WO2016204146A1 - Film stratifié multicouche - Google Patents

Film stratifié multicouche Download PDF

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Publication number
WO2016204146A1
WO2016204146A1 PCT/JP2016/067679 JP2016067679W WO2016204146A1 WO 2016204146 A1 WO2016204146 A1 WO 2016204146A1 JP 2016067679 W JP2016067679 W JP 2016067679W WO 2016204146 A1 WO2016204146 A1 WO 2016204146A1
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Prior art keywords
film
layer
multilayer
resin
laminated film
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PCT/JP2016/067679
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English (en)
Japanese (ja)
Inventor
合田亘
有家隆文
松居久登
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東レ株式会社
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Priority to CN201680022018.9A priority Critical patent/CN107533175B/zh
Priority to JP2016540086A priority patent/JP6787126B2/ja
Publication of WO2016204146A1 publication Critical patent/WO2016204146A1/fr

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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
    • 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
    • B32B7/027—Thermal 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

Definitions

  • the present invention relates to a multilayer laminated film and an optical film using the same.
  • a liquid crystal display device using a liquid crystal display panel as a display element is rapidly expanding its use as a thin display device such as a liquid crystal television, a liquid crystal monitor, and a personal computer.
  • a liquid crystal television such as a liquid crystal television, a liquid crystal monitor, and a personal computer.
  • the market for LCD TVs and mobile phones is growing significantly.
  • a polarizing plate is always used for a liquid crystal display device, but a polarizer protective film is generally used for the polarizing plate, and as the film, triacetyl cellulose (hereinafter referred to as “highly transparent” and optical isotropy) is used.
  • TAC triacetyl cellulose
  • the TAC film cannot be said to exhibit sufficient performance in terms of chemical resistance, scratch resistance, and the like, and as the liquid crystal display in recent years becomes larger and thinner, Strength, dimensional stability, high moisture permeability, and the like are issues.
  • Patent Documents 1 and 2 In order to solve the above problems, other amorphous resins such as cycloolefin polymers and acrylics have been studied in place of the TAC film (Patent Documents 1 and 2). There is a problem that costs are increased because no general-purpose resin is used.
  • PET film a polyethylene terephthalate (hereinafter referred to as PET) film is often used because it has low moisture permeability compared to a TAC film, is excellent in handling, and can be reduced in cost because it is a general-purpose resin.
  • a film made of a crystalline resin such as a PET film is generally subjected to a treatment such as uniaxial stretching or biaxial stretching, but the retardation may be increased by the stretching treatment.
  • phase difference of the film When the phase difference of the film is in a specific range, there is no effect on the visibility under natural light (non-polarized light), but there is a problem that rainbow unevenness and interference color can be seen when viewed through a polarizer such as polarized sunglasses. .
  • polarizer such as polarized sunglasses.
  • the unstretched state there is a merit that generation of light interference color can be suppressed, but in addition to the problem that the strength is remarkably reduced, it is used for a protective film for a polarizing plate in recent years where a demand for thinning is strong Was not appropriate.
  • Patent Document 4 a retardation film that uses a multilayer structure and uses structural birefringence and molecular orientation birefringence and has a strict requirement for retardation accuracy compared to a polarizer protective film.
  • the average layer thickness is very thin, 30 nm or less, and a special resin combination of an amorphous resin having negative optical anisotropy and an isotropic amorphous resin, and Since the thickness and the total number of layers are also very large, there has been a problem of high material and manufacturing costs. That is, even if the optical performance is satisfied, the characteristics are not different from those of the conventional amorphous resin, and the thin film, low cost, low moisture permeability, and dimensional stability are not satisfied.
  • the problem to be solved by the present invention is a multilayer laminated film having a biaxially oriented A layer and a weakly oriented B layer, and the respective phase differences of the A layer and the B layer are subtracted from each other.
  • a display device such as a large-screen liquid crystal display as a polarizer protective film
  • a high-quality display is obtained with little change in contrast, rainbow unevenness and interference color.
  • the present invention is as follows.
  • [1] A multilayer laminated film in which a layer A made of a biaxially orientable crystalline resin a and a layer B made of a resin b having lower crystallinity than a are alternately laminated, and the surface layer Multilayers characterized in that the total phase difference Re of the multilayer laminated film satisfies the expressions (1) and (2), where Re (k) is the phase difference in the kth layer from the first layer and n is the total number of layers.
  • Re (k) is the phase difference in the kth layer from the first layer
  • n is the total number of layers.
  • a multilayer laminate film in which at least three or more layers A are made of a biaxially orientable crystalline resin a and a B layer is made of a resin b having lower crystallinity than the crystalline resin a.
  • the refractive index in the direction giving the maximum refractive index in the in-plane direction is Nx (1)
  • the refractive index in the direction perpendicular to it is Ny (1)
  • the resin b is a multilayer laminated film containing one or more components selected from any of the component groups consisting of isophthalic acid, spiroglycol, isosorbide, fluorene, bisphenol A, and cyclohexyne dimethanol component.
  • the crystalline resin a is preferably a multilayer laminated film selected from polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.
  • the present invention Since the present invention has a low retardation, it can be used for a retardation film, a polarizer protective film having a retardation function, a substrate film for a touch panel, and the like.
  • a retardation film a polarizer protective film having a retardation function
  • a substrate film for a touch panel and the like.
  • there is little retardation in the width direction and unevenness in the orientation angle there is little change in contrast, rainbow unevenness, and interference color when mounted on a display device such as a large-screen liquid crystal display as a polarizer protective film. The effect which can obtain a simple display is produced.
  • FIG. 1 is a schematic diagram showing a light transmitting direction when different resins are stacked.
  • FIG. 2 is a schematic diagram showing a light transmitting direction when the same resin is stacked.
  • FIG. 3A is a schematic view when two single film films are stacked.
  • FIG. 3B is a schematic diagram showing the relationship of the refractive index ellipsoid when two single film films are stacked.
  • FIG. 4A is a distribution of refractive index ellipsoids in the width direction of the multilayer laminated film. (B) Distribution of the refractive index ellipsoid of the multilayer laminated film in the width direction when two multilayer laminated films are stacked.
  • FIG. 1 is a schematic diagram showing a light transmitting direction when different resins are stacked.
  • FIG. 2 is a schematic diagram showing a light transmitting direction when the same resin is stacked.
  • FIG. 3A is a schematic view when two single film films are stacked.
  • FIG. 3B is a
  • FIG. 5A is a schematic diagram of phase difference subtraction using one full-width multilayer laminated film.
  • FIG.5 (b) is a schematic diagram of the addition of the phase difference using one full width multilayer laminated film.
  • 6 is an orientation distribution of the A layer and the B layer of the multilayer laminated film of Example 11.
  • FIG. 7A shows the retardation distribution in the film width direction in the multilayer laminated film of Example 13.
  • FIG. 7B shows the orientation angle distribution in the film width direction of the multilayer laminated film of Example 13.
  • FIG. 8A shows a retardation distribution in the film width direction when the MD direction of the multilayer laminated film of Example 13 is reversed and bonded together.
  • FIG. 8B is a retardation distribution in the film width direction when two multilayer laminated films of Example 13 are bonded together with the same MD direction.
  • the in-plane retardation of the film or layer is a value represented by (Nx ⁇ Ny) ⁇ d unless otherwise specified.
  • Nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the film or layer and giving the maximum refractive index.
  • Ny represents the refractive index in the in-plane direction of the film or layer and perpendicular to the Nx direction.
  • d represents the film thickness of the film or layer.
  • the phase difference measurement wavelength is 590 nm.
  • the phase difference can be measured using a commercially available phase difference measuring apparatus (for example, “KOBRA-21ADH” manufactured by Oji Scientific Instruments, “WPA-micro” manufactured by Photonic Lattice) or the Senalmon method.
  • the multilayer laminated film of the present invention is a film in which crystalline resin a and resin b are alternately laminated at least three layers.
