WO2017208559A1 - Demi miroir et miroir ayant une fonction d'affichage d'image - Google Patents

Demi miroir et miroir ayant une fonction d'affichage d'image Download PDF

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Publication number
WO2017208559A1
WO2017208559A1 PCT/JP2017/009980 JP2017009980W WO2017208559A1 WO 2017208559 A1 WO2017208559 A1 WO 2017208559A1 JP 2017009980 W JP2017009980 W JP 2017009980W WO 2017208559 A1 WO2017208559 A1 WO 2017208559A1
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Prior art keywords
layer
liquid crystal
half mirror
circularly polarized
image display
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PCT/JP2017/009980
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English (en)
Japanese (ja)
Inventor
昭裕 安西
寛 稲田
渉 馬島
田口　貴雄
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富士フイルム株式会社
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Priority claimed from JP2016122604A external-priority patent/JP6632479B2/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2017208559A1 publication Critical patent/WO2017208559A1/fr
Priority to US16/172,192 priority Critical patent/US20190072819A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a half mirror and a mirror with an image display function.
  • a half mirror is provided on the surface of the image display unit of the image display device, and an image display function is provided to display an image in the display mode and to display a mirror reflection image as a mirror in the non-display mode such as when the image display device is turned off.
  • the mirror is described in, for example, Patent Document 1 and Patent Document 2.
  • Patent Literature 1 a liquid crystal display device is provided inside a housing for a vehicle mirror, and an image is displayed via a half mirror provided on the front surface of the vehicle mirror, thereby realizing an image display on the mirror. It is disclosed.
  • Patent Document 2 there is a disclosure relating to a mirror with an information display function applied to a mirror for interior, makeup, crime prevention, and safety.
  • Patent Document 1 does not pay attention to such a problem.
  • Patent Document 2 a reflective polarizing plate is used as a half mirror, the linearly polarized light emitted from the image display device and the transmission axis of the reflective polarizing plate are combined, light loss is eliminated, and image quality is further improved. There is description about.
  • the present inventors have examined using a cholesteric liquid crystal layer for a half mirror. This is because a display image and a mirror reflection image can be observed without direction dependency even through polarized sunglasses by using a circularly polarized reflective cholesteric liquid crystal layer. Furthermore, it has been found that a quarter wave plate can be provided between the cholesteric liquid crystal layer and the linearly polarized light emitted from the image display device can be used without loss.
  • the half mirror having such a configuration has faced a new problem that a color change occurs in a mirror reflection image under a high temperature environment.
  • a half mirror is used for a vehicle, use at a high temperature is assumed, and thus the above-described color change can be a serious problem.
  • the inventors have further studied to solve this problem, and have completed the present invention.
  • a circularly polarized light reflecting layer including a cholesteric liquid crystal layer, a barrier layer, an adhesive layer, and a front plate
  • the barrier layer is a half mirror provided between the adhesive layer and the circularly polarized light reflecting layer.
  • the cholesteric liquid crystal layer is a layer obtained by curing a liquid crystal composition containing a polymerizable liquid crystal compound and a polymerization initiator.
  • the barrier layer is a layer obtained by curing a composition containing a monomer containing a polymerizable group.
  • the half mirror according to the polymerizable groups Y 1 and the polymerizable groups Y 1 of the above monomers satisfy the polymerizable group content
  • X 1 Togashiki 1 is a value obtained by dividing the molecular weight of the monomer [7] .
  • the monomer is a urethane (meth) acrylate monomer, and the polymerizable group number Y 2 of the urethane (meth) acrylate monomer and the glass transition temperature X 2 of the composition satisfy Formula 2.
  • [7] to [10 ] Is a half mirror. Y 2 > ⁇ 0.0066 X 2 +5.33 Equation 2
  • the half mirror includes a quarter-wave plate, The half mirror according to any one of [1] to [13], including the quarter-wave plate, the circularly polarized light reflection layer, and the front plate in this order.
  • a mirror with an image display function comprising the half mirror according to any one of [1] to [15] and an image display device, the image display device, the circularly polarizing reflection layer, and the front plate in this order.
  • a novel half mirror and a mirror with an image display function using the same are provided.
  • a bright display image and mirror reflection image can be observed without direction dependency even through polarized sunglasses.
  • FIGS. 1a) to 1g) are diagrams schematically showing an example of the layer configuration of a half mirror.
  • FIG. 2 (a) is a graph of TOF-SIMS measurement results showing the material distribution in the film thickness direction of the laminate before and after the laminate including the circularly polarized light reflection layer and the adhesive layer was left at high temperature. The initiator distribution is shown.
  • FIG. 2 (b) is a graph of TOF-SIMS measurement results showing the material distribution in the film thickness direction of the laminate before and after the laminate including the circularly polarized light reflection layer and the adhesive layer was left at high temperature. The distribution of decomposition products of the initiator is shown.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • an angle such as “45 °”, “parallel”, “vertical” or “orthogonal” is within a range where the difference from the exact angle is less than 5 ° unless otherwise specified. Means. The difference from the exact angle is preferably less than 4 °, more preferably less than 3 °.
  • (meth) acrylate is used to mean “one or both of acrylate and methacrylate”.
  • “selective” for circularly polarized light means that either the right circularly polarized light component or the left circularly polarized light component has more light than the other circularly polarized light component.
  • the degree of circular polarization of light is preferably 0.3 or more, more preferably 0.6 or more, and even more preferably 0.8 or more. More preferably, it is substantially 1.0.
  • sense for circularly polarized light means right circularly polarized light or left circularly polarized light.
  • the sense of circularly polarized light is right-handed circularly polarized light when the electric field vector tip turns clockwise as time increases when viewed as the light travels toward you, and left when it turns counterclockwise. Defined as being circularly polarized.
  • the term “sense” is sometimes used for the twist direction of the spiral of the cholesteric liquid crystal.
  • the twist direction (sense) of the spiral of the cholesteric liquid crystal is right, the right circularly polarized light is reflected and the left circularly polarized light is transmitted.
  • the cholesteric liquid crystal spiral sense is on the left, it reflects left circularly polarized light and transmits right circularly polarized light.
  • Visible light is light having a wavelength visible to the human eye among electromagnetic waves, and indicates light having a wavelength range of 380 nm to 780 nm.
  • Infrared rays are electromagnetic waves in the wavelength range that are longer than visible rays and shorter than radio waves.
  • near infrared light is an electromagnetic wave having a wavelength range of 780 nm to 2500 nm.
  • the surface of the half mirror on the front plate side with respect to the circularly polarized reflective layer and the surface of the mirror with an image display function on the front plate side with respect to the circularly polarized reflective layer may be referred to as the front surface, respectively.
  • image for a mirror with an image display function means an image that can be viewed and observed when the image is displayed on the image display unit of the image display device.
  • mirror reflection image for a mirror with an image display function means an image that can be viewed and observed when the image is not displayed on the image display unit of the image display device.
  • the front phase difference is a value measured using an AxoScan manufactured by Axometrics.
  • the front phase difference is a value measured by making light in a wavelength range of visible light such as the central wavelength of selective reflection of the cholesteric liquid crystal layer incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). You can also When selecting the measurement wavelength, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
  • the front phase difference is sometimes referred to as “Re”.
  • reflectance when “reflectance” at a predetermined wavelength is referred to, it is a measured value of reflectivity when set to each wavelength using a spectrophotometer. Specifically, the reflectance at each wavelength can be measured using a spectrophotometer V-670 (manufactured by JASCO Corporation).
  • the half mirror of the present invention includes a circularly polarized light reflecting layer, an adhesive layer, and a front plate.
  • the half mirror of the present invention may include a circularly polarized light reflecting layer, an adhesive layer, and a front plate in this order, or may include an adhesive layer, a circularly polarized light reflecting layer, and a front plate in this order.
  • the half mirror of the present invention may be a half mirror with a polarizer including a front plate, a circularly polarized light reflection layer, and a polarizer in this order.
  • the half mirror of the present invention further includes a barrier layer between the circularly polarized light reflecting layer and the adhesive layer.
  • the half mirror may include other layers such as an adhesive layer other than the adhesive layer or a quarter wave plate.
  • FIGS. 11a) to 1g) schematically show examples of the layer structure of the half mirror of the present invention.
