WO2023054117A1 - 多層積層フィルム及び投影画像表示部材 - Google Patents
多層積層フィルム及び投影画像表示部材 Download PDFInfo
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- WO2023054117A1 WO2023054117A1 PCT/JP2022/035170 JP2022035170W WO2023054117A1 WO 2023054117 A1 WO2023054117 A1 WO 2023054117A1 JP 2022035170 W JP2022035170 W JP 2022035170W WO 2023054117 A1 WO2023054117 A1 WO 2023054117A1
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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
- B32B7/023—Optical properties
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/017—Head mounted
- G02B27/0172—Head mounted characterised by optical features
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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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
- B32B2250/00—Layers arrangement
- B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/0101—Head-up displays characterised by optical features
- G02B2027/0118—Head-up displays characterised by optical features comprising devices for improving the contrast of the display / brillance control visibility
Definitions
- the present invention provides a multilayer laminated film that can reduce the brightness difference of an image due to a difference in projection angle when used as a projection member for an augmented reality device, a projection image display member using the multilayer laminated film, and an augmented reality device. Regarding.
- transparent glass and transparent resin films have a high transmittance of light from the front direction.
- the incident angle increases and the reflectance decreases, and after reaching 0%, the reflectance tends to increase again, and if the S wave is used, the incident angle increases.
- the reflectance also tends to increase along with the increase.
- the P-wave is polarized light whose oscillation direction is parallel to the plane of incidence when the light is incident on the interface
- the S-wave is polarized light whose oscillation direction is perpendicular to the plane of incidence.
- Patent Document 1 discloses a multi-layer laminate film that has a high transmittance of light from the front direction and also has an increase in the reflectance of both the P wave and the S wave as the incident angle increases with respect to the light from an oblique direction. is also proposed.
- the multi-layer stack of US Pat. No. 5,200,000 is for use as a beam splitter to split a single light beam in an optical device into two directions, where the reflectivity of both P and S waves increases with increasing angle of incidence. , the difference in reflectance between the P-wave and the S-wave is small.
- An augmented reality device is, for example, a device that virtually augments the world in front of you by displaying virtual visual information superimposed on a real landscape.
- One of these devices is a head-mounted display (hereinafter referred to as HMD).
- HMD head-mounted display
- Patent Document 1 as a projection image display member such as an HMD, the transmittance of light from the front direction is high, and the reflection of light from an oblique direction is used, and as the incident angle increases, the reflectance of the P wave increases.
- the use of increasing multilayer laminate films is disclosed.
- the P-wave reflectance increases as the incident angle increases. Therefore, when the film disclosed in Patent Document 1 is used as a projection member for an augmented reality device or the like to project a P-wave image, the reflectance varies depending on the angle at which the P-wave image is projected, and the brightness of the projected image varies. There are issues that make a difference. That is, in the multilayer laminated film disclosed in Patent Document 1, as the incident angle increases, the reflectance of the P wave increases, and the average reflectance of the P wave in visible light in the wavelength range of 400 nm to 700 nm is The deviation (standard deviation) of the P-wave reflectance in angle tends to be large. Furthermore, if the reflectance is too high, in addition to the P-wave image being projected, there is a problem that a reflected image due to natural light is likely to occur.
- the present invention consists of the following configurations. That is, a multilayer laminated film in which 51 or more layers of a plurality of different thermoplastic resin layers are alternately laminated, wherein the transmittance of visible light perpendicularly incident on the surface of the multilayer laminated film is 50% or more and 100% or less, P-wave reflectance when visible light is incident on the surface of the multilayer laminated film at angles of 20°, 30°, 40°, 50°, 60°, and 70° with the normal Rp20 (%), Rp30 (%), Rp40 (%), Rp50 (%), Rp60 (%), Rp70 (%), the standard deviation of Rp20, Rp30, Rp40 and Rp50 is 5% or less , Rp60 and Rp70 of 3% or more and 50% or less.
- the present invention it is possible to obtain a multilayer laminate film and a projection image display member that can reduce the luminance difference of the image due to the difference in the projection angle when used for the projection image display member of an augmented reality device or the like. That is, even if the incident angle changes, the reflectance of the P wave does not easily change, the deviation in visible light in the wavelength range of 400 nm to 700 nm is small, and the brightness of the projected image is less likely to vary. you can get the film.
- FIG. 10 is a graph showing the incident angle dependency of the reflectance of a conventional light-reflecting multilayer laminated film with respect to incident P-wave and S-wave light with a wavelength of 550 nm.
- 2 is a graph showing an example of the incident angle dependence of the reflectance of the multilayer laminated film described in Patent Document 1 with respect to incident light of P wave and S wave with a wavelength of 550 nm.
- FIG. 4 is a graph showing an example of the incident angle dependence of the reflectance of the multilayer laminate film of the present invention for incident light of P wave and S wave with a wavelength of 550 nm.
- FIG. 2 is a schematic diagram illustrating the layer thickness distribution of Layer A and Layer B of the multilayer laminated film of the present invention.
- FIG. 2 is a schematic diagram illustrating the azimuth angle of the outermost surface of the multilayer laminate film of the present invention.
- 1 is a graph showing an example of DSC1st curve of a multilayer laminated film of the present invention.
- FIG. 4 is a graph showing an example of a DSC1st curve for explaining differences in maximum values of temperature differential curves A(T) of multilayer laminate films.
- FIG. 1 is a schematic diagram showing an example of a cross section of a projection image display member of the present invention;
- FIG. 1 is a schematic diagram showing an example of a cross section of a projection image display member of the present invention;
- FIG. 1 is a schematic diagram showing an example of a cross section of a projection image display member of the present invention;
- FIG. 1 is a schematic diagram showing an example of a cross section of a projection image display member of the present invention;
- FIG. 1 is a schematic diagram showing an example of a cross section of a projection image display member of the present invention;
- FIG. 1 is a schematic diagram showing an example of
- FIG. 1 is a schematic diagram for explaining an augmented reality device of the present invention
- FIG. FIG. 4A is a schematic diagram showing oblique reflection characteristics of the prior art and (b) of the present invention.
- 1 is a schematic diagram illustrating an augmented reality device of the present invention
- FIG. 5 is a graph showing an example of the incident angle dependency of the reflectance of the projection image display member of the present invention with respect to incident light of P wave and S wave with a wavelength of 550 nm. It is a schematic diagram explaining the effect of implementing the augmented reality device of the present invention.
- the multilayer laminated film of the present invention is a multilayer laminated film in which 51 or more layers of a plurality of different thermoplastic resin layers are alternately laminated, and the transmittance of visible light incident vertically on the surface of the multilayer laminated film is 50% or more and 100%.
- the multilayer laminated film of the present invention must have a structure in which 51 or more different thermoplastic resin layers are alternately laminated.
- a plurality of types of thermoplastic resin layers having different compositions are present in the multilayer laminated film, and the refractive indices of these thermoplastic resin layers are arbitrarily selected within the plane of the film. If the difference is 0.01 or more in any of the directions perpendicular to , it can be considered that "a plurality of types of thermoplastic resin layers are present.”
- the term “alternately laminated” means that layers made of different thermoplastic resins are laminated in a regular arrangement in the thickness direction.
- the multilayer laminated film consists of a layer (layer A) made of a first thermoplastic resin and a layer (layer B) made of a second thermoplastic resin, A ( BA)n, B(AB)n (n is a natural number, the same shall apply hereinafter), which are sequentially laminated.
- the multilayer laminated film consists of a layer (layer A) made of the first thermoplastic resin, a layer (layer B) made of the second thermoplastic resin, and a layer (layer C) made of the third thermoplastic resin.
- the arrangement is not particularly limited, but for example, those stacked in order with a certain regularity such as C(BA)nC, C(ABC)n, C(ACBC)n, etc. is mentioned.
- the number of layers in the multilayer laminated film is 50 or less, high reflectance cannot be obtained in the desired wavelength band.
- the above-mentioned interference reflection can achieve a higher reflectance for light in a wider wavelength band, and a multilayer laminated film that reflects light in a desired wavelength band can be obtained.
- the number of layers of the multilayer laminate film is preferably 400 layers or more, more preferably 800 layers or more.
- the manufacturing cost increases due to the enlargement of the manufacturing apparatus, and the handling property deteriorates due to the thicker film thickness.
- the layer level is the practical range.
- the multilayer laminated film of the present invention has a transmittance of 50% or more and 100% or less for visible light incident perpendicularly to the surface of the multilayer laminated film (meaning an angle of 0° with respect to the normal to the surface of the multilayer laminated film).
- the transmittance of visible light that is perpendicularly incident on the surface of the multilayer laminated film is 50% or more and 100% or less
- the average transmittance of is 50% or more and 100% or less.
- the transmittance is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If the transmittance is 90% or more, the user can visually recognize the background without feeling the presence of the multilayer laminated film.
- the upper limit of the transmittance is preferably 99% from the viewpoint of easiness of realization.
- Such a multilayer laminated film can be obtained by reducing the refractive index difference in the direction parallel to the film surface between two thermoplastic resin layers. If the refractive index difference in the direction parallel to the film surface is 0.06 or less, the transmittance is 50% or more, and if 0.04 or less, the transmittance is 70% or more, and the refractive index difference is 0.02. If the ratio is less than 80%, the transmittance can be easily increased to 80% or more, and if the refractive index difference is 0.01 or less, the transmittance can be easily increased to 90% or more.
- the term "refractive index difference in the direction parallel to the film plane" refers to the absolute value of the in-plane refractive index difference between two types of thermoplastic resin layers. For example, when the two types of layers are layer A and layer B, the absolute value of the difference in in-plane refractive index between layer A and layer B is used.
- the multilayer laminated film of the present invention when visible light is incident on the surface of the multilayer laminated film at angles of 20°, 30°, 40°, 50°, 60°, and 70° with the normal, Rp20 (%), Rp30 (%), Rp40 (%), Rp50 (%), Rp60 (%), Rp70 (%), Rp20, Rp30, Rp40, Rp50
- the standard deviation should be 5% or less.
- the P wave reflectance referred to here is the average reflectance of the P wave in the wavelength range of 400 to 700 nm.
- the reflectance of the P-wave in the case of a general transparent substrate such as transparent glass or transparent resin film, if the incident angle is gradually increased from 20° with respect to the surface normal, The reflectance of the P wave, which is the first wave, decreases, and the reflectance becomes 0% at an angle called Brewster's angle. Therefore, it is difficult for a general transparent substrate to transmit light in the front direction and reflect oblique P waves.
- the standard deviations of Rp20, Rp30, Rp40, and Rp50 take values greater than 5%. Therefore, when such a film is used as a projection member for a head-up display or the like to project a P-wave image, it is difficult to reduce the difference in brightness of the projected image due to the angle at which the P-wave image is projected.
- the multilayer laminated film of the present invention does not have Brewster's angle and is capable of reflecting P waves incident obliquely on the film surface. Furthermore, in reflectance, since the standard deviation of Rp20, Rp30, Rp40, and Rp50 is 5% or less, the brightness of the projected image according to the angle at which the P-wave image is projected when the P-wave image is projected on the multilayer laminated film can reduce the difference.
- the most preferred value for the standard deviation of Rp20, Rp30, Rp40, Rp50 is 0%, but from a feasibility point of view it would be 0.1%.
- the film between adjacent layers of two thermoplastic resin layers A method of adjusting the refractive index difference in the direction perpendicular to the plane and the number of layers can be used. At this time, by increasing the refractive index difference in the direction perpendicular to the film surface, it becomes possible to reflect the P wave incident from the oblique direction, and the refractive index difference is preferably 0.01 or more. On the other hand, if the difference is too large, the standard deviation of Rp20, Rp30, Rp40, and Rp50 will become larger than 5%, so the refractive index difference is preferably 0.13 or less.
- the in-plane refractive index difference in the direction parallel to the film surface between the adjacent layers of the two thermoplastic resin layers is small.
- the thermoplastic resin in which the refractive index in the direction parallel to the film surface of the thermoplastic resin having the smaller refractive index in the direction perpendicular to the film surface among the adjacent layers and the refractive index in the direction perpendicular to the film surface is larger It is preferably smaller than the refractive index in the direction parallel to the film surface of the resin, more preferably the difference between the two is larger than 0.01, but the in-plane refractive index difference is small.
- the in-plane refractive index difference is too large, the average transmittance of light with a wavelength of 400 to 700 nm incident perpendicularly to the surface of the multilayer laminated film becomes less than 50%, so the in-plane refractive index difference is 0.06.
- the following are preferable.