  • the term “alternately laminated” here means that layers made of different resins are laminated in a regular arrangement in the thickness direction. For example, when the layers are made of crystalline resin a and resin b, each layer is designated as A layer. , B layers are stacked in a regular arrangement such as A (BA) n (n is a natural number).
  • the outermost layer of this multilayer laminated film may have a C layer made of resin c and may have a configuration such as C ⁇ A (BA) n ⁇ C.
  • the total retardation Re of the multilayer laminated film satisfies the following formula (1).
  • k is a natural number.
  • phase difference Re of the entire multilayer laminated film obtained using a commercially available measuring device is smaller than the value obtained by individually measuring and calculating the phase difference of each layer and adding the respective phase differences. It means to become.
  • a film obtained by peeling each layer into a single film may be measured with a commercially available measuring device, or the surface layer as disclosed in JP-A-2014-149346. May be measured after polishing each with a plastic polishing cloth to form each layer as a single layer.
  • Re (1) is the phase difference of the outermost layer of the multilayer laminated film
  • Nx (1) and Ny (1) are the refractive index in the direction giving the maximum refractive index in the in-plane direction of the outermost layer and perpendicular thereto.
  • the refractive index in the direction, d (1) is the thickness of the outermost layer
  • D ′ is the total thickness of the layers using the same resin as the outermost layer in the multilayer laminated film. This equation will be described next.
  • the refractive index in the in-plane direction can be obtained by using a spectroscopic ellipsometer, spectrophotometer, prism coupler, Abbe refractometer or the like.
  • the phase difference of the outermost layer can be easily calculated.
  • the inner layer resin is the same resin as the outermost layer and the film forming conditions are the same, the birefringence of the outermost layer and the inner layer is assumed to be the same, and the phase difference of the inner layer can be estimated. Therefore, the phase difference can be measured for the same resin as the outermost layer of the multilayer laminated film.
  • the added value of the retardation of the layer made of the same resin as the outermost layer is larger than the total retardation Re of the multilayer laminated film, the formula (1) of claim 1 is already satisfied. That is, the retardation of the resin layer different from the outermost layer means that the effect of subtracting the retardation is acting on the multilayer laminated film.
  • the refractive index in the in-plane direction of the A layer is Nx (a) and Ny (a), respectively
  • the refractive index in the in-plane direction of the B layer is Nx (b) and Ny (b )
  • the birefringence of the A layer is (Nx (a) ⁇ Ny (a))
  • the birefringence of the B layer is (Nx (b) ⁇ Ny (b)).
  • the B layer is the same resin as the A layer and the layer is assumed to be A ′, the result is as shown in FIG.
  • d means the thickness of the two-layer film. Therefore, it is obvious that the total retardation Re of the multilayer laminated film is an added value of the retardation of each film. Therefore, generally, the sum of retardation obtained from the refractive index and thickness of each layer and the retardation of the laminated film measured using a commercially available measuring device should be the same value.
  • the total of the multilayer laminated film is more than the value obtained by adding the phase difference of each layer.
  • the phase difference Re was successfully subtracted.
  • the entire retardation Re of the multilayer laminated film that is, the in-plane direction retardation, needs to be 400 nm or less as shown in the equation (2).
  • the interference color under crossed Nicols is related to the phase difference value and is known in the Michel-Levy chart. 200 nm or less is more preferable from the viewpoint of becoming colorless when observed with crossed Nicols in which the polarizers are orthogonal. More preferably, it is 100 nm or less.
  • the achievement method is to devise a resin composition and film forming conditions described later.
  • the refractive index in the direction giving the maximum refractive index in the in-plane direction is Nx (1)
  • the refractive index in the direction perpendicular thereto is Ny (1)
  • the same resin as the outermost layer is used. It is preferable that the formula (5) is satisfied, where d (A) is the total thickness of the layers to be formed and Re is the total retardation of the multilayer laminated film.
  • the left side of the formula (5) is more preferably ⁇ 50 nm or less. More preferably, it is ⁇ 100 nm or less. Most preferably, it is ⁇ 150 nm or less.
  • the total thickness of the A layer / the total thickness of the B layer which is the lamination ratio, is preferably 1 or less from the viewpoint of aligning the B layer that is difficult to align as compared with the A layer. More preferably, it is 0.7 or less.
  • the glass transition temperature of the resin b used for the B layer is preferably 88 ° C. or higher.
  • the multilayer laminated film of the present invention needs to be formed by using a biaxially orientable crystalline resin a and a resin b having lower crystallinity than a.
  • a biaxially orientable resin is a resin whose refractive index in the in-plane direction is higher than that in the thickness direction when stretched in the film longitudinal direction and width direction. It can be easily measured using an optical measuring device such as a prism coupler.
  • the crystalline resin is a resin having a glass transition temperature Tg and a melting point Tm, and a resin having a melting enthalpy change ⁇ Hm> 0.
  • a preferable crystalline resin has a ⁇ Hm of 10 J / g or more. More preferably, it is 20 J / g.
  • the resin b needs to have lower crystallinity than the crystalline resin a, and includes an amorphous resin. Due to the difference in crystallinity between the crystalline resin a and the resin b and the film forming conditions suitable for the resin, the main orientation axes of the A layer and the B layer in the multilayer laminated film can be changed when sequentially stretched.
  • As a method for evaluating crystallinity it is known that evaluation can be performed by the magnitude of ⁇ Hm measured by DSC. The larger ⁇ Hm, the higher the energy required for melting, and the higher the crystallinity. Therefore, ⁇ Hm of the crystalline resin a needs to be higher than ⁇ Hm of the resin b. That is, the relationship ⁇ Hm (a)> ⁇ Hm (b) is established.
  • the resin b may be an adhesive having adhesiveness, an adhesive, and a curable resin.
  • the glass transition temperatures of the crystalline resin a and the resin b are separated.
  • the glass transition temperature of the crystalline resin a is preferably lower than the glass transition temperature of the resin b.
  • sequential biaxial stretching is adopted, and transverse stretching is performed after longitudinal stretching.
  • the longitudinal stretching temperature is sufficiently higher than the glass transition temperature
  • the longitudinal orientation in the longitudinal stretching does not proceed.
  • the glass transition temperature of the resin b is higher than the glass transition temperature of the crystalline resin a and the longitudinal stretching is performed under the condition of the glass transition temperature of the resin b + 5 ° C.
  • the orientation of the A layer does not advance
  • the vertical orientation of the B layer is stronger.
  • the difference in glass transition temperature is preferably 5 ° C. or more.
  • the difference in glass transition temperature is preferably 40 ° C. or less.
  • polyolefins such as polyethylene, polypropylene, poly (4-methylpentene-1), polyacetal, and cycloolefin Is a ring-opening metathesis polymerization of norbornenes, addition polymerization, biodegradable polymers such as aliphatic polyolefins, polylactic acid and polybutyl succinate, which are addition copolymers with other olefins, nylon 6, 11, 12, 66 Polyamide, aramid, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene copolymer polymethyl methacrylate, polycarbonate Polyester, polypropylene terephthalate / polyethylene
  • polymethyl methacrylate, polycarbonate, and polyester are preferably used from the viewpoint of strength, transparency, and versatility.
  • polyester Particularly preferred is polyester.
  • These may be a homopolymer, a copolymer, or a mixture of thermoplastic resins.
  • various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, thickeners, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers.
  • An agent, a dopant for adjusting the refractive index, and the like may be added.
  • polyester obtained by polymerization from a monomer mainly comprising an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and a diol is preferred.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid.
  • acids 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenyldicarboxylic acid.
  • aliphatic dicarboxylic acid examples include adipic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Among them, it is preferable to use terephthalic acid and 2,6-naphthalenedicarboxylic acid that exhibit a high refractive index. These acid components may be used alone or in combination of two or more, and further, a part of oxyacid of hydroxybenzoic acid or the like may be copolymerized.