  • FIG. 1a) has a glass substrate or a plastic film as a front plate, an adhesive layer between the front plate and the circularly polarized reflective layer, and further includes a barrier layer between the adhesive layer and the circularly polarized reflective layer. The configuration is shown.
  • FIG. 1b) shows a configuration that further includes a quarter-wave plate in the configuration of FIG. 1a).
  • FIG. 1c) shows a configuration in which the front plate includes an optical functional layer.
  • FIG. 1d) shows a configuration in which a laminate of a high Re retardation film and an optical functional layer is bonded to the surface of a glass substrate or a plastic film.
  • FIG. 1a) has a glass substrate or a plastic film as a front plate, an adhesive layer between the front plate and the circularly polarized reflective layer, and further includes a barrier layer between the adhesive layer and the circularly polarized reflective layer. The configuration is
  • FIGS. 1f) and 1g) show examples of the layer structure of a half mirror with a polarizer.
  • an optical functional layer is formed on the surface of the support and the alignment layer when the circularly polarized light reflecting layer is formed to constitute a front plate.
  • a barrier layer is formed on the surface of the circularly polarized light reflecting layer, and a quarter wave plate and then a polarizer are bonded. The barrier layer is provided on the polarizer side when viewed from the circularly polarized light reflecting layer.
  • the area of the main surface of the front plate may be larger than the area of the main surface of the circularly polarized light reflecting layer, or may be the same or smaller.
  • “main surface” refers to the surface (front surface or back surface) of a plate-like or film-like member.
  • the circularly polarized light reflecting layer may be bonded to a part of the main surface of the front plate, and another type of reflecting layer such as a metal foil may be bonded or formed at other portions. With such a configuration, an image can be displayed on a part of the mirror. On the other hand, a circularly polarized light reflecting layer may be adhered to the entire front plate main surface.
  • the film thickness of the half mirror is not particularly limited, but is preferably 100 ⁇ m to 20 mm, more preferably 200 ⁇ m to 15 mm, and even more preferably 300 ⁇ m to 10 mm.
  • the half mirror may be plate-shaped or film-shaped, and may have a curved surface.
  • the half mirror may be flat or curved.
  • a curved half mirror can be produced using a curved front plate.
  • ⁇ Circularly polarized reflective layer> When the circular mirror is used as a mirror with an image display function, an image is displayed on the front surface of the mirror with an image display function by transmitting light emitted from the image display device when the image is displayed. On the other hand, when the image is not displayed, it is a layer that reflects at least part of incident light from the front surface and functions so that the front surface of the mirror with the image display function becomes a mirror.
  • the half mirror includes a circularly polarized light reflection layer, incident light from the front surface can be reflected as circularly polarized light, and incident light from the image display device can be transmitted as circularly polarized light. Therefore, the mirror with an image display function including the half mirror according to the present invention does not depend on the relationship between the transmission axis direction of the polarized sunglasses and the horizontal direction of the mirror with the image display function, even through the polarized sunglasses. A mirror reflection image can be observed.
  • the circularly polarized light reflection layer includes a cholesteric liquid crystal layer.
  • the circularly polarized light reflection layer preferably includes at least three cholesteric liquid crystal layers.
  • the circularly polarized light reflecting layer may include four or more cholesteric liquid crystal layers.
  • the circularly polarized light reflecting layer may include other layers such as an alignment layer in addition to the cholesteric liquid crystal layer, or may be composed of only the cholesteric liquid crystal layer.
  • the plurality of cholesteric liquid crystal layers are preferably in direct contact with adjacent cholesteric liquid crystal layers.
  • the film thickness of the circularly polarized light reflecting layer is preferably in the range of 2.0 ⁇ m to 300 ⁇ m, more preferably in the range of 6.0 ⁇ m to 100 ⁇ m.
  • a cholesteric liquid crystal layer means a layer in which a cholesteric liquid crystal phase is fixed.
  • the cholesteric liquid crystal layer is sometimes simply referred to as a liquid crystal layer.
  • the cholesteric liquid crystal phase selectively reflects the circularly polarized light of either the right circularly polarized light or the left circularly polarized light in a specific wavelength range and selectively transmits the circularly polarized light of the other sense. It is known to show.
  • the circularly polarized light selective reflection is sometimes simply referred to as selective reflection.
  • the cholesteric liquid crystal layer may be a layer that maintains the orientation of the liquid crystal compound that is in the cholesteric liquid crystal phase.
  • a polymerizable liquid crystal compound is brought into an alignment state of a cholesteric liquid crystal phase, and then polymerized and cured by ultraviolet irradiation or heating to form a non-flowable layer, and an alignment form by an external field or an external force. Any layer may be used as long as it is changed to a state that does not cause any change.
  • the cholesteric liquid crystal layer it is sufficient that the optical properties of the cholesteric liquid crystal phase are maintained in the layer, and the liquid crystal compound in the layer may no longer exhibit liquid crystallinity.
  • the polymerizable liquid crystal compound may have a high molecular weight due to a curing reaction and may no longer have liquid crystallinity.
  • the selective reflection center wavelength and the half value width of the cholesteric liquid crystal layer can be obtained as follows.
  • the center wavelength of selective reflection means the center wavelength when measured from the normal direction of the cholesteric liquid crystal layer.
  • the reflection spectrum of the cholesteric liquid crystal layer is measured using a spectrophotometer V-670 (Shimadzu Corporation)
  • a reflection peak is observed in the selective reflection region.
  • the wavelength value on the short wavelength side is ⁇ l (nm)
  • the wavelength value on the long wavelength side is ⁇ h (nm )
  • the center wavelength and the full width at half maximum of selective reflection can be expressed by the following equations.
  • the reflection spectrum is observed from the normal reflection direction ( ⁇ 5 ° from the normal direction) when light is irradiated from the + 5 ° direction from the normal direction of the cholesteric liquid crystal layer.
  • the central wavelength ⁇ of selective reflection possessed by the cholesteric liquid crystal layer thus obtained usually coincides with the wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer.
  • the center wavelength of selective reflection can be adjusted by adjusting the pitch of the spiral structure.
  • the center wavelength ⁇ can be adjusted in order to selectively reflect either the right circularly polarized light or the left circularly polarized light with respect to light of a desired wavelength by adjusting the n value and the P value.
  • n ⁇ P the center wavelength of selective reflection when a light beam passes at an angle of ⁇ 2 with respect to the normal direction of the cholesteric liquid crystal layer (helical axis direction of the cholesteric liquid crystal layer) is ⁇ d .
  • ⁇ d n 2 ⁇ P ⁇ cos ⁇ 2
  • the center wavelength of selective reflection of the cholesteric liquid crystal layer included in the circularly polarized light reflecting layer it is possible to prevent the visibility of the image from being viewed obliquely.
  • the pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used together with the polymerizable liquid crystal compound or the concentration of the chiral agent, the desired pitch can be obtained by adjusting these.
  • For the method of measuring spiral sense and pitch use the methods described in “Introduction to Liquid Crystal Chemistry Experiments”, edited by the Japanese Liquid Crystal Society, Sigma Publishing 2007, page 46, and “Liquid Crystal Handbook”, Liquid Crystal Handbook Editing Committee, page 196. be able to.
  • the central wavelength of selective reflection of the cholesteric liquid crystal layer By adjusting the central wavelength of selective reflection of the cholesteric liquid crystal layer to be used according to the emission wavelength range of the image display device and the usage mode of the circularly polarized light reflection layer, a bright image can be displayed with high light utilization efficiency.
  • the usage of the circularly polarized light reflecting layer include an incident angle of light to the circularly polarized light reflecting layer, an image observation direction, and the like.
  • the circularly polarized light reflection layer includes a cholesteric liquid crystal layer having a central wavelength of selective reflection in a red light wavelength range, a cholesteric liquid crystal layer having a central wavelength of selective reflection in a wavelength range of green light, and blue It is preferable to include a cholesteric liquid crystal layer having a central wavelength of selective reflection in the wavelength region of light.
  • the reflective layer is, for example, a cholesteric liquid crystal layer having a central wavelength of selective reflection in 400 nm to 500 nm, a cholesteric liquid crystal layer having a central wavelength of selective reflection in 500 nm to 580 nm, and a cholesteric liquid crystal having a central wavelength of selective reflection in 580 nm to 700 nm. It is preferable to include a layer. Further, when the circularly polarized light reflection layer includes a plurality of cholesteric liquid crystal layers, it is preferable that the cholesteric liquid crystal layer closer to the image display device has a longer selective reflection center wavelength. With such a configuration, it is possible to suppress a color change during oblique observation in the image and the mirror reflection image.