- the method of adjusting the reflection wavelength range of the multilayer laminated film to the wavelength range of 400 to 700 nm includes the difference in the perpendicular refractive index between the two thermoplastic resin layers, the number of layers laminated, the layer thickness distribution, the film forming conditions (e.g. draw ratio, draw speed , stretching temperature, heat treatment temperature, heat treatment time), and the like.
- the perpendicular refractive index is the refractive index in the direction perpendicular to the surface of the multilayer laminated film
- the perpendicular refractive index difference means the difference in the perpendicular refractive index between adjacent layers.
- the multi-layer laminate film of the present invention has a structure in which two thermoplastic resin layers are alternately laminated, and the layer made of the first thermoplastic resin is referred to as layer A, and the layer made of the second thermoplastic resin is used.
- layer A contains a crystalline thermoplastic resin
- the layer B contains an amorphous thermoplastic resin as a main component.
- the layer A contains a crystalline thermoplastic resin as a main component
- the layer B contains an amorphous thermoplastic resin as a main component.
- the layer A is made of a crystalline thermoplastic resin
- the layer B is made mainly of an amorphous thermoplastic resin.
- the term "main component” refers to a component contained in an amount of 60% by mass or more and 100% by mass or less when all components constituting the layer are taken as 100% by mass.
- the difference in the normal refractive index between the layers A and B is preferably as high as possible within the range where the standard deviation of Rp20, Rp30, Rp40, and Rp50 does not exceed 5%.
- the optical thicknesses of the layers A and B adjacent to each other satisfy the following formula (A).
- ⁇ is the reflected wavelength
- nA is the normal refractive index of layer A
- dA is the thickness of layer A
- nB is the normal refractive index of layer B
- dB is the thickness of layer B.
- the layer thickness distribution should be a constant layer thickness distribution from one side of the multilayer laminated film to the opposite side, or a layer thickness distribution that monotonically increases or decreases from one side of the multilayer laminated film to the opposite side. a layer thickness distribution in which the layer thickness increases from one side of the multilayer laminated film toward the center of the film and then decreases; It is preferable to have a layer thickness distribution that is uniform and a combination of these distributions. As for how the layer thickness distribution changes, there are continuous changes such as linear, geometrical, and stepwise progression, and about 10 to 50 layers have almost the same layer thickness, and the layer thickness changes stepwise. Variable is preferred.
- a layer having a thickness of 1% or more of the total thickness of the multilayer laminated film can be preferably provided as a protective layer, and the thickness of the protective layer is preferably relative to the entire thickness of the multilayer laminated film. It is preferably 4% or more.
- the thickness of the multilayer laminated film of the present invention is not particularly limited, it is preferably 20 ⁇ m to 300 ⁇ m, for example. When the thickness is 20 ⁇ m or more, the multi-layer laminate film becomes stiff and the handleability can be ensured. Further, when the thickness is 300 ⁇ m or less, the stiffness of the multilayer laminated film is not excessively increased, and the moldability is improved.
- a primer layer a hard coat layer, an abrasion-resistant layer, an anti-scratch layer, an anti-reflection layer, a color correction layer, an ultraviolet absorption layer, a light stabilization layer, a heat absorption layer, and a print are provided on at least one surface of the multilayer laminated film.
- Functional layers such as layers, gas barrier layers, and adhesive layers may be formed. These layers may have a single-layer structure or a multi-layer structure, and one layer may have multiple functions. Additives such as ultraviolet absorbers, light stabilizers (HALS), heat absorbers, crystal nucleating agents, and plasticizers may also be contained in the multilayer laminated film. These components can be used in combination as long as the effects of the present invention are not impaired.
- Thermoplastic resins used in the multilayer laminated film of the present invention include linear polyolefins such as polyethylene, polypropylene, poly(4-methylpentene-1), and polyacetal, ring-opening metathesis polymers of norbornenes, addition polymers, and other olefins.
- Biodegradable polymers such as alicyclic polyolefins, polylactic acid, polybutylsuccinate, etc., polyamides such as nylon 6, nylon 11, nylon 12, nylon 66, aramid, polymethyl methacrylate, poly Vinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglycolic acid, polystyrene, styrene copolymer polymethyl methacrylate, polycarbonate, polypropylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2, Polyester such as 6-naphthalate, polyether sulfone, polyether ether ketone, modified polyphenylene ether, polyphenylene sulfide, polyetherimide, polyimide, polyarylate, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride Resin,
- Polyester is a resin that has a molecular structure in which dicarboxylic acid units and diol units are linked by ester bonds.
- a polyester obtained by polymerization of monomers containing aromatic dicarboxylic acid or aliphatic dicarboxylic acid and diol as main constituents is preferable.
- aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and the like.
- aliphatic dicarboxylic acids examples include adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid and their ester derivatives.
- terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred because they exhibit a high refractive index.
- These acid components may be used alone, or two or more of them may be used in combination.
- oxyacids such as hydroxybenzoic acid may be partially copolymerized.
- diol components 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. Among them, ethylene glycol is preferably used. These diol components may be used alone or in combination of two or more.
- the absolute value of the SP value difference is 1.0 or less, delamination is less likely to occur.
- polymers having different optical properties are combined with the same basic skeleton.
- the basic skeleton here is a repeating unit that constitutes the thermoplastic resin and is the most contained unit. To give a specific example, if the thermoplastic resin is polyethylene terephthalate, the basic skeleton is an ethylene terephthalate skeleton becomes.
- thermoplastic resins when polyethylene terephthalate is used as one of the thermoplastic resins, it preferably contains an ethylene terephthalate skeleton, which is the same basic skeleton as polyethylene terephthalate, from the viewpoint of easily realizing a highly accurate laminated structure.
- the thermoplastic resins having different optical properties are resins containing the same basic skeleton, lamination accuracy is improved, and delamination at the lamination interface is less likely to occur.
- additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, electrifying agents, etc.
- Inhibitors, nucleating agents and the like can be added singly or in combination to the extent that the properties are not impaired.
- P-waves and S-waves can be defined as follows.
- the P-wave is an electromagnetic wave whose electric field component is parallel to the plane of incidence (linearly polarized light that oscillates parallel to the plane of incidence)
- the S-wave is an electric field. It represents an electromagnetic wave whose components are perpendicular to the plane of incidence (linearly polarized light oscillating perpendicular to the plane of incidence).
- FIG. 1 shows a general transparent substrate made of a conventional transparent resin film or the like
- FIG. 2 shows a conventional multilayer laminated film that reflects light
- FIG. 3 shows a multilayer laminated film described in Patent Documents 1 and 2
- FIG. 1 is a graph (one example) showing the angular dependence of reflectance when P-wave and S-wave light with a wavelength of 550 nm is incident on each film from the air for the multilayer laminated film of the present invention.
- the wavelength of 550 nm is shown as an example, but the reflectance of other visible light wavelengths and the average reflectance of wavelengths of 400 nm to 700 nm for the entire visible light range are roughly the same as those shown in FIGS. 1 to 4, respectively. have a similar relationship.
- reference numerals 1 and 2 represent the reflectance 1 of the P wave and the reflectance 2 of the S wave, respectively.
- a general transparent substrate follows Fresnel's formula, and the P-wave reflectance 1 tends to decrease as the incident angle increases, reach 0%, and then increase again.
- the S-wave reflectivity 2 increases with increasing angle of incidence.
- conventional multi-layer laminated films that reflect light have a constant high reflectance (in other words, low transmittance) at an incident angle of 0 degrees for both P and S waves, and as the incident angle increases, the P wave , S-wave reflectivity increases.
- FIG. 1 a constant high reflectance (in other words, low transmittance) at an incident angle of 0 degrees for both P and S waves
- the multilayer laminate films described in Patent Documents 1 and 2 have low reflectance (in other words, high transmittance) for both the P wave and S wave at an incident angle of 0 degrees, and as the incident angle increases, the P It is characterized by increased reflectance of both waves and S waves.
- the S-wave reflectivity 2 increases with increasing angle of incidence.
- the multilayer laminated film of the present invention has a small change in reflectance at an incident angle of 20° to 50° for P waves and a small standard deviation.
- the standard deviation of the P-wave reflectance 1 of Rp20, Rp30, Rp40 and Rp50 at an incident angle of 20° to 50° in FIGS. 3 and 4 is 7% in FIG. 3 and 1% in FIG. .
- the multilayer laminate film of the present invention must have Rp60 and Rp70 of 3% or more and 50% or less.
- Rp60 is the value at the incident angle of 60° in the curve of reflectance 1 of the P wave in FIG. 4, and is about 17% in one example.
- the projected image has sufficient brightness for visual recognition even when the projection angle is 60° or 70° when the P-wave image is projected on the multilayer laminated film.
- Rp60 and Rp70 are 50% or less, the transmittance of the light reflecting the background does not become excessively low, the reflection of the surrounding scenery other than the image is reduced, and the reflection image due to natural light is also generated. This reduces the difficulty in seeing the background through the multilayer laminated film.
- Rp60 and Rp70 are more preferably 10% or more and 50% or less, and still more preferably 20% or more and 50% or less.
- the difference in refractive index in the direction perpendicular to the film plane between adjacent layers of two thermoplastic resin layers in the multilayer laminated film can be used, and it is preferable to set the perpendicular refractive index difference to 0.12 or less. Further, it is preferable that the difference in refractive index in the direction parallel to the film surface between adjacent layers of the two thermoplastic resin layers is small.
- thermoplastic resin film surface of which the refractive index in the direction parallel to the film surface of the thermoplastic resin with the smaller refractive index in the direction perpendicular to the film surface is the larger refractive index in the direction perpendicular to the film surface is preferably smaller than the refractive index in the direction parallel to . More preferably, the thermoplastic resin film in which the refractive index in the direction parallel to the film surface of the thermoplastic resin having the higher refractive index in the direction perpendicular to the film surface and the refractive index in the direction perpendicular to the film surface is smaller. The difference in refractive index in the direction parallel to the plane is greater than 0.01.
- the average transmittance of light with a wavelength of 400 to 700 nm incident perpendicular to the surface of the multilayer laminated film will be less than 50%, so the in-plane refractive index difference should be 0.06 or less. is preferred.
- Rp60 and Rp70 can also be increased by increasing the number of layers.
- the multilayer laminate film of the present invention preferably has a minimum value of Rp20, Rp30, Rp40, Rp50, Rp60, and Rp70 of 3% or more and 50% or less. Since the reflectance in the oblique direction is at least 3% or more, when a P-wave image is projected onto the multilayer laminated film, the projected image has sufficient brightness for viewing over a wide range of angles. can let In order to set the minimum value of Rp20 to Rp70 to 3% or more, the difference in refractive index in the direction perpendicular to the film surface between adjacent layers of two thermoplastic resin layers in the multilayer laminated film and the number of layers are adjusted. method can be used, and the normal refractive index difference is preferably 0.06 or more.
- Rp30, Rp40, Rp50, Rp60, and Rp70 it is preferable that any one of Rp30, Rp40, and Rp50 takes the minimum value in the multilayer laminated film of the present invention.
- at least one of Rp30, Rp40 and Rp50 is preferably the minimum value.
- the standard deviation of Rp20, Rp30, Rp40 and Rp50 can be reduced by setting the minimum value to one of Rp30, Rp40 and Rp50 among Rp20, Rp30, Rp40, Rp50, Rp60 and Rp70.
- the film surface between the two adjacent thermoplastic resin layers in the multilayer laminated film A method of adjusting the refractive index difference and the number of layers in the direction parallel to the film surface can be used, and the refractive index in the direction parallel to the film surface of the thermoplastic resin with the smaller refractive index in the direction perpendicular to the film surface is
- the refractive index in the direction perpendicular to the plane is preferably smaller than the refractive index in the direction parallel to the film plane of the thermoplastic resin, and more preferably the in-plane refractive index difference is greater than 0.01. .
- the difference in the perpendicular refractive index is too small, Rp60 and Rp70 will be 3% or less, so the difference in the perpendicular refractive index is preferably 0.06 or more. , Rp40, and Rp50 become larger than 5%, the normal refractive index difference is preferably 0.13 or less.
- the reflected light when a P wave is incident on the surface of the multilayer laminated film at an angle of 60° with the normal, the reflected light preferably has a saturation of 20 or less, More preferably, the reflected light has a saturation of 5 or less.
- the saturation of the reflected light of the P wave when it is incident at an angle of 60° with the normal to the surface of the multilayer laminated film may be referred to as “the saturation of the reflected light of the P wave”.