  • diol component examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4- Hydroxyethoxyphenyl) propane, isosorbate, spiroglycol and the like. Of these, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.
  • polyesters polyethylene terephthalate and copolymers thereof, polyethylene naphthalate and copolymers thereof, polybutylene terephthalate and copolymers thereof, polybutylene naphthalate and copolymers thereof, and polyhexamethylene terephthalate and copolymers thereof. It is preferable to use a polymer, polycyclohexylenedimethylene terephthalate, and a copolymer thereof.
  • the most suitable resin combination of the present invention comprises any one of polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate as a biaxially orientable crystalline resin a, which is more crystalline than crystalline resin a.
  • a copolymer of the crystalline resin a is preferable.
  • the resin b is preferably a copolyester having at least one component selected from any of the component groups consisting of isophthalic acid, spiroglycol, isosorbide, fluorene, bisphenol A, and cyclohexyne dimethanol component.
  • a resin containing any one of isophthalic acid copolymerized polyethylene terephthalate, spiroglycol copolymerized polyethylene terephthalate, isosorbide copolymerized polyethylene terephthalate, fluorene copolymerized polyethylene terephthalate, bisphenol A copolymerized polyethylene terephthalate, and polycyclohexylenedimethylene terephthalate is used.
  • the copolymer component is preferably 5 mol% or more and 50 mol% or less from the viewpoint of exhibiting the lamination property with the crystalline resin a and the effect of subtracting the retardation. If the amount is less than 5 mol%, the effect of addition tends to be manifested.
  • the amount is 50 mol% or more, the subtraction may not be involved. From the viewpoint of setting the total retardation Re of the multilayer laminated film to 400 m or less, it is more preferably 10 mol% or more and 40 mol% or less.
  • the glass transition temperature of the crystalline resin a of the present invention is preferably lower than the glass transition temperature of the resin b.
  • the sequential biaxially stretched film forming step by setting the stretching temperature in the longitudinal direction to be equal to or higher than the glass transition transition of the resin b, the B layer composed of the resin b is oriented in the longitudinal direction, but the A layer composed of the resin a. Are not oriented vertically.
  • the layer A made of the resin a is easily oriented in the transverse direction, while the layer B made of the resin b is guided to the heat treatment process while the longitudinal orientation remains. . Therefore, orientation crystallization proceeds in the lateral direction in the A layer.
  • the bowing phenomenon is added, and crossed alignment states in which the main alignment axes of the A layer and the B layer are different are realized, and a phase difference subtraction effect is likely to occur.
  • the glass transition temperature of the resin b is preferably higher than the resin a by 10 ° C. or more, more preferably 20 ° C. or more.
  • the glass transition temperature of the resin b is preferably 88 ° C. or higher. More preferably, it is 90 ° or more, further preferably 95 ° C. or more.
  • crystalline resin a and resin b are prepared in the form of pellets or the like.
  • the pellets are dried in hot air or under vacuum as necessary, and then supplied to a separate extruder.
  • the resin melted by heating to a temperature equal to or higher than the melting point is made uniform in the amount of resin extruded by a gear pump or the like, and foreign matter or denatured resin is removed through a filter or the like.
  • Crystalline resin a and resin b sent out from different flow paths using these two or more extruders are then fed into the multilayer laminating apparatus.
  • the multilayer laminating apparatus a multi-manifold die, a feed block, a static mixer, or the like can be used. These may be combined arbitrarily.
  • a multi-manifold die or a feed block capable of individually controlling the thickness of each layer is preferable.
  • the structure of the feed block has at least one member in a comb-shaped slit plate having a large number of fine slits, and the crystalline resin a and the resin b supplied from two extruders pass through each manifold. Introduced into the slit plate.
  • the crystalline resin a and the resin b alternately flow through the introduction plate, finally, a multilayer structure of A / B / A / B /... Can be formed. Further, it is possible to increase the number of layers by overlapping the slit plates.
  • the thickness of the layer can be controlled by adjusting the slit shape (length, gap). Moreover, it is also possible to attach C layer which consists of resin c to the outermost layer of this multilayer laminated film using another 3rd extruder.
  • the laminating apparatus and the method for producing the multilayer laminated film are described in detail in JP-A-2007-307893 and JP-A-2007-79349, and it is preferable to employ them.
  • the number of stacked layers is preferably 9 or more from the viewpoint of additionally producing functions such as phase difference control and optical interference reflection by a layer of light wavelength level. More preferably, it is 50 layers or more, More preferably, it is 200 layers or more.
  • the average layer thickness is preferably 0.04 to 10 ⁇ m. If it is less than 0.04 ⁇ m, the optical characteristics and material characteristics of each layer are lost, which is not preferable. On the other hand, if it exceeds 10 ⁇ m, the thickness of the film becomes too thick, which is not preferable. From the viewpoint of imparting ultraviolet reflection and maintaining transparency, 0.04 to 0.06 ⁇ m or 0.11 to 5 ⁇ m is preferable.
  • the melt laminated in this way is extruded into a sheet form from a slit-shaped die, adhered to the casting drum by a method such as electrostatic application, cooled and solidified into an unstretched sheet, and then stretched in two directions. It is preferable to heat-treat.
  • particles may be added to the film raw material. Careful attention to the material is required. The addition amount is preferably very small, and more preferably no addition. As described above, it is preferable to assist the traveling property (slidability) of the film with the additive particles of the easy adhesion layer.
  • additives such as heat stabilizers, oxidation stabilizers, weathering stabilizers, ultraviolet absorbers, lubricants such as polyimide, polyamideimide, polymethyl methacrylate, formaldehyde resin, phenol resin
  • lubricants such as polyimide, polyamideimide, polymethyl methacrylate, formaldehyde resin, phenol resin
  • Organic fine particles such as cross-linked polystyrene, and inorganic fine particles such as wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin and clay can also be used.
  • biaxial stretching refers to stretching in the longitudinal direction (longitudinal direction) and the width direction (transverse direction).
  • the stretching is performed sequentially in two directions.
  • restretching may be performed in the longitudinal direction and / or the width direction.
  • stretching in the longitudinal direction refers to stretching for imparting molecular orientation in the longitudinal direction to the film, and is usually performed by a difference in peripheral speed of the roll, and this stretching may be performed in one step. Alternatively, a plurality of roll pairs may be used in multiple stages.
  • the stretching ratio varies depending on the type of resin, it is usually preferably 2 to 15 times, and 2 to 7 times is particularly preferred when PET is used as one of the resins constituting the multilayer laminated film.
  • the stretching temperature is preferably from the glass transition temperature of the resin constituting the multilayer laminated film to the glass transition temperature + 100 ° C.
  • a preferred stretching condition for strengthening the orientation is to stretch the glass transition temperature in the range of ⁇ 10 ° C. to + 10 ° C. Therefore, if the glass transition temperature of the resin b is higher, the glass transition temperature of the resin b is ⁇ 10 ° C.
  • the film is preferably stretched by 2.8 to 3.7 times. More preferably, it is 3.3 to 3.7 times within the glass transition temperature of resin b + 10 ° C.
  • the uniaxially stretched film thus obtained is subjected to surface treatment such as corona treatment, flame treatment, and plasma treatment as necessary, and then functions such as slipperiness, easy adhesion, and antistatic properties are provided. It may be applied by in-line coating.
  • the stretching in the width direction refers to stretching for imparting the orientation in the width direction to the film, and usually a tenter method is used. This is carried while holding both ends of the film with clips and stretched in the width direction.
  • the stretching ratio varies depending on the type of resin, it is usually preferably 2 to 15 times, and 2 to 7 times is particularly preferred when PET is used as one of the resins constituting the multilayer laminated film.
  • the stretching temperature is preferably from the glass transition temperature of the resin constituting the multilayer laminated film to the glass transition temperature + 120 ° C.