  • a cholesteric liquid crystal layer having a central wavelength of selective reflection in the infrared light region may be included in the circularly polarized light reflection layer.
  • the center wavelength of selective reflection in the infrared light region may specifically be in the range of 780 to 900 nm, and preferably in the range of 780 to 850 nm.
  • the cholesteric liquid crystal layer having a central wavelength of selective reflection is provided in the infrared light region, it is preferable that the cholesteric liquid crystal layer having a central wavelength of selective reflection in the visible light region is on the image display device side.
  • the central wavelength of selective reflection of each cholesteric liquid crystal layer is 5 nm or more with the wavelength of the emission peak of the image display device. It is preferable to make them different. This difference is more preferably 10 nm or more.
  • the peak wavelength only needs to be a peak wavelength in the visible light region of the emission spectrum, and includes, for example, an emission peak wavelength ⁇ R of red light, an emission peak wavelength ⁇ G of green light, and an emission peak wavelength ⁇ B of blue light. Any one or more selected from the group may be used.
  • the central wavelength of selective reflection of the cholesteric liquid crystal layer is 5 nm or more for any of the above-described red light emission peak wavelength ⁇ R, green light emission peak wavelength ⁇ G, and blue light emission peak wavelength ⁇ B of the image display device, preferably It is preferably different by 10 nm or more.
  • the central wavelength of selective reflection of all the cholesteric liquid crystal layers is different from the wavelength of the peak of light emitted from the image display device by 5 nm or more, preferably 10 nm or more. do it.
  • the image display device is a full-color display device showing an emission peak wavelength ⁇ R of red light, an emission peak wavelength ⁇ G of green light, and an emission peak wavelength ⁇ B of blue light in the emission spectrum during white display
  • All of the central wavelengths of selective reflection of the cholesteric liquid crystal layer may be different from each of ⁇ R, ⁇ G, and ⁇ B by 5 nm or more, preferably 10 nm or more.
  • the circularly polarized light reflection layer includes three cholesteric liquid crystal layers having different selective reflection center wavelengths represented by ⁇ 1, ⁇ 2, and ⁇ 3, the relationship of ⁇ B ⁇ 1 ⁇ G ⁇ 2 ⁇ R ⁇ 3 is satisfied. It is preferable that
  • each cholesteric liquid crystal layer a cholesteric liquid crystal layer whose spiral sense is either right or left is used.
  • the sense of reflected circularly polarized light in the cholesteric liquid crystal layer coincides with the sense of a spiral. It is preferable that the spiral senses of the plurality of cholesteric liquid crystal layers are all the same.
  • the sense of the spiral at that time is a circle that is more contained in the light immediately after being emitted from the image display device and transmitted through the quarter wave plate as each cholesteric liquid crystal layer. What is necessary is just to determine according to the sense of polarization.
  • a cholesteric liquid crystal layer having a spiral sense that transmits circularly polarized light of sense contained more in light immediately after being emitted from the image display device and transmitted through the quarter-wave plate may be used.
  • ⁇ n can be adjusted by adjusting the kind of the polymerizable liquid crystal compound and the mixing ratio thereof, or by controlling the temperature at the time of fixing the alignment.
  • a plurality of cholesteric liquid crystal layers having the same pitch P and the same spiral sense may be stacked. By laminating cholesteric liquid crystal layers having the same pitch P and the same spiral sense, the circularly polarized light selectivity can be increased at a specific wavelength.
  • the half mirror of the present invention includes a front plate.
  • the front plate may be a plate shape or a film shape, and may have a curved surface.
  • the front plate may be flat or curved.
  • Such a curved front plate can be produced by a plastic processing method such as injection molding.
  • injection molding for example, a resin product can be obtained by melting raw plastic pellets with heat, injecting them into a mold, and then cooling and solidifying.
  • the front plate is directly bonded to the circularly polarized light reflecting layer and the adhesive layer, or the front plate and the circularly polarized light reflecting layer are in direct contact with each other.
  • the material of the front plate is not particularly limited.
  • the front plate should just contain the glass plate and plastic film which are used for preparation of a normal mirror.
  • plastic film materials include polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivatives such as triacetylcellulose, silicone, polyester such as polyethylene terephthalate (PET), polyacetal, polyarylate, and the like.
  • the support used when forming the cholesteric liquid crystal layer may be a front plate. At this time, the front plate may include an alignment layer.
  • the film thickness of the front plate may be about 100 ⁇ m to 10 mm, preferably 200 ⁇ m to 5 mm, more preferably 500 ⁇ m to 2 mm, and still more preferably 500 ⁇ m to 1000 ⁇ m.
  • the front plate may include a high Re retardation film.
  • the plastic film may include a high Re retardation film, or may include a high Re retardation film in addition to the plastic film not corresponding to a glass plate or a high Re retardation film.
  • the front plate may include an optical function layer.
  • the term “high Re phase difference film” means a phase difference film having a high front phase difference, which is distinguished from a quarter wave plate (phase difference plate).
  • the front retardation of the high Re retardation film is preferably 3000 nm or more, and more preferably 5000 nm or more.
  • the front retardation of the high Re retardation film is preferably as large as possible, but may be 100000 nm or less, 50000 nm or less, 40000 nm or less, or 30000 nm or less in consideration of manufacturing efficiency and thinning.
  • the high Re retardation film can eliminate light / dark unevenness or color unevenness that may occur in a mirror reflection image or image. Brightness / darkness unevenness or color unevenness can occur in a mirror reflection image for the following reason, for example.
  • tempered glass for example, tempered glass that is not a laminated glass
  • vehicle window glass particularly rear glass
  • tempered glass has a birefringence distribution.
  • light and dark unevenness or color unevenness occurs in the mirror reflection image based on the light that passes through the rear glass of the vehicle and enters the front surface of the mirror with an image display function.
  • the high Re retardation film examples include a birefringent material such as a plastic film and a quartz plate.
  • the plastic film examples include polyester films such as polyethylene terephthalate (PET), polycarbonate films, polyacetal films, polyarylate films, and the like. JP-A-2013-257579, JP-A-2015-102636, and the like can be referred to for a retardation film having a high retardation including PET.
  • Commercial products such as optical Cosmo Shine (registered trademark) super birefringence type (Toyobo) may be used.
  • plastic films with high phase difference are melt-extruded from resin, cast on a drum, etc., and formed into a film shape. While heating this, it is stretched 2 to 5 times uniaxially or biaxially. It can be formed by stretching at a magnification.
  • a heat treatment called “heat setting” may be performed at a temperature exceeding the stretching temperature after stretching.
  • optical functional layer examples include a hard coat layer, an antiglare layer, an antireflection layer, and an antistatic layer.
  • the optical functional layer is preferably a cured layer of a polymerizable composition provided on a glass plate or a plastic film.
  • the optical functional layer is preferably provided so that the optical functional layer, the glass plate or plastic film, and the circularly polarized light reflecting layer are in this order.
  • the hard coat layer may be included as the outermost layer of the half mirror, and another layer may be further provided outside the hard coat layer.
  • the hard coat layer refers to a layer that, when formed, increases the pencil hardness of the half mirror surface. Specifically, it is a layer having a pencil hardness (JIS K5400) of H or higher after the hard coat layer lamination.
  • the pencil hardness after laminating the hard coat layer is preferably 2H or more, and more preferably 3H or more.
  • the thickness of the hard coat layer is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 1.0 ⁇ m to 70 ⁇ m, and further preferably 2.0 ⁇ m to 50 ⁇ m.
  • the hard coat layer may also serve as an antireflection layer or an antistatic layer.
  • the hard coat layer include a layer formed from a composition containing an ultraviolet curable polymerizable compound.
  • the composition may contain other components such as particles.
  • As the ultraviolet curable polymerizable compound (meth) acrylate is preferable.
  • As for the material and the production method of the hard coat layer reference can be made to JP-A-2016-071085, JP-A-2012-168295, JP-A-2011-225846, and the like.
  • the antiglare layer is a layer for imparting antiglare properties based on surface scattering.
  • the antiglare layer may be included as the outermost layer of the half mirror, and another layer may be further provided outside the antiglare layer.
  • the antiglare layer can be formed from a composition containing a binder resin-forming compound for the antiglare layer and particles for the antiglare layer.
