEG C of glass transition temperature), remove this In addition, the preparation with coating A1 is carried out similarly, and is prepared for coating A4.Coating A4 is used instead of coating A1, such as by stretching condition Table 1 changes like that, in addition to this, is performed in the same manner as in Example 2, and has obtained phase difference film 6.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 6 instead of phase difference film 1 Piece and assemble the display device 6 of the polarizing film.Have rated the display characteristic of display device 6 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be very good display characteristic.
[embodiment 7]
(manufacture of phase difference film)
Stretching condition is changed as was the case with table 1, in addition to this, is performed in the same manner as in Example 2, has obtained phase difference Film 7.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 7 instead of phase difference film 1 Piece and assemble the display device 7 of the polarizing film.Have rated the display characteristic of display device 7 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be good display characteristic.
[embodiment 8]
(manufacture of phase difference film)
Stretching condition is changed as was the case with table 1, in addition to this, is performed in the same manner as in Example 2, has obtained phase difference Film 8.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film 8 instead of phase difference film 1 Piece and assemble the display device 8 of the polarizing film.Have rated the display characteristic of display device 8 similarly to Example 1, as a result with Compared before replacement, throughout it is comprehensive be good display characteristic.
[comparative example 1]
(manufacture of phase difference film)
As inorganic particulate, using the plate like inorganic particle of mean radius R=80 (nm), in addition to this, with coating A1's Preparation is carried out similarly, and is prepared for coating A5.Coating A5 is used instead of coating A1, stretching condition is changed as was the case with table 1, In addition to this, it is performed in the same manner as in Example 2, has obtained phase difference film c1.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film c1 instead of phase difference film 1 Piece and assemble the display device c1 of the polarizing film.The display characteristic of display device c1 is had rated similarly to Example 1, as a result Furthermore poor contrast does not have and spreads comprehensive good display characteristic.
[comparative example 2]
(manufacture of phase difference film)
By the weight ratio of inorganic particulate and thermoplastic resin A in coating become 30: 70 in a manner of adjust inorganic particulate and The additive amount of thermoplastic resin A, in addition to this, the preparation with coating A1 are carried out similarly, and are prepared for coating A6.Instead of coating A1 Using coating A6, stretching condition is changed as was the case with table 1, in addition to this, is performed in the same manner as in Example 2, has obtained phase Potential difference film c2.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film c2 instead of phase difference film 1 Piece and assemble the display device c2 of the polarizing film.The display characteristic of display device c2 is had rated similarly to Example 1, as a result Furthermore poor contrast does not have and spreads comprehensive good display characteristic.
[comparative example 3]
(manufacture of phase difference film)
Inorganic particulate and heat are adjusted in such a way that the weight ratio of inorganic particulate and thermoplastic resin A in coating becomes 3: 97 The additive amount of plastic resin A, in addition to this, the preparation with coating A1 are carried out similarly, and are prepared for coating A7.Make instead of coating A1 With coating A7, stretching condition is changed as was the case with table 1, in addition to this, is performed in the same manner as in Example 2, has obtained phase Poor film c3.
(manufacture of polarizing film and display device)
It is carried out, is polarized similarly to Example 1 in addition to this using phase difference film c3 instead of phase difference film 1 Piece and assemble the display device c3 of the polarizing film.The display characteristic of display device c3 is had rated similarly to Example 1, as a result Without throughout comprehensive good display characteristic.
The result of embodiment and comparative example is shown in table 1." inorganic particulate ratio " indicates to include inorganic particulate and heat in table 1 The content ratio (wt%) of inorganic particulate in the layer A of plastic resin A, " thickness " indicate the thickness of phase difference film.
[table 1]
Table 1
From above result it is found that the phase difference film haze value of Examples 1 to 8 is low, the phase of Examples 1 to 8 has been used Poor film all has good display characteristic throughout comprehensive.On the other hand, it is known that used the phase difference film of comparative example 1~3 Display device can not be realized throughout comprehensive good display characteristic.
It is found that the phase difference film of Examples 1 to 8 has the characteristic as 1/2 wave plate, the viewing angle compensation as display device Purposes is suitable.

Claims (9)

1. a kind of phase difference film, comprising the layer A containing thermoplastic resin A and inorganic particulate I,
The NZ coefficient of 540nm is more than 0.1 and less than 1.0,
Postponing Re in the face of 540nm is more than 50nm and less than 300nm,
The thermoplastic resin A is the resin with negative intrinsic birefringence value,
The inorganic particulate I is the inorganic particulate of plate,
The mean radius of the board direction of the inorganic particulate I be 10nm or more and 60nm hereinafter,
The content ratio of the inorganic particulate I in the layer A is 5 weight % or more and 20 weight % or less.
2. phase difference film according to claim 1, wherein the thermoplastic resin A includes polymer, the polymer packet Containing styrene units and selected from one or more of maleic anhydride units, methacrylic acid unit and maleimide amine unit list Member.
3. phase difference film according to claim 1 or 2, wherein further include a layer B, the layer B contains thermoplastic resin B is as principal component, and 50% energy of rupture is 1.0 × 10-2J or more.
4. phase difference film according to claim 3, wherein the glass transition temperature Tg A of the thermoplastic resin A and institute The glass transition temperature Tg B for stating thermoplastic resin B meets the relationship of TgA > TgB, and the unit of the TgA and TgB are DEG C.
5. phase difference film according to claim 3 or 4, wherein postponing Re (B) in the face of the 540nm of the layer B is 0nm More than and less than 10nm, the absolute value of the delay Rth (B) of the thickness direction of 540nm is 0nm more than and less than 10nm.
6. a kind of manufacturing method of phase difference film,
The phase difference film includes the layer A containing thermoplastic resin A and inorganic particulate I,
The NZ coefficient of the phase difference film of 540nm is more than 0.1 and less than 1.0,
Postponing Re in the face of the phase difference film of 540nm is more than 50nm and less than 300nm,
The thermoplastic resin A is the resin with negative intrinsic birefringence value,
The inorganic particulate I is the inorganic particulate of plate,
The content ratio of the inorganic particulate I in the layer A be 5 weight % or more and 20 weight % hereinafter,
The mean radius of the board direction of the inorganic particulate I be 10nm or more and 60nm hereinafter,
The method includes following processes:
The process for obtaining the stretching cephacoria comprising layer a, the layer a contain the thermoplastic resin A and the inorganic particulate I, and The content ratio of the inorganic particulate I be 5 weight % or more and 20 weight % hereinafter, and
The process for stretching cephacoria is stretched along at least one direction.
7. the manufacturing method of phase difference film according to claim 6, wherein the phase difference film further includes a layer B, institute It states a layer B and contains thermoplastic resin B as principal component, and 50% energy of rupture is 1.0 × 10-2J or more,
The stretching cephacoria further includes the layer b containing the thermoplastic resin B.
8. a kind of polarizing film includes phase difference film described in the polarizer and Claims 1 to 5 wantonly 1.
9. a kind of display device includes polarizing film according to any one of claims 8.
CN201780065876.6A 2016-12-28 2017-12-20 Retardation film, method for producing same, polarizing plate, and display device Active CN109863431B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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