  • the film is stretched stepwise when stretching in the film width direction in order to suppress the retardation in the film width direction and to improve the uniformity of the retardation and orientation angle in the film width direction. It is also preferable to employ a method in which the temperature is raised from a low temperature to a high temperature, or a method in which the film is stretched at a high stretch ratio and then stretched at a low stretch ratio during stretching in the film width direction.
  • One of the causes of the decrease in the uniformity in the width direction of the phase difference and the orientation angle is often accompanied by stretching stress acting in the film flow direction during stretching in the width direction.
  • the transverse stretching temperature is preferably 100 ° C. or more and stretched by 3.3 to 4.6 times.
  • the ratio of longitudinal stretching ratio / lateral stretching ratio is preferably close to 1.
  • the ratio is preferably 0.6 or more, and more preferably 0.7 or more.
  • the biaxially stretched film is preferably subjected to a heat treatment not less than the stretching temperature and not more than the melting point in the tenter in order to impart flatness and dimensional stability.
  • a heat treatment not less than the stretching temperature and not more than the melting point in the tenter in order to impart flatness and dimensional stability.
  • the multilayer laminated film of the present invention in order to suppress unevenness in retardation in the film width direction, it is also preferable to perform heat treatment after being stretched in the film width direction and once cooled to a glass transition temperature or lower. .
  • the temperature at the end of stretching in the film width direction is T1
  • the temperature at the start of heat treatment is T2
  • the maximum temperature of the heat treatment step is T3
  • T2 is T1 + 10 ° C. or higher and T3-10 ° C. or lower
  • T2 is in the range of (T1 + T3) / 2 ⁇ 10 ° C.
  • the multilayer laminated film of this invention it is also preferable to extend
  • the heat treatment step almost no stress is generated in the longitudinal direction of the film, so that the uniformity of retardation and orientation angle in the width direction can be improved.
  • the draw ratio in the film width direction in the heat treatment step is larger than 1.2 times, the film has uneven thickness, and the phase difference may be worsened.
  • the thickness of the obtained multilayer laminated film is preferably 30 ⁇ m or less from the viewpoint of thinning. More preferably, it is 20 ⁇ m or less.
  • the multilayer laminated film of the present invention is a multilayer laminated film having an inclination of the main orientation axis of 10 to 80 ° relative to the width direction of the multilayer laminated film, wherein the main orientation axis of the A layer and the main orientation axis of the B layer included in the multilayer laminated film are formed.
  • the angle is preferably 60 to 120 °.
  • the main orientation axis indicates an orientation in which the refractive index is the highest in the in-plane refractive index, and is sometimes referred to as an orientation angle with respect to the reference line.
  • the inclination of the main alignment axis here is an absolute value.
  • the main orientation axis can be obtained by examining the ratio of ⁇ in increments of 15 ° in the in-plane direction.
  • isosorbide-copolymerized polyethylene terephthalate has a ratio of peak intensity of 1097 cm ⁇ 1 / peak intensity of 1410 cm ⁇ 1 which is a peak peculiar to isosorbide
  • spiroglycol copolymer polyethylene terephthalate has a peak intensity of 1165 cm ⁇ 1 / 1410 cm
  • the main alignment axis can be obtained by examining the ratio of the peak intensity of ⁇ 1 in the in-plane orientation with the orientation parameter as the orientation parameter.
  • the angle formed between the main orientation axis of the A layer and the main orientation axis of the B layer contained in the multilayer laminated film is less than 60 ° or more than 120 °, the effect of subtracting the phase difference is reduced. 110 °. More preferably, the angle is 80 ° to 100 °.
  • requiring the orientation parameter of A layer and B layer independently can be measured by performing dry polishing in the thickness direction.
  • the multilayer laminated film of the present invention preferably has a retardation unevenness in the film width direction of 50 nm / 200 mm or less. If the retardation unevenness exceeds 50 nm / 200 mm, color unevenness occurs when used as a polarizer protective film in display applications.
  • the multilayer laminated film of the present invention preferably has a reflectance of 20% or more at a wavelength of 350 nm. This is because in polarizing plate applications, UV protection is required for the polarizer protective film in order to prevent light deterioration of the polarizer.
  • the C layer comprising a liquid crystal material to be described later light in the vicinity of the I line having a wavelength of 365 nm is mainly used for the curing reaction by radical polymerization with light.
  • the multilayer laminated film itself reflects ultraviolet rays, the ultraviolet light used for the photoreaction is retroreflected without escaping from the lower surface of the coating film, and is again irradiated to the coating film.
  • the assembled multilayer laminated film according to the present invention is a first multilayer in which an A layer made of a crystalline resin a and a B layer made of a resin b having lower crystallinity than the crystalline resin a are laminated.
  • the laminated film, the second multilayer laminated film, and the k-th multilayer laminated film are sequentially assembled.
  • the total retardation SRe as an aggregate of the multilayer laminated films satisfies the following formula (3). is required. k is a natural number.
  • SRe is preferably a phase difference of 400 nm or less. More preferably, it is 250 nm or less.
  • the natural number n which is the number of stacked multilayer laminated films, is 2 or more from the viewpoint of expressing the phase difference subtraction effect. Further, it is preferably a multiple of 2. This is because it is easy to subtract the phase difference when the multi-layer laminated films are alternately laminated so that the main orientation axes are orthogonal to each other.
  • An adhesive, an adhesive, or air may intervene between the laminations of each multilayer laminated film.
  • These may contain various additives such as ultraviolet absorbers, dyes, and light stabilizers.
  • the metal or metal oxide obtained by vapor deposition etc. which are hardly concerned with a phase difference may be given.
  • the multilayer laminated film to be overlapped may be a sampling position difference in the width direction of the multilayer laminated film obtained from the same film formation. Or the multilayer laminated film from which a resin composition differs may be sufficient.
  • the Boeing phenomenon is a linear curve of magic ink drawn in the film width direction before the tenter in the sequential biaxially stretched film manufacturing method, and at the tenter outlet, a bow-like curve with the tenter clip position fixed and rotated.
  • the generation mechanism is that the shrinkage stress based on the Poisson's ratio acts in the transverse direction in the opposite direction to the running direction, and draws the film in the heat setting region into the stretching region.
  • FIG. 4A shows the distribution of refractive index ellipsoids in the width direction of the multilayer laminated film. It is distribution of the refractive index ellipsoid in the film width direction cut out from the full width sample of the multilayer laminated film.
  • C position shows the film width direction center part.
  • Film formation by sequential biaxial stretching is characterized by a large birefringence (phase difference) at the film width direction end and a large inclination (orientation angle) of the main alignment axis due to the bowing phenomenon described above.
  • FIG. 4B shows the distribution of the refractive index ellipsoid of the multilayer laminated film in the width direction when two multilayer laminated films are stacked. It is the distribution of refractive index ellipsoids of two full width multilayer laminated films that are overlapped with the traveling direction reversed by 180 ° for the same multilayer laminated film cut out from different positions in the longitudinal direction.
  • FIG.5 (a) shows the schematic diagram of the subtraction of phase difference at the time of using one multilayer laminated film. It is an example in which the multi-layer laminated film of the full width shown in FIG. 4 (a) is halved and the traveling direction is reversed by 180 ° and overlapped. Like FIG. 4 (b), the refractive index ellipsoids intersect, It can be seen that the phase difference subtraction effect works. On the other hand, FIG. 5B shows that the refractive index ellipsoids overlap when the traveling direction is the same and folded at the center, and the effect of adding the phase difference works. These are examples in which the phase difference is controlled by making good use of the line symmetry of the optical characteristics.
  • the assembled multilayer laminated film of the present invention in order to satisfy the formula (3), at least one set of two multilayer laminated films having at least a main orientation axis orthogonal or a relationship of 60 to 120 ° is present. is necessary.
  • the number of the multilayer laminated films having the above relationship is about n / 2 to (n-6) / 2 (n ⁇ 2).
  • the retardation SRe (k) of the multilayer laminated film itself of the formula (3) is synonymous with the total retardation Re of the formula (1), but the retardation here is not particularly limited. This is because the final form used is important for the phase difference.