  • material and production method of the antiglare layer reference can be made to the descriptions of 0101 to 0109 of JP2013-178484A, JP2016-053601A, and the like.
  • the antireflection layer is preferably included on the outermost surface of the half mirror. By providing the antireflection layer, the reflected light on the outermost surface is suppressed, and a mirror reflection image based on an image derived from the light from the polarizing reflection plate can be clearly observed.
  • the description in 0049 to 0053 of WO2015 / 050202 can be referred to.
  • the antistatic layer is preferably contained on the outermost surface of the half mirror.
  • the material and manufacturing method of the antistatic layer reference can be made to the descriptions in 0020 to 0028 of JP 2012-027191 A.
  • the half mirror of the present invention includes a circularly polarizing reflection layer and an adhesive layer for adhesion of the front plate.
  • the adhesive layer for bonding the circularly polarized light reflecting layer and the front plate is an adhesive layer included between the circularly polarized light reflecting layer and the front plate.
  • Adhesive layer is acrylate, urethane, urethane acrylate, epoxy, epoxy acrylate, polyolefin, modified olefin, polypropylene, ethylene vinyl alcohol, vinyl chloride, chloroprene rubber, cyanoacrylate, polyamide Any adhesive may be used as long as it is formed from an adhesive containing a compound such as polyimide, polystyrene, or polyvinyl butyral.
  • acrylate, urethane acrylate, epoxy acrylate, and the like are preferable.
  • the adhesive there are a hot melt type, a thermosetting type, a photocuring type, a reaction curing type, and a pressure-sensitive adhesive type that does not require curing from the viewpoint of a curing method. From the viewpoint of workability and productivity, the photocuring type is preferred as the curing method.
  • the adhesive layer for bonding the circularly polarized light reflecting layer and other layers is not a hot melt type. That is, it is preferably not a thermoplastic weld layer.
  • a thermoplastic welding layer is a layer which melt
  • the adhesive layer for bonding the circularly polarized light reflection layer and other layers is made of a pressure-sensitive adhesive type adhesive that does not require curing. Examples of pressure-sensitive adhesives include acrylate-based, urethane-based, and silicone-based adhesives, and acrylate-based adhesives are particularly preferable.
  • the adhesive may be a sheet or a liquid.
  • the sheet-like adhesive include a pressure-sensitive adhesive type that does not require curing, and a type that performs thermal curing or photocuring after placing the sheet.
  • an OCA tape highly transparent adhesive transfer tape
  • OCA tapes are generally marketed in the form of having a peelable protective sheet on one or both sides of the adhesive layer, and this adhesive layer can be used as the adhesive layer.
  • the liquid adhesive include OCR (highly transparent optical resin).
  • the sheet-like adhesive When the sheet-like adhesive is used as an adhesive layer for adhesion of the circularly polarized reflective layer and other layers, the above problem that the color change occurs in the mirror reflection image under high temperature conditions is specifically becomes particularly prominent when the adhesive layer in the OCA tape is used.
  • the sheet-like adhesive generally has a low Tg and a high fluidity, and therefore, it is considered that the substance easily flows from the outside in a high temperature environment. Therefore, the effect of providing the barrier layer is particularly remarkable when a sheet-like adhesive is used for forming the adhesive layer.
  • the sheet-like adhesive examples include acrylates, urethanes, and silicones, and acrylates are particularly preferable.
  • OCA tape that can be used as a sheet-like adhesive
  • a commercially available product for an image display device particularly a product marketed for the surface of an image display unit of an image display device may be used.
  • Examples of commercially available products include PANAC Corporation pressure sensitive adhesive sheets (PD-S1 and the like), Nichiei Kako MHM series pressure sensitive adhesive sheets, 3M Corporation OCA8146, and the like.
  • the film thickness of the adhesive layer is preferably 0.50 ⁇ m or more and 50 ⁇ m or less, and more preferably 1.0 ⁇ m or more and 25 ⁇ m or less.
  • the half mirror of the present invention includes a barrier layer.
  • the barrier layer is included between the adhesive layer and the circularly polarized light reflecting layer.
  • the barrier layer and the circularly polarized light reflecting layer are preferably in direct contact.
  • the barrier layer is preferably in direct contact with the cholesteric liquid crystal layer in the circularly polarized light reflecting layer.
  • a half mirror including a cholesteric liquid crystal layer may cause a color change in a mirror reflection image under a high temperature condition, particularly a high temperature and high humidity condition.
  • a color change can occur in an environment of 40 ° C. to 200 ° C., particularly in an environment of 65 ° C. to 110 ° C.
  • color changes can occur in an environment of 85 ° C. to 110 ° C. at a relative humidity of 40%, and in an environment of 65 ° C. to 85 ° C. at a relative humidity of 85%.
  • the color change is based on the fact that the selective reflection center wavelength of a cholesteric liquid crystal layer described later is shifted by a short wavelength under a high temperature environment.
  • the inventors have obtained a result that a substance is considered to have moved from the cholesteric liquid crystal layer to the adhesive layer in a high temperature environment, and provided a barrier layer for suppressing this movement. The above problem was solved.
  • the film thickness of the cholesteric liquid crystal layer is reduced due to the movement of the material constituting the cholesteric liquid crystal layer to the outside at high temperatures.
  • the pitch P is reduced and the selective reflection center wavelength is shifted by a short wavelength.
  • the barrier layer is a layer that can suppress the movement of components in the cholesteric liquid crystal layer to the outside in a high temperature environment.
  • a layer capable of suppressing the movement of components in the cholesteric liquid crystal layer to the adhesive layer is preferable.
  • the barrier layer is preferably a layer in which the components in the cholesteric liquid crystal layer are difficult to move.
  • the component in the cholesteric liquid crystal layer whose movement is suppressed by the barrier layer include a polymerization initiator, an unreacted polymerizable liquid crystal compound, and any of the above decomposition products. Among these, it is preferable that the movement of the component selected from the polymerization initiator and the decomposition product of the polymerization initiator is suppressed.
  • That the movement can be suppressed means that the amount of components detected in the cholesteric liquid crystal layer is increased compared to the amount of components detected in the cholesteric liquid crystal layer of the half mirror having the same configuration except that there is no barrier layer. It means that you can.
  • the detection at this time may be performed by cutting the half mirror and analyzing the surface of the cholesteric liquid crystal layer.
  • the fact that movement can be suppressed is detected by the barrier layer and the adhesive layer compared to the amount of components in the cholesteric liquid crystal layer detected by the adhesive layer of the half mirror having the same configuration except that there is no barrier layer. This means that the amount of components in the cholesteric liquid crystal layer can be reduced.
  • the detection at this time may be performed by cutting the half mirror and performing surface analysis of both the adhesive layer or the barrier layer and the adhesive layer. Specifically, the above-described detection is performed for each half mirror after being left in a high temperature environment, and the amount may be substantially reduced. Examples of the surface analysis include X-ray photoelectric spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Moreover, the leaving in a high temperature environment should just be performed at 110 degreeC for 160 hours.
  • XPS X-ray photoelectric spectroscopy
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the barrier layer is preferably transparent in the visible light region.
  • Transparent in the visible light region means that the light transmittance in the visible light region is 80% or more, preferably 85% or more.
  • the light transmittance used as a measure of transparency is the light transmittance determined by the method described in JIS A5759. That is, the transmittance at a wavelength of 380 nm to 780 nm is measured with a spectrophotometer, and the weight obtained from the spectral distribution of CIE (International Commission on Illumination) daylight D65, the wavelength distribution of CIE light adaptation standard relative luminous sensitivity, and the wavelength interval. The light transmittance is obtained by multiplying the coefficient and performing a weighted average.
  • the barrier layer preferably has a small birefringence.
  • the front phase difference may be 20 nm or less, preferably less than 10 nm, and more preferably 5 nm or less.
  • the barrier layer may be an inorganic layer or an organic layer, for example.
  • barrier layer When the barrier layer is an organic layer, it is preferably a barrier layer formed from a composition having a high glass transition temperature (Tg). This is because it is strong in a high temperature environment.