- the fact that the saturation of the reflected light of the P wave is 20 or less means that uniform reflection (the change in reflectance at each visible light wavelength is small) can be achieved over the entire wavelength range of visible light.
- coloring due to reflected light can be suppressed.
- the color of the reflected light can be prevented from changing and being colored with respect to the color of the incident light. Therefore, when the multi-layer laminated film is used as a projection material for an augmented reality device, etc., the color of the projected image displayed when the projected image is projected with P waves is reproduced as almost the same color as the image projected from the display. Therefore, it is preferable in that coloring does not change.
- the reason why the saturation of the reflected light of the P wave is 20 or more is that the standard deviation of the reflectance spectrum in the wavelength range of 400 nm to 700 nm is large and the reflectance of the wavelength of a specific color is high, or the wavelength of a specific color The reason for this is that the reflectance of the Therefore, it is preferable to make the reflectance uniform in the wavelength range of 400 nm to 700 nm. An evenly distributed arrangement is preferred. A uniform distribution arrangement of the thicknesses of the layer A and the layer B that reflect the wavelength range of 400 nm to 700 nm will be described with reference to FIG.
- FIG. 5 is a graph in which the horizontal axis represents the positions of Layer A and Layer B in the multilayer stack, and the vertical axis represents the thickness (nm) of Layer A and Layer B.
- the layer thickness is continuously changed from the thickness of the layers A and B reflecting the wavelength of 400 nm toward the thickness of the layers A and B reflecting the wavelength of 700 nm.
- the standard deviation of the reflectance in the wavelength band can be made 10% or less.
- FIG. 5 shows a multilayer laminated film having 401 layers, with the layer A having a perpendicular refractive index (nA) of 1.5 and the layer B having a perpendicular refractive index (nB) of 1.6.
- nA perpendicular refractive index
- nB perpendicular refractive index
- 1 shows an example of ideal layer thickness distribution of layers A and B from position 1 to layer position 401 on the opposite film surface.
- an error from the ideal layer thickness as shown in FIG. 5 occurs.
- the average error at each layer position from layer position 1 to layer position 401 counted from the surface is within about ⁇ 10%. If so, the saturation of the reflected light of the P wave when incident at an angle of 60° with respect to the normal to the multilayer laminated film can be reduced to 20 or less.
- a multilayer laminated structure can be obtained by melting two types of thermoplastic resins, alternately laminating them using a laminating device, and extruding the molten laminate into a sheet using a T-shaped die or the like. Suppressing the disorder of the layers of the fused laminate leads to suppressing errors in thickness.
- a thick layer may be provided as the outermost layer of the fused laminate. The thickness of the outermost layer is preferably 1% or more, more preferably 4% or more, relative to the thickness of the entire fused laminate. Moreover, it is more preferable to thicken not only one outermost layer but both outermost layers.
- the azimuth angle variation of reflectance is 5% or less when a P wave is incident on the surface of the multilayer laminated film at an angle of 60° with the normal. preferable.
- the azimuth angle means each azimuth when the azimuth angle in the main orientation axis direction is 0° in the plane of the film surface of the multilayer laminated film 3 constituting the laminate of the present invention. Represents an angle (0°, 45°, 90°, 135°, 180°).
- the direction of the main orientation axis means the direction in which the degree of orientation is the largest in the plane of the film.
- the degree of orientation can be measured by a known molecular orientation meter.
- the molecular orientation meter for example, a molecular orientation meter MOA-7015 manufactured by current Oji Scientific Instruments Co., Ltd. can be used.
- the azimuth angle variation is Rp60 (0 °), Rp60 (45 °), Rp60 (90 °), Rp60 (135 ° ) and the difference between the maximum and minimum values of Rp60 (180°).
- the azimuth angle which is the direction of inclination, is defined as 0°, 45°, 90°, 135°, and 180° in the clockwise direction, with the azimuth angle in the direction of the main orientation axis of the multilayer laminate film being 0°. adopt. Since the azimuth angle variation of Rp60 is 5% or less, displayability such as brightness of the information can be maintained at the same level even if the image is projected from any azimuth.
- Stretching may be performed so as to reduce the difference in the orientation state between the longitudinal direction and the width direction of the film during biaxial stretching.
- the stretching conditions for reducing the difference in the orientation state between the longitudinal direction and the width direction differ depending on the thermoplastic resin used and the combination thereof, but when using a polyester resin, for example, the stretching ratio in the width direction is slightly higher than that in the longitudinal direction.
- Preferred conditions include: This effect is one of the features of the multilayer laminate film of the present invention, and is an effect that cannot be achieved with a polarizing reflective film.
- the multilayer laminated film of the present invention has a structure in which a layer (layer A) made of a first thermoplastic resin and a layer (layer B) made of a second thermoplastic resin are alternately laminated, and the first It is preferable that the thermoplastic resin contains a crystalline polyester as a main component, and the second thermoplastic resin contains a polyester containing a structure derived from naphthalenedicarboxylic acid as a main component.
- a polyester containing a structure derived from naphthalenedicarboxylic acid can be wholly or partially amorphous polyester.
- first thermoplastic resin refers to the entire resin component that constitutes the layer A
- second thermoplastic resin refers to the entire resin component that constitutes the layer B.
- the layer A contains crystalline polyester as a main component means that the first thermoplastic resin contains 60% by mass or more and 100% by mass or less of crystalline polyester.
- Layer B is mainly composed of a polyester containing a structure derived from naphthalenedicarboxylic acid” means a polyester containing a structure derived from 60% by mass or more and 100% by mass or less of naphthalenedicarboxylic acid in the second thermoplastic resin is included.
- thermoplastic resin layer A which of the two types of thermoplastic resin layers that are alternately laminated is to be layer A is determined by comparing the perpendicular refractive indices. More specifically, the layer having a relatively smaller refractive index perpendicular to the plane is referred to as layer A, and the thermoplastic resin constituting this layer is referred to as the "first thermoplastic resin".
- the second thermoplastic resin is mainly composed of a polyester containing a structure derived from naphthalenedicarboxylic acid, it becomes easy to increase both the in-plane refractive index and the perpendicular refractive index.
- the first thermoplastic resin is mainly composed of a crystalline polyester
- the second thermoplastic resin is mainly composed of a polyester containing a structure derived from naphthalene dicarboxylic acid.
- the thermoplastic resin (first The refractive index in the direction parallel to the film surface of the thermoplastic resin) is the refractive index in the direction perpendicular to the film surface.
- the refractive index in the direction parallel to the film surface of the thermoplastic resin (second thermoplastic resin) and it is easy to make the difference larger than 0.01.
- Each layer of the first thermoplastic resin and the second thermoplastic resin can be a relatively highly crystalline layer and a relatively less crystalline layer.
- the second thermoplastic resin preferably contains a structure derived from alkylene glycol having a number average molecular weight of 200 or more.
- a thermoplastic resin containing a structure derived from alkylene glycol with a number average molecular weight of 200 or more with another thermoplastic resin, the average refractive index of the in-plane refractive index and the normal refractive index of the thermoplastic resin It is possible to efficiently lower the glass transition temperature while maintaining the Stretching is also facilitated. This is because the reflectance characteristics of the polyester containing the structure derived from naphthalenedicarboxylic acid, which is the main component of the second thermoplastic resin, are not impaired, and the effect of stabilizing the polyester is high.
- Alkylene glycol includes polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and the like. Moreover, the molecular weight of the alkylene glycol is preferably 200 or more and 2000 or less. When the molecular weight of the alkylene glycol is 200 or more, the volatility of the alkylene glycol is kept low, so the alkylene glycol is sufficiently incorporated into the polymer when synthesizing the thermoplastic resin, and as a result, the glass transition temperature is lowered. You can get enough effect to make it. In addition, when the molecular weight of the alkylene glycol is 2000 or less, the decrease in reactivity during production of the thermoplastic resin is suppressed, making the thermoplastic resin more suitable for producing multilayer laminated films.
- the second thermoplastic resin contains a structure derived from two or more aromatic dicarboxylic acids and two or more alkyldiols, and has an alkylene diol having a number average molecular weight of 200 or more. It contains a structure derived from glycol.
- the molecular weight of alkylene glycol can be calculated from the 1 H-NMR spectrum, and details such as measurement conditions will be described later.
- both the first thermoplastic resin and the second thermoplastic resin in the multilayer laminated film are plane-oriented, and the strength of the plane orientation is greater than that of the first thermoplastic resin.
- the refractive index difference in the direction perpendicular to the film surface of the multilayer laminated film is in the range of 0.06 to 0.12, and the refractive index difference in the direction parallel to the film surface
- the refractive index in the direction parallel to the film surface of the thermoplastic resin (first thermoplastic resin) with the smaller refractive index in the direction perpendicular to the film surface is the one with the larger refractive index in the direction perpendicular to the film surface. It can be made smaller than the refractive index in the direction parallel to the film surface of the thermoplastic resin (second thermoplastic resin), and it becomes easy to make the difference larger than 0.01.
- the first thermoplastic resin is mainly composed of crystalline polyester
- the second thermoplastic resin is mainly composed of polyester containing a structure derived from naphthalenedicarboxylic acid
- the first thermoplastic resin is mainly composed of polyethylene terephthalate
- the second thermoplastic resin is mainly composed of polyester obtained by copolymerizing 15 mol% to 25 mol% or 75 mol% to 85 mol of naphthalenedicarboxylic acid with respect to the entire acid component. is preferred.
- a multilayer laminate film obtained by biaxially stretching the melting point of the first thermoplastic resin higher than the melting point of the second thermoplastic resin, and heat-treating the second thermoplastic resin after the biaxial stretching at a temperature below the melting point of the second thermoplastic resin. is mentioned. That is, the multilayer laminated film of the present invention has two or more peaks showing a melting enthalpy ( ⁇ Hm) of 3 J/g or more by differential scanning calorimetry (DSC), and 3 J on the lower temperature side than the peak showing the melting enthalpy. A multilayer laminated film having a peak of less than /g is preferred.
- the second thermoplastic resin contains a structure derived from an alkylene glycol having a number average molecular weight of 200 or more, it becomes easier to achieve the above properties.
- Patent Document 1 describes a preferred structure of a multilayer laminated film, which is composed of two kinds of thermoplastic resins, the resin constituting the layer A contains a crystalline polyester, and the resin constituting the layer B is an amorphous polyester.
- a film is disclosed.
- the resin exhibiting amorphous property is a resin heated from 25°C to 300°C at a heating rate of 20°C/min (1st RUN ), held in that state for 5 minutes, then rapidly cooled to a temperature of 25° C. or less, and again heated from room temperature to 300° C. at a rate of 20° C./min, resulting in a 2nd RUN.
- the heat of crystal fusion ⁇ Hm obtained from the peak area of the melting peak is 5 J/g or less, and more preferably the resin does not show a peak corresponding to crystal melting. ing.
- the multilayer laminated film of Patent Document 1 when a multilayer laminated film using a crystalline polyester for the layer A and a resin exhibiting amorphousness as defined above for the layer B is heated at a temperature of 150 ° C. for 2 hours, the multilayer laminated film The present inventors have discovered the problem that the internal haze of is increased.
- the multilayer laminated film of the present invention has a reflection characteristic with a small P-wave reflectance and a small standard deviation, and is composed of a layer with relatively low crystallinity and a layer with relatively high crystallinity, A layer with relatively low crystallinity can be obtained, for example, by oriented crystallization of a copolymerized thermoplastic resin exhibiting a melting point.
- Such a multilayer laminate film can be determined by the following measurements. That is, the multilayer laminated film of the present invention is measured by differential scanning calorimetry (DSC) at the temperature at which the absolute value of the absorbed heat is maximum, that is, the multilayer laminated film is measured by differential scanning calorimetry (DSC) from 25 ° C. to 300 ° C.
- DSC differential scanning calorimetry
- Tm °C
- T* °C
- Tmin(°C) the minimum value of A(T) is Amin and the temperature at that time is Tmin(°C)
- Tn (°C) that is the minimum temperature among Tn (°C) that always satisfies A(T) ⁇ 0.2Amin in the temperature range from Tn to Tn + 5°C ) is defined as T* (°C).
- Tm ⁇ T*>27 not only the layer A but also the layer B of the multilayer laminated film of the present invention are oriented and crystallized. can be suppressed, and the internal haze can be suppressed to 0.8% or less.
- Tm ⁇ T* ⁇ 27 it means that the oriented crystallization of the layer B is weak and the ratio of the amorphous portion in which thermal crystallization proceeds by heating at 150° C. for 2 hours is high. Therefore, when Tm ⁇ T* ⁇ 27, the internal haze of the multi-layer laminated film is greatly increased by heating at 150° C. for 2 hours, and the internal haze may exceed 0.8%.