  • the composite multilayer laminate film according to the present invention is a multilayer laminate in which A layers made of crystalline resin a and B layers made of resin b having lower crystallinity than crystalline resin a are alternately laminated.
  • the liquid crystal material includes a polymerizable liquid crystal composition and has a structure containing a liquid crystal compound having a polymerizable functional group in a molecule (rod-like liquid crystal structure).
  • the liquid crystal compound has a refractive index anisotropy and exhibits a desired retardation function by imparting various alignment forms.
  • Examples of the liquid crystal compound include materials that exhibit a liquid crystal phase such as a nematic phase, a cholesteric phase, and a smectic phase. Since the liquid crystal compound has a polymerizable functional group, several kinds of liquid crystal compounds can be polymerized and fixed.
  • radical photopolymerization type and photocation polymerization type are mentioned.
  • the radical polymerization type include a vinyl group and an acrylate group (a generic term including an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group).
  • the liquid crystal material of the present invention preferably contains a photosensitive liquid crystal polymer. Moreover, it is preferable that a mesogenic component is contained in the liquid crystal polymer.
  • a side chain type liquid crystalline polymer material containing a mesogenic component in the side chain.
  • the material constituting the main chain include hydrocarbon, acrylate, methacrylate, vinyl, siloxane, maleimide, N-phenyl maleimide and the like.
  • the mesogenic component is composed of an aromatic ring such as a benzene ring, a naphthalene ring or a fluorene ring, or an aliphatic ring such as a cyclohexane ring, and a linking group that binds the ring.
  • biphenyl, terphenyl, phenylbenzoate, azobenzene and the like are examples of the material constituting the main chain.
  • Such a liquid crystalline polymer material may be a single polymer composed of the same repeating unit or a copolymer of units having side chains having different structures. Moreover, you may add the crosslinking agent for improving heat resistance and solvent resistance to such an extent that liquid crystallinity is not impaired.
  • crosslinking agents such as isocyanate material and an epoxy material, can be mentioned.
  • Solvents for dissolving the liquid crystal material include hydrocarbon solvents such as benzene and hexane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, 1,2-dimethoxyethane, propylene glycol monoethyl ether, methyl tert- Ether solvents such as butyl ether, 1,4-dioxane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1,3-dioxolane and 2-methyltetrahydrofuran, alkyl halide solvents such as chloroform and dichloromethane, methyl acetate, ethyl acetate Ester solvents such as butyl acetate, propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, dimethyls Sulfoxide solvents such as sul
  • the solution to be the C layer containing the liquid crystal material When the solution to be the C layer containing the liquid crystal material is applied on the multilayer laminated film, it can be achieved by gravure, flexo, die slit, spin coating.
  • the photosensitive liquid crystal polymer can be formed by a condensation reaction as described in, for example, Japanese Unexamined Patent Publication No. 2007-232934 and Japanese Unexamined Patent Publication No. 2012-177087. Next, ultraviolet rays having a wavelength of 250 to 400 nm are irradiated to cure the C layer and impart refractive index anisotropy.
  • the irradiated light may be circularly polarized light or elliptically polarized light, but linearly polarized light is preferable from the viewpoint of anisotropically aligning the mesogen portion in the photosensitive liquid crystal polymer.
  • the multilayer laminated film preferably reflects ultraviolet rays having a wavelength of 400 nm or less. This is because the photocuring efficiency of the C layer is increased by reflecting the ultraviolet rays.
  • the reflectance at a wavelength of 350 nm is preferably 30% or more. More preferably, it is 50% or more.
  • a negative C plate irradiates light on the coating surface from a normal direction or a direction inclined from an oblique normal line.
  • the light source any light source that emits ultraviolet rays, such as a high-pressure mercury lamp or a xenon light source, may be used.
  • the irradiation amount may be about 20 to 300 mJ / cm2.
  • the thickness of the liquid crystal material of the present invention is preferably 0.1 ⁇ m or more and 10 ⁇ m or less from the viewpoint that thinning is required and from the viewpoint of imparting anisotropy and developing a retardation in the thickness direction. More preferably, it is 0.5 ⁇ m to 5 ⁇ m. Since the multilayer laminated film of the present invention uses the crystalline resin a capable of biaxial orientation, it tends to be a strong negative C plate. In the multilayer laminated film of the present invention, in order to eliminate the interference color due to the viewing angle under crossed Nicols, the subtraction effect of the thickness direction retardation is required, so the C layer containing the liquid crystal material is a positive C plate. preferable.
  • the negative C plate is a refractive index ellipsoid whose refractive index Nx, Ny in the in-plane direction is higher than the refractive index Nz in the thickness direction, while the positive C plate is a refractive index in the thickness direction.
  • Nz means a material having a refractive index ellipsoid higher than the refractive indexes Nx and Ny in the in-plane direction.
  • the method of creating a positive C plate is to irradiate linearly polarized ultraviolet light from an orientation inclined at 45 ° or more and less than 90 ° from the normal direction of the coated surface, and then heat-treat, so that the thickness direction of the liquid crystal material Induced and achieved an increase in refractive index.
  • An incident angle means the inclination
  • the layer composed of the biaxially orientable crystalline resin a generally has an in-plane refractive index of 1.5 to 1.8 and a refractive index in the thickness direction of less than 1.6. Therefore, when the C layer satisfies the expressions (6) and (7), the thickness direction retardation Rth ′ of the composite multilayer film can be made smaller than the total thickness direction retardation Rth of the multilayer film. . That is, there is an effect of subtracting the thickness direction retardation.
  • the in-plane refractive indexes of N X and N Y are not particularly limited, but are preferably 1.54 to 1.62 from the viewpoint of reducing reflection at the interface with the multilayer laminated film.
  • formed by the main orientation axis ⁇ c of the C layer and the main orientation axis ⁇ ab of the multilayer laminated film has a relationship of 50 ° to 90 °.
  • the main alignment axis of the C layer can be controlled by rotating linearly polarized light for photocuring the liquid crystal material in the in-plane direction.
  • Linearly polarized light can be created by using a polarizing plate made of a polarizer stretched by impregnating iodine in polyvinyl alcohol, or a Glan Taylor prism that extracts polarized light using a Brewster angle formed by two calcites.
  • the multilayer laminated film, the aggregate multilayer laminated film, and the composite multilayer laminated film according to the present invention are preferably used as an optical film.
  • the optical film is preferably used for flat panel display.
  • a cover film, a scattering prevention film, a polarizer protective film, a retardation film, a base film for a touch panel, a release film for a polarizing plate, and the like are preferably used for a polarizer protective film, a retardation film, and a touch panel substrate film from the viewpoint of low retardation.
  • the polarizer protective film is a material constituting two polarizing plates used in a liquid crystal display, and is used on the viewing side of the upper polarizing plate and on the backlight side of the lower polarizing plate.
  • the polarizing plate has a configuration in which a polarizer protective film and a retardation film are bonded to both sides of a film obtained by uniaxially stretching polyvinyl alcohol impregnated with iodine through an adhesive.
  • the multilayer laminated film of the present invention is preferably used for a touch panel.
  • the touch panel of the present invention may be any of a resistance film type, an optical type, and a capacitance type.
  • Capacitance type can be roughly divided into projection type and surface type. From the viewpoint of enabling multi-touch, the projection capacitance type is most preferable.
  • the conductive layer is made of metal such as gold, silver, platinum, palladium, rhodium, indium, copper, aluminum, nickel, chromium, titanium, iron, cobalt, tin, and alloys thereof, tin oxide, indium oxide, titanium oxide, It can be formed by a composite film such as a metal oxide film such as antimony oxide, zinc oxide, cadmium oxide, indium tin oxide (ITO), or copper iodide. A thin film can be obtained from these transparent conductive films by vacuum deposition, sputtering, reactive RF ion plating, spray pyrolysis, chemical plating, electroplating, CVD, coating, or a combination thereof.