  • Tg glass transition temperature
  • DSC differential scanning calorimetry
  • DSC device DSC6200, manufactured by SII Technology ⁇ Atmosphere in measurement chamber: Nitrogen (50 mL / min) ⁇ Raising rate: 10 ° C / min ⁇ Measurement start temperature: 0 °C -Measurement end temperature: 200 ° C ⁇ Sample pan: Aluminum pan ⁇ Measurement sample mass: 5 mg -Calculation of Tg: Tg is the intermediate temperature between the descent start point and descent end point of the DSC chart. However, the measurement is performed twice with the same sample, and the second measurement result is adopted.
  • Tg is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.
  • Tg is preferably 500 ° C. or lower, and more preferably 300 ° C. or lower.
  • the barrier layer is preferably hydrophilic.
  • the SP value Solubility Parameter (solubility parameter or solubility parameter)
  • the solubility parameter (SP value) can be determined by the Okitsu method. For details on the Okitsu method, see Journal of the Japan Adhesion Society Vol. 29, no. 6 (1993) 249-259.
  • the barrier layer which is an organic layer
  • a layer obtained by curing a composition containing a monomer containing a polymerizable group is preferable.
  • a urethane (meth) acrylate monomer, a (meth) acrylate monomer, and an epoxy monomer are mentioned.
  • the monomer preferably has a large number of polymerizable groups.
  • the monomer may be used as a mixture of two or more monomers.
  • Urethane (meth) acrylate monomer contains a urethane bond represented by formula (I) and a (meth) acryloyl group.
  • R represents a hydrogen atom or a hydrocarbon group.
  • the “hydrocarbon group” means a monovalent group composed of only carbon atoms and hydrogen atoms, and examples thereof include aromatic ring groups such as alkyl groups, cycloalkyl groups, phenyl groups, and naphthyl groups.
  • R is preferably a hydrogen atom.
  • the urethane (meth) acrylate monomer is a compound obtained from an addition reaction using a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, or an addition reaction using a polyalcohol compound and an isocyanate group-containing (meth) acrylate compound. .
  • the polyisocyanate compound is preferably diisocyanate or triisocyanate.
  • Specific examples of the polyisocyanate compound include toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and the like.
  • Examples of the hydroxyl group-containing (meth) acrylate compound include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like.
  • Examples of the polyalcohol compound include ethylene glycol, propylene glycol, glycerin, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, and the like.
  • Examples of the isocyanate group-containing (meth) acrylate compound include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
  • the urethane (meth) acrylate monomer preferably contains two or more (meth) acryloyl groups, more preferably three or more, and still more preferably four or more.
  • the upper limit of the number of (meth) acryloyl groups in the urethane (meth) acrylate monomer is not particularly limited, but may be 30 or less, more preferably 20 or less, and even more preferably 18 or less.
  • the molecular weight of the urethane (meth) acrylate monomer is preferably 400 to 8000, more preferably 500 to 5000.
  • urethane (meth) acrylate monomer Commercial products may be used as the urethane (meth) acrylate monomer. Commercially available products include U-2PPA, U-4HA, U-6LPA, U-10PA, UA-1100H, U-10HA, U-15HA, UA-53H, UA-33H, U-, manufactured by Shin-Nakamura Kogyo Co., Ltd. 200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-7100, UA-W2A and Kyoeisha Chemical Co., Ltd.
  • EBERCRYL204 EBERCRYL205, EBERCRYL210, EBERCRYL215, EBERCRYL220L 44, EBERCRYL245, EBERCRYL264, EBERCRYL265, EBERCRYL270, EBERCRYL280 / 15IB, EBERCRYL284, EBERCRYL285, EBERCRYL294 / 25HD, EBERCRYL1259, EBERCRYL1290, EBERCRYL8200, EBERCRYL8200AE, EBERCRYL4820, EBERCRYL4858, EBERCRYL5129, EBERCRYL8210, EBERCRYL8254, EBERCRYL8301R, EBERCRYL83
  • Examples of preferable urethane (meth) acrylate monomers include U-6LPA and U-4HA.
  • the urethane (meth) acrylate monomer is also preferably used in combination with a urethane polymer.
  • a urethane-based polymer is a generic term for polymers having a urethane bond in the main chain, and is usually obtained by reaction of polyisocyanate and polyol.
  • the polyisocyanate include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI).
  • examples of the polyol include ethylene glycol, propylene glycol, glycerin, and hexanetriol. It is done.
  • the urethane polymer may be a polymer obtained by subjecting polyurethane obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight.
  • polyisocyanate, polyol, and chain extension treatment for example, “Polyurethane Resin Handbook” (Akita Seida, edited by Nikkan Kogyo Shimbun, published in 1987) can be referred to.
  • 8BR-600 manufactured by Taisei Fine Chemical Co., Ltd.
  • the urethane polymer preferably has a molecular weight of 10,000 to 200,000, more preferably 15,000 to 150,000.
  • the urethane polymer is used in the composition for forming a barrier layer in an amount of 1.0 to 50 with respect to the total mass (solid content) of the composition. It is preferably contained in an amount of 10% by mass, more preferably 10 to 40% by mass.
  • the (meth) acrylate monomer for example, compounds described in paragraphs 0024 to 0036 of JP2013-43382A or paragraphs 0036 to 0048 of JP2013-43384A can be used. Further, a polyfunctional acrylic monomer having a fluorene skeleton described in WO2013 / 047524 can also be used.
  • the (meth) acrylate monomer is selected from the group consisting of Shinnakamura's DPHA and ADCP, Toagosei's SP327, and Nippon Kayaku's KAYARAD PET30, KAYARAD DPCA20, DPCA30, DPCA60, and DPCA120.
  • One or more monomers are preferred. This is because Tg is particularly high and there are many polymerizable groups.
  • the epoxy monomer may be any monomer containing an epoxy group.
  • bisphenol A hydrogenated bisphenol A, bisphenol F, hydrogenated bisphenol F, novolak, other aromatic, alicyclic, heterocyclic, glycidyl ester, or glycidylamine epoxy
  • glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like can be used.
  • epoxy monomers include EHPE3150, CEL2021P, CEL8000, Cyclomer M100 (Daicel), JER1031S, JER157S65, JER1007, JER152, JER154, JERYX6810 (Mitsubishi Chemical Corporation), Denacol EX411, Denacol EX8, EX821, Denacol EX825, Denacol EX841 (Nagase ChemteX Corporation), EPICLON HP-4032D, EPICLON EXA1514, EPICLON HP-7200, EPICLON HP7200L, EPICLON HP7200H, EPICLON N670, EPICLON N6 Of these, CEL2021P, CEL8000, cyclomer M100, and EPICLON HP-4032D are particularly preferable.
  • the monomer is preferably contained in an amount of 50 to 100% by mass, preferably 80 to 99% by mass, based on the total mass (solid content) of the composition. It is more preferable.
  • the composition for forming the barrier layer may contain a polymerization initiator.
  • a polymerization initiator is preferably 0.1 mol% or more, more preferably 0.5 to 5 mol% of the total amount of the monomers.
  • the polymerization initiator include the following cationic photopolymerization initiators in addition to the same examples as the polymerization initiators that can be used in the liquid crystal composition described later.
  • an epoxy monomer is used as the monomer, it is preferable to use a cationic photopolymerization initiator.
  • a cation can be generated as an active species by light irradiation.
  • Specific examples include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryl iodonium salts), triarylsulfonium salts, A diazonium salt, an iminium salt, etc. are mentioned. More specifically, for example, cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, JP-A-8-283320 In the paragraph 0020, those exemplified as the cationic polymerization catalyst can be exemplified.
  • Examples of commercially available cationic photopolymerization initiators include CI-1370, CI-2064, CI-2397, CI-2624, CI-2634, CI-2734, CI-2758, CI-2758 manufactured by Nippon Soda Co., Ltd. 2823, CI-2855 and CI-5102, PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974, UVI-6990 manufactured by Union Carbide, and CPI-10P manufactured by San Apro.
  • a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoints of sensitivity of the photopolymerization initiator to light and stability of the compound. Moreover, an iodonium salt is more preferable from the point of weather resistance.
  • iodonium salts examples include B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Co., Ltd., WPI-113, WPI-124, WPI- manufactured by Wako Pure Chemical Industries, Ltd. 169, WPI-170, and DTBPI-PFBS manufactured by Toyo Gosei.
  • Specific examples of the iodonium salt compound that can be used as the cationic photopolymerization initiator include the following compounds PAG-1 and PAG-2.
  • composition for forming the barrier layer may further contain other components such as a surfactant.
  • the number of polymerizable groups Y 1 and the polymerizable group content X 1 of the monomer in the composition satisfy Formula 1.