- Tm-T* (° C.)
- Tm-T* is 50 or less because the internal haze does not fall below 0.1% when Tm-T* is a certain value or more.
- Tm ⁇ T* ⁇ 27 the oriented crystallization of the layer B is weak and the ratio of the amorphous portion in which thermal crystallization proceeds by heating at 150° C. for 2 hours is high, so the internal haze after heating under these conditions is It exceeds 0.8%, and when used in an augmented reality device, the visibility of the outside scenery may deteriorate.
- Tm-T* indicates the crystalline state of the layer B composed of the second thermoplastic resin in the multilayer laminated film, and the larger this value, the more crystalline. Therefore, as described above, in order to suppress the internal haze after heating at 150° C. for 2 hours, it is preferable that the layer B composed of the second thermoplastic resin is maintained in a crystalline state.
- the first thermoplastic resin is mainly composed of a crystalline resin
- the melting point of the second thermoplastic resin is the same as that of the first thermoplastic resin.
- a thermoplastic resin is selected so that it is lower than the melting point of the second thermoplastic resin, and after biaxial stretching, heat treatment is performed at a temperature below the melting point of the second thermoplastic resin. It is preferably 5°C lower than the melting point, more preferably 10°C.
- Layer A composed of the first thermoplastic resin and layer B composed of the second thermoplastic resin in the multilayer laminate film are obtained by heat-treating at a temperature below the melting points of the first and second thermoplastic resins after biaxial stretching. In both cases, the crystal size is dense and strong orientation crystallization progresses, and even if the crystal structure is heated at 150° C. for 2 hours, the crystal structure hardly changes, so that the increase in internal haze can be suppressed.
- the melting point of the second thermoplastic resin when the melting point of the second thermoplastic resin is equal to or lower than the heat treatment temperature, the second thermoplastic resin in the multilayer laminated film melts its oriented crystallized structure due to the heat treatment, and thermal crystallization progresses into an amorphous state. High proportion of parts. If this state is heated at 150° C. for 2 hours, the amorphous portion of the second thermoplastic resin is recrystallized and grown as coarse crystals, which undesirably increases the internal haze.
- FIG. 7 shows DSC1st curves of multilayer laminated films satisfying Tm ⁇ T*>27 (code 4) and Tm ⁇ T* ⁇ 27 (code 5), respectively.
- the temperature differential curve of the DSC1st curve, A(T) dDSC/dT (mW/°C)
- indicates the slope of the tangent line of the DSC1st curve at each temperature, and when A(T) 0, the DSC1st curve is minimal. or show a local maximum.
- thermoplastic resin preferably exhibits crystallinity, and more preferably contains a crystalline polyester as a main component, as will be described later.
- T* obtained by the above-described measurement method is the temperature at which A(T) is below a certain value, that is, the slope of the tangent line of the DSC1st curve is below a certain value, that is, a weak endothermic peak is observed. Indicates the minimum temperature.
- the DSC1st curve (solid line, code 4) of the multilayer laminated film with Tm ⁇ T*>27 is 200° C. compared to the DSC1st curve (dotted line, code 5) of the multilayer laminated film with Tm ⁇ T* ⁇ 27. Heat absorption can be seen from the surroundings, and the degree of reduction is increasing as the tendency of the graph. That is, in FIG.
- the multilayer laminated film (reference numeral 6) satisfying Tm ⁇ T*>27 has a smaller A(T) value than the multilayer laminated film (reference numeral 7) satisfying Tm ⁇ T* ⁇ 27. It is shown that. This is because the layer B composed of the second thermoplastic resin other than the first thermoplastic resin is in a crystalline state and melts to absorb heat. .
- the layer B composed of the second thermoplastic resin is not in a crystalline state, and the refractive index in the direction parallel to the film plane and the refractive index in the direction parallel to the film plane are It is an isotropic amorphous state in which the difference from the perpendicular refractive index is less than about 0.01. Therefore, there is no heat absorption near 200° C., and only the melting peak derived from the first thermoplastic resin is measured in the DSC1st curve.
- T* is the minimum temperature among the tangents of the DSC1st curve that have a slope below a certain level.
- Amin is the minimum value of A(T) at 150° C. ⁇ T ⁇ Tm
- Tmin is T at that time
- the temperature differential curve always satisfies A(T) ⁇ 0.2 Amin in the range of Tn to Tn + 5 ° C. , the minimum Tn is T*.
- T3 and T5 that always satisfy A(T) ⁇ 0.2Amin in the temperature range of T (° C.) to T+5° C. at each Tn. becomes.
- T3 indicates the melting peak derived from the second thermoplastic resin
- T5 indicates the melting peak of the first thermoplastic resin.
- T1 T where A (T) ⁇ 0.2 Amin even partially in the range of T to T + 5 ° C. shows the melting peak of the thermally crystalline portion of the first thermoplastic resin due to heat treatment. .
- the maximum value of A(T) at 150°C ⁇ T ⁇ Tm is preferably 0.040 or less.
- a (T) if the maximum value at 150 ° C. ⁇ T ⁇ Tm is 0.040 or less, the reflectance (% ) becomes 10% or more, and the brightness can be maintained to the extent that a clear projected image is obtained.
- FIG. 10 shows DSC1st curves of multilayer laminated films with maximum values of A(T) of 0.040 or less (code 8) and over 0.040 (code 9) at 150° C. ⁇ T ⁇ Tm, respectively.
- FIG. 11 is a graph of temperature differential curves: A(T) of reference numerals 8 and 9 in FIG. At 150° C. ⁇ T ⁇ Tm, A(T)>0 is established in the temperature region where the melting peak of the second thermoplastic resin has passed and the temperature tends to rise as shown in FIG.
- Layer B is in the crystalline state.
- the maximum value of A(T) is less than or equal to 0.040, which means there is no peak or peaks below 3 J/g, layer B is in a crystallographically relaxed state.
- the maximum value of A(T) is 0.040 or less because the melting enthalpy of the melting peak derived from thermal crystallization by heat treatment of the first thermoplastic resin is less than 3 J/g.
- thermoplastic resin is selected so that the melting point of the second thermoplastic resin is higher than that of the second thermoplastic resin, and heat treatment is performed at a temperature of ⁇ 20° C. or higher, the melting point of the second thermoplastic resin, after biaxial stretching. Furthermore, a method of performing heat treatment at the melting point of the second thermoplastic resin of ⁇ 10° C. or higher is preferred. When the second thermoplastic resin does not have a melting point, a method of carrying out the heat treatment after the biaxial stretching at a temperature of ⁇ 60° C. or higher, which is the melting point of the first thermoplastic resin, may be used.
- the crystals of the layer B in the multilayer laminated film are relaxed, the normal refractive index in the direction perpendicular to the film surface increases, and the normal refractive index in the direction perpendicular to the film surface between the two thermoplastic resin layers
- the reflectance becomes 3% or more when the P-wave light is incident on the film surface at 60°.
- this normal refractive index difference it is preferable to set this normal refractive index difference to 0.06 or more.
- the upper limit of the heat treatment temperature as described above, the crystal state of the layer B is relaxed and the refractive index in the direction perpendicular to the film surface increases, while the internal haze increases after heating at 150 ° C. for 2 hours.
- the melting point of the second thermoplastic resin is about the melting point, and if there is no melting point, the melting point of the first thermoplastic resin is -30°C.
- A(T) when the maximum value at 150° C. ⁇ T ⁇ Tm is greater than 0.040, the layer B is in a crystalline state, so the direction perpendicular to the film plane of the crystalline resin layer A is less than 0.050 and there is no difference. As a result, the reflectance (%) is less than 3% when a P-wave light beam is incident at 60°, and a projected image that is obliquely incident cannot be clearly viewed.
- a laminated structure of 51 or more layers can be produced by the following method.
- the first thermoplastic resin and the second thermoplastic resin are supplied in a molten state from two extruders A corresponding to layer A and extruder B corresponding to layer B, and A molten thermoplastic resin is laminated into 51 or more layers using a known lamination apparatus such as a multi-manifold type feed block and a square mixer, or a comb type feed block alone.
- the molten laminate is melt-extruded into a sheet using a T-shaped die or the like, and then cooled and solidified on a casting drum to obtain an unstretched multilayer laminate film.
- the methods described in JP-A-2007-307893, JP-A-4691910, and JP-A-4816419 are preferable.
- the layer (layer A) made of the first thermoplastic resin is mainly composed of crystalline polyester
- the layer (layer B) made of the second thermoplastic resin is polyester containing a structure derived from naphthalene dicarboxylic acid. It is preferable to select each thermoplastic resin so as to be the main component.
- this unstretched multilayer laminate film is stretched and heat-treated.
- the stretching method a known sequential biaxial stretching method or simultaneous biaxial stretching method is preferable.
- the stretching temperature is preferably in the range from the glass transition temperature of the unstretched laminated film to the glass transition temperature +80°C.
- the draw ratio is preferably 2 to 8 times in both the longitudinal direction and the width direction, more preferably 3 to 6 times, and preferably the difference in draw ratio between the longitudinal direction and the width direction is small.
- Stretching in the longitudinal direction is preferably carried out using a peripheral speed difference between rolls of a longitudinal stretching machine.
- the tenter clip for stretching and heat treatment in the present invention is driven by a linear motor system.
- the linear motor method is superior in that the draw ratio can be freely changed because each clip has a high degree of freedom.
- the heat treatment temperature is preferably in the range of the stretching temperature or higher to the melting point or lower of the thermoplastic resin of the layer B.
- After the heat treatment it is also preferable to pass through a cooling step at the heat treatment temperature -30° C. or lower.
- a cooling step at the heat treatment temperature -30° C. or lower.
- the relaxation ratio is preferably in the range of 1% to 10%, more preferably in the range of 1% to 5%.
- FIG. 12 shows a configuration including the multilayer laminate film 3 of the present invention as an example of the projection image display member of the present invention.
- FIG. 12 shows a structure in which an arbitrary antireflection layer 12 and a functional layer 13 are laminated on the multilayer laminate film of the present invention.
- the antireflection layer 12 is a layer that prevents reflection on the surface of the projection image display member, and is preferably positioned on at least one surface of the multilayer laminate film 13 . As shown in FIG.
- the antireflection layer 12 by providing the antireflection layer 12 on at least one surface of the multilayer laminate film 3, oblique reflection of S waves on the surface of the projection image display member can be suppressed.
- the projection image display member of the present invention is used as the projection member of the augmented reality device, it is possible to suppress the reflection of the surrounding scenery other than the image.
- the projection image display member preferably has a functional layer 13 on at least one surface of the multilayer laminated film 3 (in the embodiment shown in FIG. 13).
- the functional layer 13 includes a hard coat layer, an abrasion-resistant layer, an anti-scratch layer, an anti-reflection layer, a color correction layer, an ultraviolet absorption layer, a light stabilization layer, a heat absorption layer, a printing layer, a gas barrier layer, an adhesive layer, and the like. These layers may have a single-layer structure or a multi-layer structure, and one layer may have a plurality of functions.
- a laminate in which the transparent support 14 and the multilayer laminated film 3 are laminated, and a laminate in which the multilayer laminated film 3 is positioned between the transparent supports 14 (FIGS. 14A to 14C).
- lamination of the antireflection layer 12 and the functional layer 13 is optional.
- the laminated transparent support 4 may be glass or a transparent resin substrate, and the thickness thereof is preferably 1 mm or more in order to provide support. The upper limit of the thickness of the transparent support 14 is not particularly limited.
- the glass of the transparent support 14 not only single-layer glass, but also laminated glass and tempered glass used for windshields, side glasses, and rear glasses of automobiles, plate glass for glass building materials, tempered glass, multi-layer glass, vacuum glass, and the like are used. be able to.
- the transparent resin base material of the transparent support 14 polyethylene terephthalate, polycarbonate, acryl, polyvinyl chloride, polyethylene, polypropylene, polymethylpentene and its copolymer, acrylonitrile-butadiene-styrene copolymer, and the like are preferable.
- These transparent resin substrates may be a single component or a mixture of multiple types.
- direct lamination may be performed as shown in A of FIG. 13 and A of FIG.
- bonding or the like is also possible by forming an adhesive layer 15 using a pressure-sensitive adhesive, an adhesive, or the like.