  • the conductive polymer polypyrrole, polyaniline, polyacetylene, polythiophene, polyphenylene vinylene, polyphenylene sulfide, poly-p-phenylene, polyheterocycle vinylene, particularly preferably (3,4-ethylenedioxythiophene) ) (PEDOT).
  • PEDOT polyethylenedioxythiophene
  • carbon nanotubes and nano silver are preferable because they exhibit high conductivity.
  • the out-cell type touch sensor is roughly classified into a glass sensor and a film sensor.
  • Glass sensor types include GG, GG2, G2, and G1M.
  • GG is cover glass / ITO / glass / ITO
  • GG2 is cover glass / glass / ITO / insulating layer / ITO
  • G2 (OGS) is cover glass / ITO / insulating layer / ITO
  • G1M is cover glass / ITO Is a basic configuration.
  • the multilayer laminated film of the present invention is preferably used between the touch panel and the liquid crystal panel.
  • the glass sensor type is particularly preferably used.
  • GFF is cover glass / ITO / film / ITO / film
  • GF2 is cover glass / ITO / film / ITO, or cover glass / ITO / insulating layer / ITO / film
  • G1F is cover glass / ITO / ITO.
  • GF1 is a cover glass / ITO / film
  • PFF is a cover plastic / ITO / film / ITO / film
  • P1M cover plastic / ITO.
  • the layer thickness, the number of layers, and the layered structure layer configuration were determined by observation with a transmission electron microscope (TEM) or a scanning electron microscope (SEM) for a sample cut out of a cross section using a microtome.
  • the transmission electron microscope uses H-7100FA type (manufactured by Hitachi, Ltd.), observes the cross section of the film at a magnification of 40000 times under the condition of an acceleration voltage of 75 kV, takes a cross-sectional photograph, and measures the layer configuration and each layer thickness. did.
  • a staining technique using known RuO 4 or OsO 4 was used.
  • JSM-6700F (JEOL Ltd.) was used, and the cross section of the film was magnified 1500 times under the condition of an acceleration voltage of 3 kV, a cross-sectional photograph was taken, and the layer configuration and each layer thickness were measured.
  • Refractive index of outermost layer A prism coupler (SPA-4000) manufactured by Sairon Technology was used.
  • the in-plane refractive index of the outermost layer was measured by placing a film sample cut out at 3.5 cm ⁇ 3.5 cm in the apparatus, irradiating with a 633 nm laser, and measuring in TE mode. By measuring in TM mode, the thickness direction refractive index of the outermost layer was measured.
  • the refractive index in the longitudinal direction was measured by setting the MD direction of the film parallel to the apparatus, and the refractive index in the width direction was measured by installing the film in the direction perpendicular to the apparatus. Sampling was performed from the center of a film roll having a width of 600 mm.
  • the C layer prepared in Example 17 was transferred onto a glass substrate, and the in-plane and straight (thickness direction) refractive indexes were measured by the same method.
  • a retardation measuring device (KOBRA-21ADH) manufactured by Oji Scientific Instruments was used.
  • a film sample cut out at 3.5 cm ⁇ 3.5 cm was placed in the apparatus, and the retardation at a wavelength of 590 nm at an incident angle of 0 ° was measured. Sampling was performed from the center of a film roll having a width of 600 mm.
  • the retardation in the thickness direction was the retardation at an incident angle of 50 °.
  • FT-IR Fourier transform infrared spectrophotometer
  • the sample is taken from a position 250 mm from the center in the film width direction, the film longitudinal direction is set to 0 °, and the polarization measurement is performed once every 15 ° in the in-plane direction, and the intensity distribution in the plane of the spectrum is obtained.
  • the intensity ratio with a high value was taken as the main orientation axis.
  • orientation evaluation in the thickness direction was performed using dry polishing.
  • Orientation evaluation spectral intensity ratio of spiroglycol copolymer polyethylene terephthalate layer Peak ratio A1165 cm -1 / A1410 cm -1
  • Orientation evaluation spectrum intensity ratio of isosorbide copolymerized polyethylene terephthalate layer Peak ratio A1097cm -1 / A1410cm -1
  • Alignment evaluation spectrum intensity ratio of polyethylene terephthalate layer Peak ratio A1340cm -1 / A1410cm -1 (8) Measurement of relative spectral reflectance at wavelength of 350 nm A 5 cm square sample was cut out from the central part of the multilayer laminated film in the film width direction.
  • the spectral transmittance and the relative reflectance at an incident angle ⁇ 10 degrees were measured.
  • the inner wall of the attached integrating sphere is barium sulfate, and the standard plate is aluminum oxide.
  • the measurement wavelength was 250 nm to 800 nm, the slit was 2 nm (visible), the gain was set to 2, and the scanning speed was measured at 600 nm / min.
  • Resin 2 24 mol% isophthalic acid copolymerized polyethylene terephthalate (PET-I24): glass transition temperature 74 ° C.
  • Resin 3 6 mol% isophthalic acid copolymerized polycyclohexylenedimethylene terephthalate (PCT-I6): glass transition temperature 90 ° C.
  • Resin 5 Nylon 6 Resin 6 6 mol% ethylene copolymer polypropylene resin 7 17 mol% isophthalic acid copolymer polyethylene terephthalate (PET-I17) : Glass transition temperature 76 ° C Resin 8 12 mol% isophthalic acid copolymerized polyethylene terephthalate (PET-I12) : Glass transition temperature 78 ° C Resin 9 30 mol% spiroglycol copolymer polyethylene terephthalate: glass transition temperature 100 ° C.
  • Resin 10 Copolymerized polyethylene terephthalate copolymerized with 20 mol% spiroglycol component and 30 mol% cyclohexanedicarboxylic acid: Glass transition temperature 80 ° C (Example 1) Resin 1 was used as crystalline resin a, and resin 2 was used as resin b. Crystalline resin a and resin b were respectively supplied to two separate extruders after drying at 120 ° C. for 5 hours after pre-crystallization with a mixer at 180 ° C. for 3 hours. Crystalline resin a and resin b were each melted at 270 ° C.
  • the phase difference of the outermost layer of the obtained multilayer laminated film was calculated using a prism coupler and SEM, and the retardation Re of the entire multilayer laminated film was measured using KOBRA.
  • the results are shown in Table 1. From this result, it can be seen that the total retardation Re (A) of the A layer composed of the same crystalline resin a as the outermost layer is larger than the retardation of the laminated film. Therefore, the B layer subtracts the phase difference from the A layer.
  • the retardation Re of the multilayer laminated film was 277 nm, which was a low retardation film lower than 400 nm. Therefore, when rainbow unevenness was observed on the LCD, it was not visible at all.
  • Example 3 The same resin as in Example 1 was merged in a feed block using a slit plate having 9 slits to obtain a laminate.
  • the slit gap was designed to have the same thickness in adjacent layers.
  • the conditions were the same as in Example 1.
  • the results are shown in Table 1.
  • Example 2 resulted in a higher subtraction effect for the B layer. This is thought to be because the effect of subtracting the phase difference worked more than in Example 1 because the increase in the thickness of the B layer relative to the total thickness.
  • Example 4 In Example 3, a laminate was formed using the resin 4 as the resin b.
  • the longitudinal stretching temperature was 103 ° C.
  • the longitudinal stretching ratio was 3.3 times
  • the transverse stretching temperature was 120 ° C.
  • the transverse stretching ratio was 3.3 times
  • the heat treatment temperature was 230 ° C.
  • Tables 1 and 2 Even when the resin is used as the resin b, the phase difference of the B layer is subtracted from the multilayer laminated film.
  • Example 5 The same resin as in Example 4 was used, and the same conditions as in Example 4 were performed except that the longitudinal draw ratio was 3.5 times and the transverse draw ratio was 3.3 times. The results are shown in Table 2. Since the stretching ratio in the MD direction was increased, the overall phase difference was increased, but the subtraction effect was hardly changed.