  • the inventors have found that when the formula 1 is satisfied, the generation of cracks in the barrier layer can be more effectively prevented.
  • Equation 1 if the number of polymerizable groups in the monomer is too large, cracks are likely to occur, and if the molecular weight relative to the number of polymerizable groups is large, cracks are likely to occur even if the number of polymerizable groups is lower.
  • the polymerizable group content is a value obtained by dividing the number of polymerizable groups of the monomer by the molecular weight (number of polymerizable groups / molecular weight).
  • Y 1 and X 1 is an average value in consideration of the percentage of the total monomer weight of the monomer weight of each composition. Therefore, it is preferable to use a monomer that does not satisfy Formula 1 alone as a mixture with other monomers and a composition that satisfies Formula 1.
  • the barrier layer is a layer obtained by curing a composition containing a urethane (meth) acrylate monomer
  • the number of polymerizable groups Y 2 of the urethane (meth) acrylate monomer and the glass transition temperature (Tg) X 2 of the composition are It is preferable to satisfy Equation 2.
  • the present inventors have found that when the formula 2 is satisfied, the heat resistance of the barrier layer becomes higher.
  • the number of polymerizable groups of the urethane (meth) acrylate monomer is preferably large, as can be seen from Formula 2, when Tg is large, the number of polymerizable groups may be relatively low.
  • the composition comprises a plurality of monomers
  • Y 2 and X 2 is an average value in consideration of the percentage of the total monomer weight of the monomer weight of each composition. Therefore, it is preferable to use a monomer that does not satisfy Formula 2 alone as a mixture with other monomers and a composition that satisfies Formula 2.
  • the barrier layer is a layer obtained by curing a composition containing an epoxy monomer
  • the polymerizable group number Y 3 of the epoxy monomer and the glass transition temperature (Tg) X 3 of the composition satisfy the formula 3.
  • the present inventors have found that when Formula 3 is satisfied, generation of cracks in the barrier layer can be more effectively prevented.
  • the number of polymerizable groups of the epoxy monomer is preferably large, but as can be seen from Formula 3, when the Tg of the composition containing the epoxy monomer is large, the number of polymerizable groups may be relatively low.
  • the composition comprises a plurality of monomers
  • Y 3 and X 3 is an average value in consideration of the percentage of the total monomer weight of the monomer weight of each composition. Therefore, it is preferable to use a monomer that does not satisfy Formula 3 alone as a mixture with other monomers and a composition that satisfies Formula 3.
  • the film thickness of the barrier layer which is an organic layer is preferably 0.1 ⁇ m or more and 20 ⁇ m or less, more preferably 0.5 ⁇ m or more and 10 ⁇ m or less, and further preferably 1.2 ⁇ m or more and 3.0 ⁇ m or less. .
  • the formation of the barrier layer from the above composition is preferably performed by a method including applying the composition for forming the barrier layer on the cholesteric liquid crystal layer, preferably on the surface of the cholesteric liquid crystal layer.
  • the composition for forming the barrier layer may contain a solvent for good application.
  • the layer after application may be dried and cured by a method suitable for the composition used to form a barrier layer. Curing is preferably performed by photocuring.
  • the solvent, coating method, and photocuring condition that may be contained in the composition for forming the barrier layer the description for the liquid crystal composition described later can be referred to.
  • the barrier layer is an inorganic layer
  • a high density is desirable. This is to make it difficult to pass components in the cholesteric liquid crystal layer.
  • the density of the inorganic layer is preferably 2.1 to 2.4 g / cm 3 . Low density inorganic layers tend to have low barrier performance. On the other hand, if the density is too high, the flexibility is lowered, and peeling or cracking due to stress tends to occur.
  • the density of the inorganic layer shown in this specification is determined by XRR (X-ray reflectivity). The calculation of the density from the XRR measurement result may be performed by simulation using software.
  • XRR measurement can be performed by, for example, ATX (manufactured by Rigaku Corporation).
  • the simulation can be performed using, for example, analysis software GXRR (manufactured by Rigaku Corporation). It is assumed that the inorganic layer is a single layer.
  • the inorganic layer preferably contains, for example, metal oxide, metal nitride, metal oxynitride or metal carbide.
  • metal oxide, metal nitride, metal oxynitride or metal carbide preferably contains one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, Nb, Zr, and La Nitride carbide or the like.
  • a metal oxide, nitride, or oxynitride selected from Si, Ti, Nb, Zr, and La is preferable. Specific examples include silicon oxide, tantalum oxide, zirconium oxide, titanium oxide, niobium oxide, and lanthanum titanate.
  • the inorganic layer can be formed by any method that can form a target thin film.
  • vapor deposition may be ion-assisted vapor deposition
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • Etc plating and sol-gel methods Etc.
  • the film thickness of the barrier layer, which is an inorganic layer is preferably 1.0 nm or more and 1000 nm or less, more preferably 3.0 nm or more and 500 nm or less, and further preferably 5.0 nm or more and 100 nm or less.
  • the half mirror of the present invention may include a quarter wavelength plate.
  • a half mirror including a quarter wavelength plate and forming a mirror with an image display function as a configuration including a quarter wavelength plate between the image display device and the circularly polarized light reflection layer. Therefore, the light reflected by the circularly polarized light reflection layer and returning to the image display device side can be greatly reduced, and a bright image can be displayed.
  • the quarter wave plate may be a retardation layer that functions as a quarter wave plate in the visible light region.
  • the quarter-wave plate include a single-layer quarter-wave plate, a broadband quarter-wave plate in which a quarter-wave plate and a half-wave retardation plate are stacked, and the like.
  • the front phase difference of the former 1 ⁇ 4 wavelength plate may be 1 ⁇ 4 of the emission wavelength of the image display device. Therefore, for example, when the emission wavelength of the image display device is 450 nm, 530 nm, and 640 nm, the wavelength of 450 nm is 112.5 nm ⁇ 10 nm, preferably 112.5 nm ⁇ 5 nm, more preferably 112.5 nm, and 530 nm.
  • Inverse dispersion phase difference such that the phase difference is 5 nm ⁇ 10 nm, preferably 132.5 nm ⁇ 5 nm, more preferably 132.5 nm, 160 nm ⁇ 10 nm, preferably 160 nm ⁇ 5 nm, more preferably 160 nm at a wavelength of 640 nm
  • a layer is most preferable as a quarter-wave plate, but a retardation plate having a small retardation wavelength dispersion or a forward dispersion retardation plate can also be used.
  • the reverse dispersion means a property that the absolute value of the phase difference becomes larger as the wavelength becomes longer, and the forward dispersion means a property that the absolute value of the phase difference becomes larger as the wavelength becomes shorter.
  • the laminated quarter-wave plate is formed by laminating a quarter-wave plate and a half-wave retardation plate at an angle of 60 ° with the slow axis, and the side of the half-wave retardation plate is linearly polarized. It is arranged on the incident side and the slow axis of the half-wave retardation plate is used so as to cross 15 ° or 75 ° with respect to the polarization plane of the incident linearly polarized light. Can be suitably used because of its good resistance.
  • quartz plate stretched polycarbonate film, stretched norbornene polymer film, transparent film containing inorganic particles exhibiting birefringence such as strontium carbonate, and oblique deposition of inorganic dielectric on support Thin films and the like.
  • the quarter wavelength plate examples include (1) a birefringent film having a large retardation and a birefringence having a small retardation described in JP-A-5-27118 and JP-A-5-27119.
  • a commercial item can also be used as a quarter wavelength plate, As a commercial item, brand name: Pure Ace WR (made by Teijin Ltd.) etc. are mentioned, for example.
  • the quarter wavelength plate may be formed by arranging and fixing a polymerizable liquid crystal compound or a polymer liquid crystal compound.
  • a liquid crystal composition is applied to the surface of a temporary support, an alignment film, or a front plate, and a polymerizable liquid crystal compound in the liquid crystal composition is formed into a nematic alignment in a liquid crystal state, and then photocrosslinked. It can be formed by immobilization by thermal crosslinking. Details of the liquid crystal composition or the production method will be described later.
  • the quarter wavelength plate is formed by applying a liquid crystal composition on a surface of a temporary support, an alignment film or a front plate to form a nematic alignment in a liquid crystal state, and then cooling the composition containing a polymer liquid crystal compound. It may be a layer obtained by fixing the orientation.