- adhesives and adhesives include vinyl acetate resin, vinyl chloride/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl ether, nitrile rubber, styrene/ Butadiene rubber-based, natural rubber-based, chloroprene rubber-based, polyamide-based, epoxy resin-based, polyurethane-based, acrylic resin-based, cellulose-based, polyvinyl chloride, polyacrylic acid ester, polyisobutylene, and the like.
- pressure-sensitive adhesives and adhesives may be used alone or in combination of multiple types, and may also be used as adhesiveness modifiers, plasticizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, Agents, lubricants, coloring agents, cross-linking agents, etc. may be added.
- the forms of these adhesives before processing include liquid, gel, mass, powder, and film.
- Solvent volatilization, moisture curing, heat curing, curing agent mixing, anaerobic curing, ultraviolet curing, heat melting cooling, pressure sensing, and the like can be used as methods for solidifying the adhesive layer.
- Lamination methods include lamination molding, injection molding, vacuum molding, air pressure molding, vacuum and air pressure molding, and the like, and the projection image display member is produced by using the above-described method of heating, pressurizing, and solidifying the adhesive layer. .
- the augmented reality device of the present invention is an augmented reality device that includes the multilayer laminated film of the present invention or the projected image display member of the present invention, and an image projection device that irradiates the display surface with light.
- a form of use thereof includes wearing on the head, and more specifically, a spectacles type form and the like.
- FIG. 15 shows one embodiment of the augmented reality device of the present invention.
- the projection image 17 emitted from the image projection device 16 passes through the light guide member 18, is reflected by the reflection member 19, and is reflected by the projection image display member 20, thereby ensuring the visibility of the background 21.
- the image is projected on the eyes 22 of the augmented reality device user.
- Examples of the image projection device 16 include a liquid crystal projector, RGB laser, DLP (Digital Light Processing), LCOS (Liquid crystal on silicon), liquid crystal display, organic EL display, and the like.
- Examples of the reflecting member 19 include a mirror in which a metal layer or a dielectric multilayer film is provided on the surface of a support, and a multilayer laminate film in which thermoplastic resins having different refractive indices are alternately laminated.
- the light guide member 18 is preferably transparent with little absorption of the projected image and has a small phase difference so as not to disturb the polarized light of the projected image. Olefins, polymethylpentene and its copolymers, and acrylonitrile/butadiene/styrene copolymers are preferred.
- the intensity of the P wave in the intensity of the light incident on the display surface of the projection image display member 20 is 51. % or more.
- the intensity of the P wave which accounts for the intensity of the light incident on the display surface of the projection image display member, may be simply referred to as "the intensity of the P wave".
- the conventional projection image display member 23 using glass or a transparent resin film reflects S waves and transmits P waves incident obliquely.
- the S wave is used as the light of the projection image incident on the display surface of the projection image display member.
- the double image of the display image is caused by the reflection of light on the front and back surfaces of the image display member 23, and the light beams are shifted to cause the display image to appear double.
- the projection image display member 20 using the multilayer laminated film of the present invention reflects the obliquely incident P wave, so that the P wave is incident on the display surface of the projection image display member.
- P-waves can be used as light for projection images. P-waves are reflected only inside the film and not on the front and back surfaces, thus reducing the double image problem.
- the intensity of the P wave is preferably 51% or more, more preferably 90% or more, and the upper limit is about 99% from the viewpoint of polarization control accuracy.
- the incident angle of the light forming the image is preferably 20° or more, more preferably in the range of 50° to 70°.
- the P-wave reflectance decreases from an incident angle of 30° or more, and particularly significantly decreases in the range of 50° to 70°. Therefore, by making the projection image of the P wave incident on the projection image display member at the above incident angle, the effect of suppressing the double image is increased.
- FIG. 17 Another application form of the augmented reality device using the multilayer laminated film or projection image display member of the present invention is the video projection device shown in FIG.
- the augmented reality apparatus of the present invention shown in FIG. 17 irradiates a projected image 17 from an image projector 16 onto a projected image display member 20 to project the image onto the projected image display member 20 of the augmented reality apparatus. Furthermore, by passing the background 21, which is information about the surrounding scenery, through the projection image display member 20, the eyes 22 of the augmented reality device user can visually recognize the image and the surrounding scenery superimposed.
- the projection image display member of the present invention has a transmittance of 50% or more and 100% or less for visible light incident perpendicularly to the surface of the projection image display member, and the projection image display member surface has an angle formed with a normal line thereof.
- the reflectance of the P wave when visible light is incident at 20°, 30°, 40°, 50°, 60°, and 70° is Rp20 (%), Rp30 (%), and Rp40 (%) in that order.
- Rp50 (%), Rp60 (%), Rp70 (%), the standard deviation of Rp20, Rp30, Rp40 and Rp50 is 5% or less
- Rp60 and Rp70 are 3% or more and 50% or less
- the projection image display member of the present invention has a transmittance of 50% or more and 100% for visible light incident perpendicularly to the surface of the projection image display member (meaning an angle of 0° with respect to the normal line of the surface of the projection image display member). % or less.
- the transmittance of visible light that is vertically incident on the surface of the projection image display member is 50% or more and 100% or less
- the wavelength of 400 to 700 nm that is vertically incident on the surface of the projection image display member is means that the average transmittance of light is 50% or more and 100% or less.
- the transmittance is preferably 70% or higher, more preferably 80% or higher, and still more preferably 90% or higher. If the transmittance is 90% or more, the user can visually recognize the background without feeling the presence of the projection image display member.
- the upper limit of the transmittance is preferably 99% from the viewpoint of easiness of realization.
- the transmittance of light perpendicularly incident on the projection image display member is obtained by measuring the transmittance of light with a wavelength of 400 to 700 nm at an incident angle ⁇ of 0° with a spectrophotometer in increments of 1 nm, and calculating the average value. can be measured.
- the projection image display member of the present invention in which the standard deviations of Rp20, Rp30, Rp40 and Rp50 are 5% or less does not have Brewster's angle and reflects P waves incident obliquely on the surface of the projection image display member. is possible. Therefore, when the P-wave image is projected onto the projection image display member, it is possible to reduce the difference in brightness of the projected image due to the angle at which the P-wave image is projected.
- the most preferred value for the standard deviation of Rp20, Rp30, Rp40, Rp50 is 0%, but from a feasibility point of view it would be 0.1%.
- the projection image display member of the present invention preferably has Rp60 and Rp70 of 3% or more and 50% or less.
- Rp60 and Rp70 are 3% or more, the projected image has sufficient brightness for visual recognition even when the projection angle is 60° or 70° when the P-wave image is projected onto the projection image display member. can have
- Rp60 and Rp70 are 50% or less, the transmittance of the light reflecting the background does not become excessively low, thereby reducing the difficulty of visually recognizing the background through the projection image display member.
- Rp60 and Rp70 are more preferably 10% or more and 50% or less, and still more preferably 20% or more and 50% or less.
- FIG. 18 shows an example of a graph showing the angular dependence of the reflectance when P-wave and S-wave light with a wavelength of 550 nm is incident on each film from the air for the transparent projection image display member of the present invention.
- the wavelength of 550 nm is shown here, other visible light wavelengths and the reflectance of the entire visible light range, such as the average reflectance of wavelengths of 400 nm to 700 nm, have substantially the same relationship as shown in FIG.
- reference numerals 1 and 2 denote the P-wave reflectance and the S-wave reflectance, respectively.
- the multilayer laminated film of the present invention has a small standard deviation of reflectance at an incident angle of 20° to 50° for P waves, so that when an image of P waves is projected onto a projection image display member, the image of P waves is displayed. It is possible to reduce the luminance difference of the projected image due to the projection angle.
- At least one of Rp20, Rp30, Rp40, Rp50, Rp60, and Rp70 has a minimum value of 3% or more among Rp20, Rp30, Rp40, Rp50, Rp60, and Rp70. Since the reflectance in the oblique direction is at least 3% or more in this way, when a P-wave image is projected onto the projection image display member, the projected image has sufficient luminance to be visually recognized over a wide range of angles. can have.
- the projection image display member of the present invention preferably has a minimum value of Rp30 to Rp50 among Rp20 to Rp70.
- the standard deviation of Rp20 to Rp50 can be further reduced by setting the minimum value to any one of Rp30 to Rp50 among Rp20 to Rp70.
- the reflected light when a P wave is incident on the surface of the projection image display member at an angle of 60° with the normal line, the reflected light has a saturation of 20 or less. Preferably, it is 5 or less.
- the saturation of the reflected light of the P wave when it is incident at an angle of 60° with the normal to the surface of the projection image display member may be referred to as “the saturation of the reflected light of the P wave”.
- the fact that the saturation of the reflected light of the P wave is 20 or less means that uniform reflection can be achieved over the entire wavelength range of visible light. It is possible to suppress coloring caused by. Therefore, when the projection image display member is used as a projection member for an augmented reality device, etc., the color of the projected image displayed when the projected image is projected with P waves is almost the same color as the image emitted from the display. reproduced.
- the projection image display member of the present invention has an azimuth angle variation of 5 in the reflectance (Rp60) when a P wave is incident on the surface of the projection image display member so that the angle formed with the normal line thereof is 60°. % or less. Since the azimuth angle variation of Rp60 is 5% or less, displayability such as brightness of the information can be maintained at the same level even if the image is projected from any azimuth.
- the multilayer laminate film and the projection image display member of the present invention will be described in more detail below using examples. However, the multilayer laminate film and projection image display member of the present invention are not limited to this.
- the TEM image was processed using the image processing software Image-Pro Plus ver. 4 was used to open this file and perform image analysis.
- image analysis processing the relation between the position in the thickness direction and the average brightness of the area sandwiched between two lines in the width direction was read as numerical data in the vertical thick profile mode.
- spreadsheet software "Excel" registered trademark
- position (nm) and brightness data were subjected to numerical processing of a 5-point moving average.
- VBA Visual Basic for Applications
- the number of laminations was determined by counting the total number of the layers in the bright and dark areas, regarding each of the bright and dark layers in the change in brightness as one layer.
- Rp20, Rp30, Rp40, Rp50, Rp60, Rp50, Rp60, Rp20, Rp30, Rp40, Rp50, Rp60, Rp70 was determined. Also, standard deviations of Rp20, Rp30, Rp40, and Rp50 were calculated. The direction of inclination of each incident angle was the direction along the main orientation axis of the film for the multilayer laminated film, and the direction along the short side for the projection image display member.
- Calculated using the XYZ value under the C light source using the reflectance spectrum of the P wave, the spectral distribution of the C light source, and the XYZ color matching function, and the XYZ value, and the saturation C * value a * and b * was calculated as the square root of the sum of the squares of
- Rp60 (0 °), Rp60 (45 °), Rp60 (90 °), Rp60 as the average reflectance of P wave in the wavelength range of 400 nm to 700 nm at an incident angle of 60 ° in each azimuth direction (135°) and Rp60 (180°) were obtained. Furthermore, the difference between the maximum and minimum values of Rp60 (0°), Rp60 (45°), Rp60 (90°), Rp60 (135°), and Rp60 (180°) was defined as the azimuth angle variation.
- Main orientation axis direction A sample size was set to 10 cm x 10 cm, and a sample was cut out at the center in the film width direction. The degree of orientation was measured using a molecular orientation meter MOA-7015 manufactured by Oji Keisokuki Co., Ltd., and the direction with the highest degree of orientation was taken as the main orientation axis direction.
- the main orientation axis direction is the direction of the in-plane azimuth angle of 0° on the outermost surface.
- Tm and T* 5 mg of the multilayer laminated film was weighed with an electronic balance, sandwiched between aluminum pans, and measured using a robot DSC-RDC220 differential scanning calorimeter manufactured by Seiko Instruments Inc., using a JIS-K- 7122 (2012), the temperature was raised from 25° C. to 300° C. at a rate of 20° C./min, and measurements were made at intervals of 1° C. to obtain a DSC 1st curve.
- Tm (° C.) was defined as the melting peak temperature at which the absolute value of the heat absorption was maximized
- T* (° C.) was defined as the temperature determined by the following measuring method.
- Tmin(°C) the minimum value of A(T) is Amin and the temperature at that time is Tmin(°C)
- Tn (°C) that is the minimum temperature among Tn (°C) that always satisfies A (T) ⁇ 0.2Amin in the temperature range from Tn to Tn + 5°C ) is defined as T*(°C).
- the refractive index of the resin pellet was measured using an Abbe refractometer at 25° C. using a sodium D line (wavelength of 589 nm) as a light source and methylene iodide as a mounting liquid. Measurement of the refractive index of the resin pellets is performed by melting the resin pellets vacuum-dried at 70° C. for 48 hours at 280° C., pressing with a press, and then rapidly cooling to prepare a sheet having a thickness of 200 ⁇ m. was measured.