  • Example 6 Using the same resin as that of Example 4, a layered feed block having a structure in which one slit plate having 491 slits was used was joined to obtain a laminate in which 491 layers were alternately laminated in the thickness direction.
  • the slit width for forming the thick film layer positioned at both ends is designed to be more than twice the slit width for forming the other thin film layer, and the minimum width for forming the thin film layer is used.
  • the slope which is the ratio of the layer thickness to the maximum layer thickness, is set to 0. 3 Designed.
  • the slit width (gap) was all constant, and only the length was changed.
  • the obtained laminate was formed under the same conditions as in Example 5 except that the longitudinal stretching temperature was 98 ° C., the longitudinal stretching ratio was 3.3 times, the transverse stretching temperature was 140 ° C., and the transverse stretching ratio was 4.6 times.
  • the results are shown in Table 2. As a result, the subtraction effect was increased as compared with Example 4.
  • Example 7 In Example 6, all were performed under the same conditions except that the longitudinal stretching temperature was increased to 101 ° C. The results are shown in Table 2. Compared to the examples, the longitudinal orientation was weakened and the lateral magnification remained as it was, so the overall phase difference was increased, but the orientation of the B layer was not changed, so the subtraction effect was great.
  • Example 8 In Example 7, all were performed on the same conditions except having reduced the horizontal draw ratio. The results are shown in Table 2. Compared to Example 7, since the lateral magnification was reduced, the overall phase difference was reduced, but the subtraction effect was almost the same as Example 7.
  • Example 9 In Example 8, in order to reduce the shrinkage rate in the MD direction, additional stretching was performed during the heat treatment, and the final magnification was stretched to the same conditions as in Example 7. The results are shown in Table 2. Compared to Example 8, the overall phase difference was also reduced, and the subtraction effect was the largest.
  • Example 1 (Comparative Example 1)
  • the resin 5 is used as the crystalline resin a and the resin 1 is used as the resin b.
  • the longitudinal stretching temperature is 80 ° C.
  • the longitudinal stretching ratio is 3.3 times
  • the transverse stretching temperature is 105 ° C.
  • the transverse stretching ratio is 3.9.
  • the same procedure was performed except that the heat treatment temperature was changed to 190 ° C.
  • the results are shown in Table 1. It was found that the retardation of the surface nylon was lower than the total retardation of the laminated film, and the inner PET layer added to the nylon retardation.
  • Example 2 In Example 1, resin 6 is used as the crystalline resin a, resin 4 is used as the resin b, the longitudinal draw ratio is 3.3 times, the transverse draw ratio is 4.1 times, and the heat treatment temperature is changed to 90 ° C. The method of was used. It was found that this film also added the retardation of the inner layer to the retardation of the surface layer.
  • Example 3 (Comparative Example 3) In Example 1, the experiment was performed under the same conditions except that the resin b was changed to the resin 7. The results are shown in Table 1.
  • Example 4 In Example 1, the experiment was performed under the same conditions except that the resin b was changed to the resin 8. The results are shown in Table 1. It was found that when the isophthalic acid copolymerization component was smaller than those in Comparative Examples 3 and 4, the difference between the retardation of the laminated film and the retardation of the A layer was increased, and the resin b did not work as a subtraction effect.
  • Example 5 (Comparative Example 5) In Example 4, it carried out on the same conditions except having changed the longitudinal draw ratio into 3.3 times and the transverse draw ratio into 3.5 times. The results are shown in Table 2. Although the overall phase difference decreased, there was no phase difference subtraction because the vertical magnification was increased.
  • Example 6 In Example 1, all the resins were changed to Resin 1 to produce a PET single film.
  • the phase difference reduction mechanism was investigated by measuring the phase difference by superimposing the single films. The results are shown in Table 3.
  • Table 3 When the PET single films were overlapped with respect to the longitudinal direction without deviation, the total retardation of the film was equivalent to the added value of the two films.
  • the phase difference was subtracted from the phase difference at 0 °. Further, it was found that the retardation of the entire film greatly subtracted as the deviation increased. From the above results, it was proved that the phase difference is subtracted when the main orientation axes of the two overlapping films are different.
  • This concept is a result that can be considered in two or more different films, and the fast axis and the slow axis are reversed with respect to the A layer when the main orientation axes of adjacent films are different.
  • the phase difference of each layer works in the direction of subtraction, and as a result, the total phase difference is considered to be subtracted.
  • the multilayer laminated films used in some examples and comparative examples were able to examine the orientation angle of each layer by peeling at the physical interface between the layers.
  • Table 4 shows the results of the total retardation of the film and the retardation and orientation angle of each layer.
  • the orientation angle was different by about 80 ° between the A layer and the B layer, and it was found that the inner layer and the outer layer were greatly different.
  • Comparative Example 1 and Comparative Example 2 the orientation angles were the same values in the inner layer and the outer layer. From the above results, it is considered that the film formed this time has the total phase difference of the film subtracted due to the different orientation angles of the inner layer and the outer layer.
  • Resin 1 containing 0.04% by weight of agglomerated silica having an average particle size of 2.5 ⁇ m as a lubricant is vacuum-dried at 180 ° C. for 3 hours, and then charged into a single-screw extruder and melted at an extrusion temperature of 280 ° C. Kneaded. After passing through a screen filter with a filtration accuracy of 30 ⁇ m cut, fed to a T-die, formed into a sheet, and then applied on a casting drum with a surface temperature maintained at 25 ° C. while applying an electrostatic applied voltage of 7 kV with a wire And solidified rapidly to obtain an unstretched film.
  • This unstretched film was stretched between rolls by 3.5 times in the longitudinal direction of the film at 85 ° C. with a longitudinal stretching machine, and then led to a tenter holding both ends with clips at 85 ° C. in the film width direction.
  • heat treatment at 215 ° C. was then performed, and relaxation treatment was performed at 150 ° C. in the film width direction of about 3% to obtain a polyester film having a thickness of 32 ⁇ m.
  • Table 5 shows the retardation and orientation angle in the film width direction of the obtained polyester film. A uniform orientation angle distribution in which the main orientation axis was 40 to 60 ° in the film width direction was exhibited.
  • the obtained polyester film has a width of 600 mm, is cut every 1000 mm in the longitudinal direction, produces two sheets each of 600 mm ⁇ 1000 mm, reverses the winding direction of one sheet, and has a central portion, a central portion, and an end portion.
  • the optical adhesive SK-1478 made by Soken Chemical Co., Ltd. is used so that the angle between the first and second main orientation axes is 90 ° ⁇ 15 ° and the subtraction effect works. Used for dry lamination.
  • the thickness of the optical adhesive was 25 ⁇ m
  • the obtained multilayer laminated film was 3 layers, and the thickness was 89 ⁇ m.
  • the retardation of the obtained three-layer film was uniform in the film width direction, and all were 50 nm or less, and the subtraction effect was confirmed.
  • Example 11 After resin 1 is vacuum-dried at 180 ° C. for 3 hours as resin a, and resin 4 is dried at 80 ° C. under nitrogen at 80 ° C. as a resin b, respectively in a closed conveying line, a single screw extruder and a twin screw Each was put into an extruder, melted at extrusion temperatures of 280 ° C. and 280 ° C., respectively, and kneaded. Next, after removing foreign matters such as oligomers and impurities with a vacuum vent at two vent holes of a twin screw extruder at a vacuum pressure of 0.1 kPa or less, the discharge ratio (lamination ratio) is a thermoplastic resin with a gear pump.
  • the laminate is supplied to a T-die and formed into a sheet, and then rapidly cooled and solidified on a casting drum whose surface temperature is maintained at 25 ° C. while applying an electrostatic applied voltage of 8 kV with a wire, and unstretched A film was obtained.
  • This unstretched film is stretched at a temperature of 115 ° C by a longitudinal stretching machine and 3.2 times in the longitudinal direction of the film, and then guided to a tenter holding both ends with clips at 110 to 140 ° C and 4.5 times in the width direction of the film.