  • the quarter-wave plate may be bonded to the circularly polarized light reflection layer by an adhesive layer, or may be in direct contact, but the latter is preferred.
  • the quarter-wave plate is preferably laminated with the circularly polarized light reflecting layer with the same main surface area.
  • a preparation material and a preparation method of a quarter-wave plate formed from a cholesteric liquid crystal layer and a liquid crystal composition will be described.
  • the material used for forming the quarter wavelength plate include a liquid crystal composition containing a polymerizable liquid crystal compound.
  • the material used for forming the cholesteric liquid crystal layer preferably further contains a chiral agent (optically active compound).
  • a cholesteric liquid crystal layer as a support, a temporary support, an alignment film, a quarter-wave plate, or a lower layer, which is mixed with a surfactant or a polymerization initiator as necessary and dissolved in a solvent. It can apply
  • a rod-like liquid crystal compound may be used as the polymerizable liquid crystal compound.
  • the rod-like polymerizable liquid crystal compound include a rod-like nematic liquid crystal compound.
  • rod-like nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines.
  • Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
  • the polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into the liquid crystal compound.
  • the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group.
  • the polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods.
  • the number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. Examples of polymerizable liquid crystal compounds are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No.
  • the addition amount of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 80 to 99.9% by mass with respect to the solid content mass (mass excluding the solvent) of the liquid crystal composition, and is preferably 85 to 99. It is more preferably 5% by mass, particularly preferably 90 to 99% by mass.
  • the liquid crystal composition used for forming the cholesteric liquid crystal layer preferably contains a chiral agent.
  • the chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase.
  • the chiral compound may be selected according to the purpose because the helical sense or helical pitch induced by the compound is different. There is no restriction
  • Examples of chiral agents include liquid crystal device handbook (Chapter 3, Section 4-3, TN, chiral agent for STN, page 199, edited by Japan Society for the Promotion of Science, 142th Committee, 1989), Japanese Patent Application Laid-Open No. 2003-287623. And compounds described in JP-A Nos. 2002-302487, 2002-80478, 2002-80851, 2010-181852 and 2014-034581.
  • a chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent.
  • the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
  • the chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, they are derived from the repeating unit derived from the polymerizable liquid crystal compound and the chiral agent by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound.
  • the polymerizable group possessed by the polymerizable chiral agent is preferably the same group as the polymerizable group possessed by the polymerizable liquid crystal compound. Therefore, the polymerizable group of the chiral agent is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Particularly preferred.
  • the chiral agent may be a liquid crystal compound.
  • an isosorbide derivative As the chiral agent, an isosorbide derivative, an isomannide derivative, or a binaphthyl derivative can be preferably used.
  • an isosorbide derivative a commercial product such as LC-756 manufactured by BASF may be used.
  • the content of the chiral agent in the liquid crystal composition is preferably from 0.01 mol% to 200 mol%, more preferably from 1.0 mol% to 30 mol%, based on the total molar amount of the polymerizable liquid crystal compound.
  • the liquid crystal composition preferably contains a polymerization initiator.
  • the polymerization initiator to be used is preferably a photopolymerization initiator capable of initiating the polymerization reaction by ultraviolet irradiation, and particularly preferably a radical photopolymerization initiator.
  • radical photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substitution Aromatic acyloin compounds (described in US Pat. No.
  • acyl phosphine oxide compound As the polymerization initiator, it is also preferable to use an acyl phosphine oxide compound or an oxime compound.
  • acylphosphine oxide compound for example, IRGACURE819 (compound name: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) manufactured by BASF Japan Ltd. can be used.
  • Examples of the oxime compounds include IRGACURE OXE01 (manufactured by BASF), IRGACURE OXE02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831, Adeka Arcles NCI-930 Commercial products such as (ADEKA) and Adeka Arcles NCI-831 (ADEKA) can be used.
  • the content of the polymerization initiator in the liquid crystal composition is preferably 0.1 to 20% by mass, and preferably 0.5 to 5.0% by mass with respect to the content of the polymerizable liquid crystal compound. Is more preferable.
  • the liquid crystal composition may optionally contain a crosslinking agent in order to improve the film strength after curing and improve the durability.
  • a crosslinking agent one that can be cured by ultraviolet rays, heat, moisture, or the like can be suitably used.
  • polyfunctional acrylate compounds such as a trimethylol propane tri (meth) acrylate and pentaerythritol tri (meth) acrylate
  • Glycidyl (meth) acrylate Epoxy compounds such as ethylene glycol diglycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; hexa Isocyanate compounds such as methylene diisocyanate and biuret type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylto Alkoxysilane compounds such as methoxy silane.
  • a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to membrane strength and durability improvement. These may be used individually by 1 type and may use 2 or more types together.
  • the content of the crosslinking agent in the liquid crystal composition is preferably 3.0% by mass to 20% by mass, and more preferably 5.0% by mass to 15% by mass. When the content of the crosslinking agent is 3.0% by mass or more, an effect of improving the crosslinking density can be obtained. Moreover, the stability of the layer formed can be maintained by setting it as 20 mass% or less.
  • an alignment control agent that contributes to stable or rapid planar alignment may be added.
  • the alignment control agent include fluorine (meth) acrylate polymers described in paragraphs 0018 to 0043 of JP 2007-272185 A, and formulas (I) described in paragraphs 0031 to 0034 of JP 2012-203237 A, and the like.
  • To (IV) 1 type may be used independently and 2 or more types may be used together.
  • the addition amount of the alignment control agent in the liquid crystal composition is preferably 0.01% by mass to 10% by mass and more preferably 0.01% by mass to 5.0% by mass with respect to the total mass of the polymerizable liquid crystal compound. 0.02% by mass to 1.0% by mass is particularly preferable.
  • the liquid crystal composition may contain at least one selected from a surfactant for adjusting the surface tension of the coating film to make the film thickness uniform, and various additives such as a polymerizable monomer.
  • a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant, metal oxide fine particles, and the like may be added as long as the optical performance is not deteriorated. Can be added.
  • solvent there is no restriction
  • the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, ethers, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, ketones are particularly preferable in consideration of environmental load.
  • the method for applying the liquid crystal composition to the temporary support, the alignment film, the quarter-wave plate, the underlying cholesteric liquid crystal layer, etc. is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a wire bar coating method, a curtain coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, a spin coating method, a dip coating method, a spray coating method, and a slide coating method. It can also be carried out by transferring a liquid crystal composition separately coated on a support. The liquid crystal molecules are aligned by heating the applied liquid crystal composition.
  • cholesteric alignment may be performed, and in forming the quarter-wave plate, nematic alignment is preferable.
  • the heating temperature is preferably 200 ° C. or lower, and more preferably 130 ° C. or lower.
  • the heating temperature is preferably 50 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C.
  • the aligned liquid crystal compound can be further polymerized to cure the liquid crystal composition.
  • the polymerization may be either thermal polymerization or photopolymerization utilizing light irradiation, but photopolymerization is preferred. It is preferable to use ultraviolet rays for light irradiation.
  • the irradiation energy is preferably 20mJ / cm 2 ⁇ 50J / cm 2, 100mJ / cm 2 ⁇ 1,500mJ / cm 2 is more preferable.
  • light irradiation may be performed under heating conditions or in a nitrogen atmosphere.
  • the irradiation ultraviolet wavelength is preferably 350 nm to 430 nm.
  • the polymerization reaction rate is preferably high from the viewpoint of stability, preferably 70% or more, and more preferably 80% or more.
  • the polymerization reaction rate can be determined by measuring the consumption rate of the polymerizable group using an IR absorption spectrum.
  • each cholesteric liquid crystal layer is not particularly limited as long as it exhibits the above characteristics, but is preferably in the range of 1.0 to 150 ⁇ m, more preferably in the range of 4.0 to 100 ⁇ m. Good.
  • the thickness of the quarter-wave plate formed from the liquid crystal composition is not particularly limited, but is preferably 0.2 ⁇ m to 10 ⁇ m, more preferably 0.5 ⁇ m to 2.0 ⁇ m.
  • the liquid crystal composition may be applied to the support, the temporary support, or the surface of the alignment layer formed on the support or the temporary support surface to form a layer.
  • the temporary support or the temporary support and the alignment layer may be peeled off after forming the layer. For example, what is necessary is just to peel, after adhere
  • the temporary support may function as a protective film after the circularly polarized reflective layer is bonded to the front plate and further until the circularly polarized reflective layer is bonded to the image display device.