- layer B is a layer inside the multilayer laminated film, it is not a multilayer laminated film, but a film of layer B resin alone prepared under the same stretching conditions and heat treatment conditions as the multilayer laminated film.
- a prism coupler SPA-400 manufactured by Cylon Technology Co., Ltd. was used to measure the refractive index.
- the wavelength of the laser used for the measurement was 633 nm, and the in-plane refractive index was obtained by averaging the values obtained on both surfaces of the film in the direction of the main orientation axis and the direction perpendicular to the direction of the main orientation axis.
- the normal refractive index the average value of the values measured from the direction of the main orientation axis and the value measured from the side perpendicular to the direction of the main orientation axis was obtained from both surfaces of the film.
- the refractive index of the B layer of the multilayer laminated film was verified as follows. Using the layer thickness of the multilayer laminated film obtained in section (1), the refractive index of layer A of the multilayer laminated film obtained in section (10), and the refractive index of layer B obtained in section (11), the optical A simulation is performed, and the optical simulation result is compared with the reflectance measured in section (3). If the difference between the two is ⁇ 3% or less, the refractive index of layer B obtained in section (11) is the same as that of the multilayer laminated film. was taken to be the refractive index of layer B. The optical simulation was performed using a VBA program using the optical thin film characteristic matrix method (Mitsunobu Kohiyama (2006). Optical thin film filter design, Optronics Co., Ltd.).
- Augmented reality device evaluation A display (SP-133CM) manufactured by Dream Maker was used as the light source, and the projection image display member was installed at an angle of 45° to the light source (light emitted vertically from the light source The angle of incidence is 45° with respect to the normal direction to the surface of ), and the polarizing plate is placed above the light source so that the information emitted toward the projection image display member is a P wave, P-wave information was projected from the light source onto the projection image display member. As shown in FIG. 19, the user of the augmented reality device visually recognizes the image projected within the incident angle range of 20° to 70°. In FIG. 19, the arrow indicating the transparency of the background is omitted.
- thermoplastic resin used for the film The following resins were used for the production of the films used in each example and each comparative example. These are all thermoplastic resins, and resin A, resin B, resin D, resin E, resin F, resin H, resin J, resin K, resin M, resin N, and resin O are crystalline resins, Resin C, resin G, and resin I are amorphous resins.
- Refractive index 1.63
- Tg 98 ° C.
- Resin I is a resin in which the 2,6-naphthalenedicarboxylic acid component and the terephthalic acid component in the acid component are the same, but is treated as a copolymer of polyethylene terephthalate.
- a multi-layer laminate film and a film were produced in the same manner as in each example and each comparative example.
- Table 2 the standard deviations of Rp20, Rp30, Rp40, and Rp50 are the P-wave reflectance at any angle.
- a 201-layer feedblock 101 layers A and 100 layers B
- both ends in the width direction of the obtained uniaxially stretched multilayer laminated film are gripped with clips and guided to a tenter, and the film is laterally stretched at a temperature of 115°C at a stretch ratio of 3.8 times, and then heat-treated at 205°C to reduce the width to 3%.
- Directional relaxation was performed and cooled at 100°C.
- a multilayer laminate film having a thickness of 20 ⁇ m (thickness of both surface layers: 1 ⁇ m) was obtained.
- Examples 2 to 15, Comparative Examples 2 to 7 A multilayer laminated film was obtained in the same manner as in Example 1 except that the resin of each layer, the number of layers, the thickness of the surface layer, the total thickness, the lamination ratio, and the film forming conditions were as shown in Table 1.
- Table 2 shows the evaluation results of the obtained multilayer laminate film.
- the layer structure was an alternate lamination of layers A and B, and the layer A was the outermost layer on both sides.
- the thickness of each layer was controlled by a feed block designed so that the reflected wavelength of the P wave at an incident angle of 50° was in the range of 400 nm to 800 nm.
- the difference between the resin K and the resin M of the thermoplastic resins constituting the B layer is the difference in the copolymerization of polyethylene glycol, and the properties of the obtained multilayer laminate film are the same as in Example 9. and 12, but the resin M of Example 12 has a high glass transition temperature because polyethylene glycol is not copolymerized, and the glass transition temperature difference between the A layer and the B layer is large. , and the quality was poor.
- Comparative Example 7 and Example 15 the difference between the resin N and the resin O of the thermoplastic resins constituting the B layer is the difference in the amount of naphthalenedicarboxylic acid copolymerized, and the multilayer laminated film of Comparative Example 7 is perpendicular to the film surface. Since the difference in refractive index between the layers A and B in the direction (difference in refractive index perpendicular to the plane) is as small as 0.03, Rp60 shows a low value of 1%.
- the difference in the refractive index between the A layer and the B layer in the direction perpendicular to the film surface is as large as 0.14, so the standard deviation of Rp20 to Rp50 is 5% or more, and Comparative Example 3 has Rp60 and Rp70 of 50% or more.
- the difference in in-plane refractive index between the A layer and the B layer is as high as 0.08, so the transmittance of vertically incident light is as low as 33%, and the standard deviation of Rp20 to Rp50 is 5% or more.
- Comparative Example 5 is a uniaxially stretched film stretched only in one direction, and the stretching is different from the multi-layer laminated film of the present invention which is stretched biaxially in the machine direction and the transverse direction. Since the stretching is performed only in one direction, the azimuth angle variation of Rp60 exceeds 5%, which is 51%, which is very high. In addition, the transmittance of vertically incident light is as low as 44%, Rp20 to Rp70 are all 100%, and does not have the P-wave reflection characteristics of the multilayer laminate film of the present invention shown in FIG.
- the heat treatment temperature differs between Comparative Example 6 and Example 15, and the heat treatment is performed at a temperature higher than the melting point of the B layer in Comparative Example 6. Therefore, the number of ⁇ Hm peaks is one, and the difference in in-plane refractive index between the A layer and the B layer is as high as 0.07, so the transmittance of vertically incident light is as low as 46%.
- the Tm-T* was as low as 23, and the B layer was crystallized after heating at 150°C for 2 hours, and the crystal size was large, so the internal haze was as high as 1.4%.