  • heat treatment was then performed stepwise at 180 ° C. and 225 ° C., and relaxation treatment was performed in the film width direction of about 3% at 150 ° C.
  • the layer thickness of each layer of the obtained multilayer laminated film was all in the range of 35 nm to 55 nm.
  • the layer thickness distribution of the obtained multilayer laminated film was a convex layer thickness distribution in which the average layer thickness 60 nm is an asymptotic line in the average layer thickness distribution.
  • the relative reflectance of the obtained multilayer laminated film at a wavelength of 350 nm by a spectrophotometer was 61%.
  • FIG. 6 shows the results of examining the orientation distribution of the A layer and the B layer by FT-IR at a position of 250 mm from the center in the film width direction.
  • the main orientation axis of the A layer is 120 ° (300 °), whereas the main orientation axis of the B layer is 30 ° (210 °), indicating that the A layer and the B layer are orthogonal to each other. confirmed.
  • the total phase difference Re is 191 nm, while the phase difference obtained from the refractive index difference (Nx (1) -Ny (1)) of the outermost layer by the prism coupler and the total thickness d (A) of the A layer is 400 nm. Yes, subtraction of the phase difference in the in-plane direction of 209 nm could be confirmed.
  • the thickness direction retardation Rth at an incident angle of 50 ° was 450 nm, and the film was placed on a 42-inch liquid crystal display and had no rainbow unevenness even when the background color was white.
  • the retardation unevenness the change in retardation at 200 mm in the central portion in the film width direction was 20 nm.
  • Example 12 A multilayer laminated film of 255 layers was obtained in the same manner as in Example 11 except that the resin b was changed to the resin 9 and the longitudinal draw ratio was changed to 3.5 times.
  • the main orientation axis of the A layer is 135 ° (315 °)
  • the main orientation axis of the B layer is 15 ° (195 °).
  • the angle formed by the main orientation axis of the B layer was 120 °.
  • the total phase difference Re is 150 nm, while the phase difference obtained from the refractive index difference (Nx (1) -Ny (1)) of the outermost layer by the prism coupler and the total thickness d (A) of the A layer is 235 nm.
  • the thickness direction retardation Rth at an incident angle of 50 ° was 398 nm, and the film was arranged on a liquid crystal display and had no rainbow unevenness even when the background color was white.
  • the retardation unevenness the change in retardation at 200 mm in the central portion in the film width direction was 10 nm.
  • the relative reflectance of the obtained multilayer laminated film at a wavelength of 350 nm by a spectrophotometer was 90%.
  • Example 13 Next, except that the resin b is the resin 10, the laminating apparatus is 491 layers, the longitudinal stretching temperature is 105 ° C., and the lateral magnification is changed to 3.6 times, the thickness is 15.5 ⁇ m. A 491-layer multilayer laminated film was obtained. The retardation of the obtained multilayer laminated film was 17 nm. At the end in the film width direction, a film having a retardation unevenness in the width direction of 201 nm was obtained.
  • FIG. 7 shows the distribution of retardation and orientation angle in the film width direction of the multilayer laminated film obtained in Example 13.
  • FIG. 7A shows the phase difference distribution
  • FIG. 7B shows the orientation angle distribution. As shown in FIG.
  • the measurement position (X) in the film width direction was represented by a relative position ( ⁇ X / W) divided by half (W) of the entire width of the film. Since all the phase difference values were 400 nm or less, rainbow unevenness was not observed and was good. However, when observed under crossed Nicols, the brightness contrast was different in the film width direction.
  • Example 14 A 491-layer multilayer film having a thickness of 15.5 ⁇ m was obtained in the same manner as in Example 13 except that the longitudinal stretch ratio in Example 13 was changed to 3.2 times. Since the orientation of the resin b did not progress, the effect of subtracting the phase difference was as small as about 6 nm. On the other hand, rainbow spots were not observed.
  • Example 15 Comparative Example 7
  • Example 15 Using the multilayer laminated film obtained in Example 13, the relationship between (a) phase difference subtraction and (b) phase difference addition described in FIG. Cut out and film laminated with the two patterns.
  • the distribution of retardation obtained in the film width direction is shown in FIGS.
  • FIG. 8A shows a phase difference distribution when lamination is performed with the MD direction reversed.
  • a multilayer multilayer film having a uniform low retardation with no rainbow unevenness, all having a phase difference of 40 nm or less over the entire width direction was achieved. It has been confirmed that these can be suitably used in applications that require two ITO base films such as the GFF type.
  • FIG. 8B shows a phase difference distribution when the MD direction is the same and is folded and laminated. It can be seen that all the phase differences are added, and that the phase difference unevenness in the width direction is larger. At the end, the phase difference exceeds 400 nm and rainbow unevenness is visible.
  • Example 17 A multilayer laminated film of 255 layers was obtained in the same manner as in Example 11 except that the resin b was changed to the resin 10, the longitudinal stretching temperature was changed to 110 ° C., and the longitudinal magnification was changed to 3.3 times. Samples were taken from the center in the film width direction and 200 mm position, and then a liquid crystal material was applied on these multilayer laminated films to form a C layer.
  • layer C 4- (6-hydroxyhexyloxy) cinnamic acid was synthesized, and further methacrylic acid was added in the presence of p-toluenesulfonic acid for esterification to obtain compound 1.
  • the obtained compound 1 was dissolved in dioxane, azobisisobutyronitrile was added as a reaction initiator, and polymerization was performed at 70 ° C. for 24 hours to obtain a polymer.
  • This was dissolved in a tetrahydrofuran / propyl carbonate mixed solution to prepare a solution having a solid concentration of 25% by weight.
  • a photosensitive liquid crystal polymer was obtained by preheating.
  • the film is irradiated with linearly polarized ultraviolet rays using a Glan-Taylor prism at an incident angle inclined by 60 degrees or more from the normal direction of the coating surface of the film, and then heat-treated at 120 ° C. to have positive C plate characteristics.
  • a C layer containing a liquid crystal material was formed.
  • the refractive index NZ in the thickness direction of the C layer was 1.69, the refractive indexes N X and N Y in the in-plane direction were 1.56, and it was confirmed to be a positive C plate.
  • the subtraction effects of the obtained thickness direction retardation are summarized in Table 6.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Thermal Sciences (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un film stratifié multicouche formé par stratification alternée d'au moins trois couches d'une couche A qui comprend une résine a cristalline pouvant être orientée biaxialement, et d'une couche B qui comprend une résine b ayant une cristallinité inférieure à celle de la résine a, le film stratifié multicouche étant caractérisé en ce que, lorsque la différence de phase d'une k-ème couche d'une couche de surface est exprimée par Re(k) et que le nombre total de couches est exprimé par n, la différence de phase totale Re du film stratifié multicouche satisfait la formule (1) et la formule (2). L'invention concerne en outre un film à faible différence de phase, même dans le cadre de l'utilisation d'une résine qui est une résine cristalline pouvant être orientée biaxialement et ayant une haute résistance mécanique et qui est une résine ayant une biréfringence élevée.
PCT/JP2016/067679 2015-06-17 2016-06-14 Film stratifié multicouche WO2016204146A1 (fr)

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WO2019112020A1 (fr) * 2017-12-06 2019-06-13 大日本印刷株式会社 Matériau d'enveloppe pour batterie, batterie, procédés de fabrication de ce matériau d'enveloppe et de cette batterie, et film polyester

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CN108943978B (zh) * 2018-09-13 2023-09-19 东莞市赛越新材料科技有限公司 屏下指纹解锁保护膜的制作方法

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JP4849454B2 (ja) * 2006-05-12 2012-01-11 日東電工株式会社 楕円偏光板およびそれを用いた画像表示装置
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TWI730966B (zh) 2021-06-21
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CN107533175B (zh) 2021-06-11
CN107533175A (zh) 2018-01-02
TW201710069A (zh) 2017-03-16

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