- a resin B was used as a thermoplastic resin constituting the layer A. After melting at 280 ° C. with an extruder and passing through 5 FSS type leaf disk filters, it was supplied to a T die and formed into a sheet, and then while applying an electrostatic voltage of 8 kV with a wire, the surface temperature It was rapidly solidified on a casting drum kept at 25°C to obtain an unstretched film. This unstretched film was longitudinally stretched at a temperature of 95°C at a stretching ratio of 3.4 times, and both sides of the film were subjected to corona discharge treatment in the air.
- a coating liquid for forming an easy-adhesion layer consisting of (polyester resin)/(polyester resin having a glass transition temperature of 82° C.)/silica particles having an average particle size of 100 nm was applied. After that, both ends of the uniaxially stretched multilayer laminated film in the width direction are held with clips and guided to a tenter, and the film is laterally stretched at a temperature of 115°C and a stretch ratio of 3.7 times, and then subjected to a heat treatment at 230°C and a relaxation of 3% in the width direction. It was carried out and cooled at 100°C. A film having a thickness of 50 ⁇ m was thus obtained. Table 2 shows the evaluation results of the obtained film.
- the difference between the two was ⁇ 3% or less, so the refractive index of layer B obtained in section (11) was Taken as the refractive index of layer B of the film.
- a projection image display member was produced by laminating the films shown in Table 3 to a transparent acrylic plate having a thickness of 2 mm and a size of 350 mm ⁇ 290 mm with an acrylic adhesive having a thickness of 15 ⁇ m.
- Augmented reality device evaluation was carried out using the produced projection image display member.
- the projection image display member was installed so that the film surface was on the viewing side.
- Table 3 shows the evaluation results of the augmented reality device and the physical properties of the projection image display member.
- the present invention is a multi-layer laminated film that can reduce the difference in brightness of images due to differences in projection angles.
- the multilayer laminate film of the present invention can be suitably used for projection image display members, augmented reality devices, and the like.
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Abstract
Description
本発明の多層積層フィルムは、2種の熱可塑性樹脂層が交互に積層された構成を有し、第一の熱可塑性樹脂からなる層を層Aとし、第二の熱可塑性樹脂からなる層を層Bとしたときに、層Aが結晶性の熱可塑性樹脂を含み、層Bが非晶性の熱可塑性樹脂を主成分とすることが好ましい。より好ましくは、層Aが結晶性の熱可塑性樹脂を主成分とし、層Bが非晶性の熱可塑性樹脂を主成分とすることである。さらに好ましくは、層Aが結晶性の熱可塑性樹脂からなり、層Bが非晶性の熱可塑性樹脂を主成分とすることである。ここで主成分とは、層を構成する全成分を100質量%としたときに、60質量%以上100質量%以下含まれる成分をいう。また、反射率が高くなり積層数が少なく済むことから、層Aと層Bの面直屈折率差は、Rp20、Rp30、Rp40、Rp50の標準偏差が5%より大きくならない範囲で高い方が好ましい。また、層厚み分布は隣接する層Aと層Bの光学厚みが下記(A)式を満たすことが好ましい。
P波及びS波は以下のように定義することができる。電磁波(光)が物体の表側の面に対し斜め方向から入射した際において、P波とは電界成分が入射面に平行な電磁波(入射面に平行に振動する直線偏光)、S波とは電界成分が入射面に垂直な電磁波(入射面に垂直に振動する直線偏光)を表す。このP波とS波の反射特性について、図面を参照しながら説明する。
本発明の多層積層フィルムは、第一の熱可塑性樹脂からなる層(層A)と第二の熱可塑性樹脂からなる層(層B)が交互に積層された構成を有し、前記第一の熱可塑性樹脂が結晶性ポリエステルを主成分とし、前記第二の熱可塑性樹脂がナフタレンジカルボン酸に由来する構造を含むポリエステルを主成分とすることが好ましい。ナフタレンジカルボン酸に由来する構造を含むポリエステルは、その全部または一部が非晶性ポリエステルとなり得る。ここで、「第一の熱可塑性樹脂」とは層Aを構成する樹脂成分全体をいい、「第二の熱可塑性樹脂」とは層Bを構成する樹脂成分全体をいう。「層Aが結晶性ポリエステルを主成分とする」とは、第一の熱可塑性樹脂中に60質量%以上100質量%以下の結晶性ポリエステルが含まれることをいう。「層Bがナフタレンジカルボン酸に由来する構造を含むポリエステルを主成分とする」とは、第二の熱可塑性樹脂中に60質量%以上100質量%以下のナフタレンジカルボン酸に由来する構造を含むポリエステルが含まれることをいう。
(1)DSC1st曲線の温度微分曲線をA(T)=dDSC/dT(mW/℃)とし、温度微分曲線A(T)のグラフにおいて、150(℃)からTm(℃)までの温度範囲におけるA(T)の最小値をAmin、そのときの温度をTmin(℃)としたときに、Tmin(℃)以下の範囲における温度微分曲線A(T)と直線A’(T)=0.2Aminの複数の交点を、温度の低い順に、Tn(℃)(n=1,2,3・・・)とする。
(2)(1)を満たすTn(℃)のうち、TnからTn+5℃の温度範囲で、常にA(T)<0.2Aminを満たすTn(℃)のうち、最小の温度となるTn(℃)をT*(℃)とする。
以下、本発明の多層積層フィルムの作製について、一例を挙げて具体的に説明するが、本発明の多層積層フィルムはこれに限定されない。
以下、本発明の投影画像表示部材の態様の具体例を説明する。図12には、本発明の投影画像表示部材の態様の一例として本発明の多層積層フィルム3を含む構成を示す。図12は本発明の多層積層フィルムに任意の反射防止層12と機能層13を積層した構成である。反射防止層12は投影画像表示部材の表面の反射を防止する層であり、多層積層フィルム13の少なくとも一方の表面に位置することが好ましい。図12のAに示すように、多層積層フィルム3の少なくとも一方の表面に反射防止層12を有することで、投影画像表示部材の表面におけるS波の斜め反射を抑制することができる。その結果、本発明の投影画像表示部材を拡張現実装置の投影部材として用いた場合において、映像以外の周囲の景色の映り込みを抑制することができる。
特性値の評価方法ならびに効果の評価方法は次の通りである。
ミクロトームを用いて断面を切り出したサンプルについて、透過型電子顕微鏡(TEM)を用いて観察することにより、多層積層フィルムの積層数と表層の厚みを確認した。なお断面写真の撮影は、透過型電子顕微鏡H-7100FA型((株)日立製作所製)を用い、加速電圧75kVの条件で行った。なお、表層の厚みは顕微鏡の測長機能により測定した。
日立製作所(株)製 分光光度計(U-4100 Spectrophotomater)の標準構成(固体測定システム)にて、入射角度θ=0°における波長400~700nmの透過率を1nm刻みで測定し、その平均透過率を求め、得られた値を多層積層フィルムまたは投影画像表示部材の可視光の透過率とした。測定条件:スリットは2nm(可視)/自動制御(赤外)とし、ゲインは2と設定し、走査速度を600nm/分とした。
日立製作所(株)製 分光光度計(U-4100 Spectrophotomater)に付属の角度可変反射ユニットとグランテーラ偏光子を取り付け、入射角度θ=20°、30°、40°、50°、60°、70°における波長400~700nmの範囲のP波の反射率をそれぞれ1nm刻みで測定した。得られた反射率から入射角度20°、30°、40°、50°、60°、70°における波長400nm~700nmの範囲におけるP波の平均反射率としてRp20、Rp30、Rp40、Rp50、Rp60、Rp70を求めた。また、Rp20、Rp30、Rp40、Rp50の標準偏差を算出した。各入射角度の傾斜方向は多層積層フィルムについてはフィルムの主配向軸に沿う方向とし、投影画像表示部材については短辺方向に沿う方向とした。60°で入射したP波の反射光の彩度は、JIS-Z-8781-4(2013)に基づき、CIE1976色空間L*a*b*のうちa*、b*についてθ=60°のP波の反射率スペクトルとC光源の分光分布とXYZ系の等色関数を用いてC光源下でのXYZ値、およびXYZ値を用いて算出し、彩度C*値としてa*とb*の二乗和の平方根をもって算出した。
日立製作所(株)製 分光光度計(U-4100 Spectrophotomater)に付属の角度可変反射ユニットとグランテーラ偏光子を取り付け、多層積層フィルムについてはフィルム面の主配向軸方向の方位角0°を基準にし、投影画像表示部材については短辺方向を基準に右回りに0°、45°、90°、135°、180°の5点それぞれの方位角方向に対して、入射角度θ=60°における波長400~700nmの範囲のP波の反射率を1nm刻みで測定した。得られた反射率から各方位角方向における入射角度60°における波長400nm~700nmの範囲のP波の平均反射率として、Rp60(0°)、Rp60(45°)、Rp60(90°)、Rp60(135°)、Rp60(180°)を求めた。さらに、求めたRp60(0°)、Rp60(45°)、Rp60(90°)、Rp60(135°)、Rp60(180°)の最大値と最小値の差を方位角ばらつきとした。
サンプルサイズを10cm×10cmとし、フィルム幅方向中央において、サンプルを切り出した。王子計測機器(株)製の分子配向計MOA-7015を用いて配向度を測定し、最も配向度の大きい方向を主配向軸方向とした。主配向軸方向は、最表面の面内方位角0°の方向となる。
多層積層フィルムを電子天秤で5mg計量し、アルミニウムパンで挟み込みセイコーインスツルメント社(株)製ロボットDSC-RDC220示差走査熱量計を用いて、JIS-K-7122(2012年)に従い、25℃から300℃まで20℃/分で昇温して測定を行った。データ解析は同社製ディスクセッションSSC/5200を用いた。得られたDSCデータから融解エンタルピー(ΔHm)が3J/g以上を示すピークの個数と、融解エンタルピーを示すピークよりも低温側に3J/g未満のピークの存在の有無について解析した。
多層積層フィルム又は樹脂ペレットを電子天秤で5mg計量し、アルミニウムパンで挟み込みセイコーインスツルメント社(株)製ロボットDSC-RDC220示差走査熱量計を用いて、JIS-K-7122(2012年)に従い、25℃から300℃まで20℃/分で昇温して測定を行った。データ解析は同社製ディスクセッションSSC/5200を用いた。得られたDSCデータからガラス転移点温度(Tg)、融点(Tm)、融解エンタルピー(ΔHm)が3J/g以上を示すピーク個数、融解エンタルピーを示すピークよりも低温側にある3J/g未満のピーク個数を求めた。
多層積層フィルムを電子天秤で5mg計量し、アルミニウムパンで挟み込みセイコーインスツルメント社(株)製ロボットDSC-RDC220示差走査熱量計を用いて、JIS-K-7122(2012年)に従い、25℃から300℃まで20℃/分で昇温、1℃間隔で測定を行い、DSC1st曲線を得た。吸収熱量の絶対値が最大となる融解ピーク温度をTm(℃)とし、下記の測定方法で決定した温度をT*(℃)とし、Tm-T*を求めた。
以下の(1)、(2)により決定する。
(1)DSC1st曲線の温度微分曲線をA(T)=dDSC/dT(mW/℃)とし、温度微分曲線A(T)のグラフにおいて、150(℃)からTm(℃)までの温度範囲におけるA(T)の最小値をAmin、そのときの温度をTmin(℃)としたときに、Tmin(℃)以下の範囲における温度微分曲線A(T)と直線A’(T)=0.2Aminの複数の交点を、温度の低い順に、Tn(℃)(n=1,2,3・・・)とする。
(2)(1)を満たすTn(℃)のうち、TnからTn+5℃の温度範囲で、常にA(T)<0.2Aminを満たすTn(℃)のうち、最小の温度となるTn(℃)をT*(℃)とする。
ナトリウムD線(波長589nm)を光源とし、マウント液としてヨウ化メチレンを用い、25℃にてアッベ屈折計を用いて樹脂ペレットの屈折率を測定した。樹脂ペレットの屈折率の測定は、70℃48時間、真空乾燥した樹脂ペレットを280℃で溶融後、プレス機を用いてプレスし、その後急冷することで、厚み200μmのシートを作製し、そのシートの屈折率を測定した。
サイロンテクノロジー社製プリズムカプラSPA-400を用いて多層積層フィルム最表層の屈折率測定を行った。測定に用いたレーザーの波長は633nmであり、面内屈折率は主配向軸方向、主配向軸方向に垂直な方向それぞれの方向において両方の最表層で求めた値の平均値を求め、面直屈折率は主配向軸方向側から測定した値と主配向軸方向に垂直な方向側から測定した値の平均値それぞれにおいて、両方の最表層で求めた値の平均値を求めた。
B層は多層積層フィルム内部の層であるため多層積層フィルムではなく、多層積層フィルムと同じ延伸条件・熱処理条件で作製したB層樹脂単体のフィルムについて、サイロンテクノロジー社製プリズムカプラSPA-400を用いて屈折率測定を行った。測定に用いたレーザーの波長は633nmであり、面内屈折率は主配向軸方向、主配向軸方向に垂直な方向それぞれの方向においてフィルムの両方の面で求めた値の平均値を求め、面直屈折率は主配向軸方向側から測定した値と主配向軸方向に垂直な方向側から測定した値の平均値それぞれにおいて、フィルムの両方の面で求めた値の平均値を求めた。
フィルムをHFIP-d2(ヘキサフロロー2-プロパノール・2重水素化物)に溶解させ、1H-NMRを測定した。得られたスペクトルについて、ケミカルシフト3.8ppmのピークをもつシグナルの面積をS1、ケミカルシフト3.9ppmにピークをもちシグナルの面積をS2とした際に、S1/S2×44(44:エチレングリコールの繰り返し単位の式量)をもってアルキレングリコールの分子量とした。
溶媒としてオルトクロロフェノールを用いて、温度100℃で20分溶解した後、温度25℃でオストワルド粘度計を用いて測定した溶液粘度から算出した。
液体測定用石英セルに入れて流動パラフィンを充填した石英セル中に多層積層フィルムを入れて、(株)村上色彩技術研究所製 ヘイズメーター(HM-150N)を用いて測定(JIS K 7136:2000)を行うことで、フィルム表面ヘイズを除いた内部ヘイズを測定した。評価は多層積層フィルムの150℃2時間加熱前後の内部ヘイズを測定した。
光源にドリームメーカー社製ディスプレイ(SP-133CM)を用い、光源に対して投影画像表示部材を45°の角度で設置(光源から垂直に出た光は投影画像表示部材の面に対して法線方向に対して入射角度45°の角度を取る。)し、投影画像表示部材に向かって照射させる情報がP波となるように偏光板を光源の上に設置し、光源から投影画像表示部材に対してP波の情報を投影した。図19に示す通り拡張現実装置利用者は入射角20°から70°の範囲で投影された映像を視認する。なお、図19では背景の透過を示す矢印は省略している。この目視評価により、背景の視認性、入射角20°~50°の投影像の輝度差、入射角度60°、70°の投影像の視認性、入射角度20°~70°の投影像の輝度抜けについて以下の評価基準で評価した。
A:背景が鮮明に見える
B:背景が見える
C:背景が暗く見える
(入射角20°~50°の投影像の輝度差)
A:輝度の差を認識できない
B:輝度の差を認識できる。
(入射角度60°、70°の投影像の視認性)
A:投影映像が鮮明に見える。
B:投影映像が見える
C:投影映像が暗く見える。
(入射角度20°~70°の投影像の輝度抜け)
A:輝度の抜けが無い
B:輝度の抜けがある(映像を視認しがたい角度が存在する)
背景の視認性の評価基準において、Aが優れるが、AとBが良好で合格レベルである。入射角度60°、70°の投影像の視認性の評価基準において、Aが優れるが、AとBが良好で合格レベルである。
各実施例及び各比較例に用いたフィルムの製造には以下の樹脂を用いた。なお、これらは全て熱可塑性樹脂であり、樹脂A、樹脂B、樹脂D、樹脂E、樹脂F、樹脂H、樹脂J、樹脂K、樹脂M、樹脂N、樹脂Oが結晶性樹脂であり、樹脂C、樹脂G、樹脂Iが非晶性樹脂である。
樹脂B:IV=0.65のポリエチレンテレフタレート、屈折率=1.58、Tg=78℃、Tm=254℃。
樹脂C:IV=0.64のポリエチレンナフタレートの共重合体(パラキシレングリコール成分をジオール成分全体に対して35mol%、分子量400のポリエチレングリコールをジオール成分全体に対して8mol%共重合したポリエチレンナフタレート)、屈折率1.64、Tg=87℃、Tmは観測されなかった。
樹脂D:IV=0.64のポリエチレンナフタレートの共重合体(イソフタル酸成分を酸成分全体に対して15mol%、分子量400のポリエチレングリコールをジオール成分全体に対して5mol%共重合したポリエチレンナフタレート)屈折率=1.63、Tg=88℃、Tm=226℃。
樹脂E:IV=0.64のポリエチレンナフタレートの共重合体(イソフタル酸成分を酸成分全体に対して15mol%、分子量400のポリエチレングリコールをジオール成分全体に対して3mol%共重合したポリエチレンナフタレート)屈折率=1.63、Tg=92℃、Tm=228℃。
樹脂F:IV=0.64のポリエチレンナフタレートの共重合体(イソフタル酸成分を酸成分全体に対して20mol%、分子量200のポリエチレングリコールをジオール成分全体に対して8mol%共重合したポリエチレンナフタレート)屈折率=1.63、Tg=98℃、樹脂ペレットではTm、ΔHmは観測されなかったが、100℃で長手方向と幅方向にそれぞれ3.3倍延伸を行ったB層樹脂単体のフィルムはTm=215℃であった。
樹脂G:IV=0.73のポリエチレンテレフタレートの共重合体(シクロヘキサンジメタノール成分をジオール成分全体に対して33mol%共重合したポリエチレンテレフタレート)、屈折率=1.57、Tg=80℃、Tmは観測されなかった。
樹脂H:IV=0.64のポリエチレンナフタレート、屈折率=1.65、Tg=120℃、Tm=265℃。
樹脂I:IV=0.67のポリエチレンテレフタレートの共重合体(2,6-ナフタレンジカルボン酸成分を酸成分全体に対して50mol%共重合したポリエチレンテレフタレート)、屈折率=1.62、Tg=105℃、Tmは観測されなかった。なお、樹脂Iは酸成分中における2,6-ナフタレンジカルボン酸成分とテレフタル酸成分が等しい樹脂であるが、ポリエチレンテレフタレートの共重合体として扱う。
樹脂J:IV=0.67のポリエチレンテレフタレートの共重合体(イソフタル酸成分を酸成分全体に対して15mol%共重合したポリエチレンテレフタレート)、屈折率=1.57、Tg=75℃、Tm=220℃。
樹脂K:IV=0.64のポリエチレンナフタレートの共重合体(イソフタル酸成分を酸成分全体に対して30mol%、分子量400のポリエチレングリコールをジオール成分全体に対して6mol%共重合したポリエチレンナフタレート)屈折率=1.63、Tg=73℃、Tm、ΔHmは観測されなかった。
樹脂M:IV=0.64のポリエチレンナフタレートの共重合体(イソフタル酸成分を酸成分全体に対して30mol%共重合したポリエチレンナフタレート)屈折率=1.63、Tg=102℃、Tm、ΔHmは観測されなかった。
樹脂N:IV=0.64のポリエチレンテレフタレートの共重合体(2,6-ナフタレンジカルボン酸成分を酸成分全体に対して10mol%共重合したポリエチレンテレフタレート)屈折率=1.58、Tg=83℃、Tm233℃。
樹脂O:IV=0.64のポリエチレンテレフタレートの共重合体(2,6-ナフタレンジカルボン酸成分を酸成分全体に対して20mol%共重合したポリエチレンテレフタレート)屈折率=1.58、Tg=90℃、樹脂ペレットではTm、ΔHmは観測されなかったが、100℃で長手方向と幅方向にそれぞれ3.3倍延伸を行ったB層樹脂単体のフィルムはTm=220℃であった。
層Aを構成する熱可塑性樹脂として樹脂Aを、層Bを構成する熱可塑性樹脂として樹脂Cを用いた。樹脂Aおよび樹脂Cを、それぞれ、押出機にて280℃で溶融させ、FSSタイプのリーフディスクフィルタを5枚介した後、ギアポンプにて吐出比(積層比)が樹脂A/樹脂C=1.2になるように計量しながら、入射角50°でのP波の反射波長が400nm~800nmの範囲になるように設計した201層フィードブロック(層Aが101層、層Bが100層)にて、両表層が樹脂Aとなるように交互に合流させた。次いで、Tダイに供給し、シート状に成形した後、ワイヤーで8kVの静電印可電圧をかけながら、表面温度25℃に保たれたキャスティングドラム上で急冷固化し、未延伸多層積層フィルムを得た。この未延伸多層積層フィルムを、温度95℃、延伸倍率3.5倍で縦延伸し、その両面に空気中でコロナ放電処理を施した後、その両面に(ガラス転移温度が18℃のポリエステル樹脂)/(ガラス転移温度が82℃のポリエステル樹脂)/平均粒径100nmのシリカ粒子からなる易接着層形成膜塗液を塗布した。その後、得られた一軸延伸多層積層フィルムの幅方向両端部をクリップで把持してテンターに導き、温度115℃、延伸倍率3.8倍で横延伸した後、205℃で熱処理及び3%の幅方向リラックスを実施し、100℃で冷却した。こうして厚み20μm(両表層の厚み1μm)の多層積層フィルムを得た。
各層の樹脂、層数、表層の厚み、全体厚み、積層比、製膜条件を表1のとおりとした以外は実施例1と同様にして多層積層フィルムを得た。得られた多層積層フィルムの評価結果を表2に示す。なお、層構成はいずれも層Aと層Bの交互積層であり、かつ両側の最表層が層Aである態様とした。また、各層の厚みは入射角50°でのP波の反射波長が400nm~800nmの範囲になるように設計したフィードブロックで制御した。
層Aを構成する熱可塑性樹脂として樹脂Bを用いた。押出機にて280℃で溶融させ、FSSタイプのリーフディスクフィルタを5枚介した後、Tダイに供給し、シート状に成形した後、ワイヤーで8kVの静電印可電圧をかけながら、表面温度25℃に保たれたキャスティングドラム上で急冷固化し、未延伸フィルムを得た。この未延伸フィルムを、温度95℃、延伸倍率3.4倍で縦延伸を行い、フィルムの両面に空気中でコロナ放電処理を施し、そのフィルム両面の処理面に(ガラス転移温度が18℃のポリエステル樹脂)/(ガラス転移温度が82℃のポリエステル樹脂)/平均粒径100nmのシリカ粒子からなる易接着層形成膜塗液を塗布した。その後、一軸延伸多層積層フィルムの幅方向両端部をクリップで把持してテンターに導き、温度115℃、延伸倍率3.7倍で横延伸した後、230℃で熱処理及び3%の幅方向リラックスを実施し、100℃で冷却した。こうして厚み50μmのフィルムを得た。得られたフィルムの評価結果を表2に示す。(12)項の多層積層フィルムのB層の屈折率の検証を行った結果、両者の差は何れも±3%以下であったため、(11)項で求めた層Bの屈折率は多層積層フィルムの層Bの屈折率と見なした。
表3に示すフィルムを厚さ2mm、350mm×290mmサイズの透明アクリル板に厚み15μmのアクリル系接着剤で貼り合わせて投影画像表示部材を作製した。作製した投影画像表示部材を用いて拡張現実装置評価を実施した。この時フィルム面が視認側となるように投影画像表示部材を設置した。拡張現実装置評価結果と投影画像表示部材の物性を表3に示す。
2 S波の反射率
3 多層積層フィルム
4 Tm-T*>27を満たす多層積層フィルムのDSC1st曲線
5 Tm-T*≦27を満たす多層積層フィルムのDSC1st曲線
6 4の温度微分曲線、A(T)=dDSC/dT(mW/℃)
7 5の温度微分曲線、A(T)=dDSC/dT(mW/℃)
8 A(T)の最大値が0.040以下である多層積層フィルムのDSC1st曲線
9 A(T)の最大値が0.040を上回る多層積層フィルムのDSC1st曲線
10 8の温度微分曲線、A(T)=dDSC/dT(mW/℃)
11 9の温度微分曲線、A(T)=dDSC/dT(mW/℃)
12 反射防止層
13 機能層
14 透明支持体
15 接着層
16 映像投影装置
17 投影映像
18 導光部材
19 反射部材
20 投影画像表示部材
21 背景
22 拡張現実装置利用者の目
23 ガラスや透明樹脂フィルムを用いた従来の投影画像表示部材
24 映像のもととなる光の入射角度
25 入射角20°の投影映像
26 入射角45°の投影映像
27 入射角70°の投影映像
Claims (17)
- 異なる複数の熱可塑性樹脂層が交互に51層以上積層した多層積層フィルムであって、
前記多層積層フィルム面に垂直に入射する可視光の透過率が50%以上100%以下であり、前記多層積層フィルム面に、その法線とのなす角が20°、30°、40°、50°、60°、70°となるように可視光を入射させたときのP波の平均反射率を順にRp20(%)、Rp30(%)、Rp40(%)、Rp50(%)、Rp60(%)、Rp70(%)としたときに、Rp20、Rp30、Rp40及びRp50の標準偏差が5%以下であり、Rp60及びRp70が3%以上50%以下である、多層積層フィルム。
ここで、Rp20(%)、Rp30(%)、Rp40(%)、Rp50(%)、Rp60(%)、Rp70(%)は、分光光度計を用いて、入射角度θ=20°、30°、40°、50°、60°、70°のそれぞれの入射角度における波長400nmから700nmまでの範囲のP波の反射率を1nm刻みで測定したときの平均値である。 - 前記Rp20、前記Rp30、前記Rp40、前記Rp50、前記Rp60、前記Rp70の最小値が3%以上50%以下である、請求項1に記載の多層積層フィルム。
- 前記Rp20、前記Rp30、前記Rp40、前記Rp50、前記Rp60、前記Rp70のうち、Rp30、Rp40またはRp50の少なくとも1つが最小値をとる、請求項1又は2に記載の多層積層フィルム。
- 前記多層積層フィルムを示差走査熱量測定(DSC)で測定するとき、25℃から300℃まで20℃/分で昇温して得たDSC1st曲線において、吸収熱量の絶対値が最大となる融解ピーク温度をTm(℃)とし、下記の測定方法で決定した温度をT*(℃)とするとき、Tm-T*>27(℃)を満たす、請求項1~3の何れかに記載の多層積層フィルム。
<T*の測定方法>
以下の(1)、(2)により決定する。
(1)DSC1st曲線の温度微分曲線をA(T)=dDSC/dT(mW/℃)とし、温度微分曲線A(T)のグラフにおいて、150(℃)からTm(℃)までの温度範囲におけるA(T)の最小値をAmin、そのときの温度をTmin(℃)としたときに、Tmin(℃)以下の範囲における温度微分曲線A(T)と直線A’(T)=0.2Aminとの複数の交点を、温度の低い順に、Tn(℃)(n=1,2,3・・・)とする。
(2)(1)を満たすTn(℃)のうち、TnからTn+5℃の温度範囲で、常にA(T)<0.2Aminを満たすTn(℃)のうち、最小の温度となるTn(℃)をT*(℃)とする。 - 前記温度微分曲線A(T)において、150(℃)からTm(℃)の範囲内での最大値が0.040以下である、請求項4に記載の多層積層フィルム。
- 前記多層積層フィルム面に、その法線とのなす角が60°となるようにP波を入射させたときの反射光の彩度が20以下である、請求項1~5の何れかに記載の多層積層フィルム。
- 前記多層積層フィルム面に、その法線とのなす角が60°となるようにP波を入射させたときの反射率Rp60の面内方位角ばらつきが5%以下である、請求項1~6の何れかに記載の多層積層フィルム。
- 前記多層積層フィルムが、第一の熱可塑性樹脂からなる層(層A)と第二の熱可塑性樹脂からなる層(層B)が交互に積層された構成を有し、前記第一の熱可塑性樹脂が結晶性ポリエステルを主成分とし、前記第二の熱可塑性樹脂がナフタレンジカルボン酸に由来する構造を含むポリエステルを主成分とする、請求項1~7の何れかに記載の多層積層フィルム。
- 前記第二の熱可塑性樹脂が、数平均分子量200以上2000以下のアルキレングリコールに由来する構造を含む、請求項8に記載の多層積層フィルム。
- 前記多層積層フィルムが融点を有し、示差走査熱量測定(DSC)による融解エンタルピー(ΔHm)が3J/g以上を示す溶融ピークが2つ以上存在し、前記融解エンタルピーが3J/g以上を示す前記溶解ピークよりも低温側にさらに3J/g未満の溶解ピークが存在する、請求項1~9の何れかに記載の多層積層フィルム。
- 請求項1~10の何れかに記載の多層積層フィルムが、透明部材の少なくとも一方の面に積層されてなる投影画像表示部材。
- 請求項1~10の何れかに記載の多層積層フィルムが、少なくとも2つの透明部材間に積層されてなる投影画像表示部材。
- 投影画像表示部材の表面に垂直に入射する可視光の透過率が50%以上100%以下であり、前記投影画像表示部材面の表面に、その法線とのなす角が20°、30°、40°、50°、60°、70°となるように可視光を入射させたときのP波の反射率を順にRp20(%)、Rp30(%)、Rp40(%)、Rp50(%)、Rp60(%)、Rp70(%)としたときに、Rp20、Rp30、Rp40及びRp50の標準偏差が5%以下であり、前記Rp60及び前記Rp70が3%以上50%以下であり、前記Rp20~前記Rp70の最小値が3%以上であり、かつ、前記投影画像表示部材面にその法線とのなす角が60°となるようにP波を入射させたときの反射光の彩度が20以下である、投影画像表示部材。
ここで、Rp20(%)、Rp30(%)、Rp40(%)、Rp50(%)、Rp60(%)、Rp70(%)は、分光光度計を用いて、入射角度θ=20°、30°、40°、50°、60°、70°のそれぞれの入射角度における波長400nmから700nmまでの範囲のP波の反射率を1nm刻みで測定したときの平均値である。 - 前記Rp20、前記Rp30、前記Rp40、前記Rp50、前記Rp60、前記Rp70のうち、Rp30、Rp40またはRp50の少なくとも1つが最小値をとる、請求項13に記載の投影画像表示部材。
- 前記投影画像表示部材面に、その法線とのなす角が60°となるようにP波を入射させたときの反射率の方位角ばらつきが5%以下である、請求項13または14に記載の投影画像表示部材。
- 請求項1~10の何れかに記載の多層積層フィルム、または、請求項11~15の何れかに記載の投影画像表示部材を具備する、拡張現実装置。
- 利用者の頭部に装着して使用される、請求項16に記載の拡張現実装置。
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| US20240375375A1 (en) | 2024-11-14 |
| KR20240087694A (ko) | 2024-06-19 |
| EP4411436A4 (en) | 2025-10-08 |
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