  • the support may be left as a layer constituting the half mirror without being peeled off.
  • the front plate, the circularly polarizing reflection layer, and the support may be arranged in this order (for example, FIG. 1 (e) and FIG. 1 (g)).
  • the support may constitute a front plate (for example, FIG. 1 (f)).
  • Examples of the temporary support and the support include a plastic film or a glass plate.
  • plastic film materials include polyesters such as polyethylene terephthalate (PET), polycarbonate, acrylic resins, epoxy resins, polyurethanes, polyamides, polyolefins, cellulose derivatives such as triacetyl cellulose, and silicones.
  • PET polyethylene terephthalate
  • the temporary support is preferably a polyethylene terephthalate (PET) film, and the support is preferably a triacetyl cellulose film.
  • the alignment layer has a rubbing treatment of organic compounds such as polymers (resins such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, polyetherimide, polyamide, modified polyamide), oblique deposition of inorganic compounds, and microgrooves. It can be provided by means such as formation of a layer or accumulation of an organic compound (for example, ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate) using the Langmuir-Blodgett method (LB film).
  • organic compounds such as polymers (resins such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamideimide, polyetherimide, polyamide, modified polyamide), oblique deposition of inorganic compounds, and microgrooves. It can be provided by means such as formation of a layer or accumulation of an organic compound (for example, ⁇ -tricosanoic acid, dio
  • an alignment layer that generates an alignment function by application of an electric field, application of a magnetic field, or light irradiation may be used.
  • the alignment layer made of a polymer is preferably subjected to a rubbing treatment and then a liquid crystal composition is applied to the rubbing treatment surface.
  • the rubbing treatment can be performed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth.
  • the liquid crystal composition may be applied to the surface of the temporary support without providing the alignment layer, or to the surface on which the temporary support has been rubbed.
  • the thickness of the alignment layer is preferably 0.01 ⁇ m to 5.0 ⁇ m, and more preferably 0.05 ⁇ m to 2.0 ⁇ m.
  • ⁇ Laminated film of layers formed from polymerizable liquid crystal compound> When forming a multi-layer film composed of a plurality of cholesteric liquid crystal layers and a multi-layer film composed of a quarter-wave plate and a plurality of cholesteric liquid crystal layers, each is directly applied to the surface of the quarter-wave plate or the previous cholesteric liquid crystal layer.
  • the liquid crystal composition containing a polymerizable liquid crystal compound or the like may be applied, and the steps of alignment and fixing may be repeated.
  • a separately prepared quarter wave plate, cholesteric liquid crystal layer, or a laminate thereof is used with an adhesive or the like. However, the former is preferable. This is because the interference unevenness derived from the film thickness unevenness of the adhesive layer becomes difficult to be observed.
  • the liquid crystal on the air interface side of the cholesteric liquid crystal layer formed earlier is formed by forming the next cholesteric liquid crystal layer so as to be in direct contact with the surface of the cholesteric liquid crystal layer formed earlier. This is because the orientation direction of the molecules matches the orientation direction of the liquid crystal molecules below the cholesteric liquid crystal layer formed thereon, and the polarization property of the laminate of the cholesteric liquid crystal layer is improved.
  • the half mirror can be produced by transferring a circularly polarized light reflecting layer formed on the temporary support, or a quarter wavelength plate and a circularly polarized light reflecting layer to the front plate.
  • a cholesteric liquid crystal layer or a laminate of cholesteric liquid crystal layers is formed on a temporary support to obtain a circularly polarized light reflecting layer.
  • the surface of the circularly polarized light reflection layer is bonded to the front plate through an adhesive layer. Thereafter, if necessary, the temporary support is peeled off and a quarter-wave plate is provided to obtain a half mirror.
  • a quarter wavelength plate and a cholesteric liquid crystal layer are sequentially formed on the temporary support to obtain a laminate of the quarter wavelength plate and the circularly polarized light reflection layer. Then, the surface of the cholesteric liquid crystal (circularly polarized light reflecting layer) is bonded to the front plate through an adhesive layer. Then, a half mirror can be obtained by peeling a temporary support body as needed.
  • the half mirror can be produced by adhering a circularly polarized light reflecting layer formed on a support, or a quarter wavelength plate and a circularly polarized light reflecting layer to the front plate.
  • the circularly polarized light reflecting layer formed on the support, or the circularly polarized light reflecting layer and 1 ⁇ 4 wavelength plate formed on the support can be used as a half mirror as it is with the support as the front plate.
  • a quarter-wave plate may be separately prepared and bonded.
  • a mirror with an image display function can be produced using the half mirror.
  • the mirror with an image display function includes the half mirror and the image display device.
  • the image display device, the circularly polarized light reflection layer, and the front plate are arranged in this order.
  • the image display device and the half mirror may be in direct contact with each other, an air layer may be present therebetween, or may be directly bonded via an adhesive layer.
  • a half mirror of the main surface having the same area as the image display unit of the image display device may be used, and the main surface area is larger or smaller than the image display unit of the image display device.
  • a half mirror may be used.
  • the slow axis of the quarter wavelength plate is adjusted so that the image is brightest. That is, the relationship between the polarization direction of the linearly polarized light (transmission axis) and the slow axis of the quarter-wave plate so that the linearly polarized light is transmitted best, particularly for an image display device displaying an image by linearly polarized light. Is preferably adjusted. For example, in the case of a quarter wavelength plate, it is preferable that the transmission axis and the slow axis form an angle of 45 °.
  • the light emitted from the image display device displaying an image by linearly polarized light is circularly polarized light of either right or left sense after passing through the quarter wavelength plate.
  • the circularly polarized light reflecting layer described later only needs to be composed of a cholesteric liquid crystal layer having a twist direction that transmits the circularly polarized light of the above-described sense.
  • the image display device is not particularly limited.
  • the image display device is preferably an image display device that emits (emits light) linearly polarized light to form an image.
  • the image display device is more preferably a liquid crystal display device or an organic EL device.
  • the liquid crystal display device may be a transmission type or a reflection type, and is particularly preferably a transmission type.
  • the liquid crystal display device includes IPS (In Plane Switching) mode, FFS (Fringe Field Switching) mode, VA (Vertical Alignment) mode, ECB (Electrically Controlled Birefringence) mode, STN (Super Twisted Nematic) mode, TN (Twisted Nematic) mode, Any liquid crystal display device such as an OCB (Optically Compensated Bend) mode may be used.
  • IPS In Plane Switching
  • FFS Frringe Field Switching
  • VA Very Alignment
  • ECB Electrical Controlled Birefringence
  • STN Super Twisted Nematic
  • TN Transmission Nematic
  • Any liquid crystal display device such as an OCB (Optically Compensated Bend) mode may be used.
  • the image displayed on the image display unit of the image display device may be a still image, a moving image, or simply text information. Further, it may be a monochrome display such as black and white, a multi-color display, or a full-color display.
  • a preferable example of the image displayed on the image display unit of the image display device is an image taken by a vehicle-mounted camera. This image is preferably a moving image.
  • the image display device only needs to indicate the emission peak wavelength ⁇ R of red light, the emission peak wavelength ⁇ G of green light, and the emission peak wavelength ⁇ B of blue light in the emission spectrum during white display.
  • ⁇ R may be any wavelength in the range of 580 nm to 700 nm, preferably in the range of 610 nm to 680 nm.
  • ⁇ G may be any wavelength in the range of 500 nm to 580 nm, preferably in the range of 510 nm to 550 nm.
  • ⁇ B may be any wavelength in the range of 400 nm to 500 nm, preferably in the range of 440 nm to 480 nm.
  • the half mirror or the mirror with an image display function of the present invention may include an image display device, a circularly polarized light reflection layer, and other adhesive layers for bonding each layer.
  • the adhesive layer may be formed from an adhesive.
  • the other adhesive layer the same adhesive layer as the adhesive layer for adhering the circularly polarized light reflecting layer and the front plate can be used.
  • an adhesive layer generally made of a sheet-like adhesive is preferable.
  • the mirror with an image display function can be manufactured by arranging the half mirror on the image display side of the image display device and integrating the image display device and the half mirror. In the half mirror, the image display device, the circularly polarizing reflection layer, and the front plate are arranged in this order.
  • the integration of the image display device and the half mirror may be performed by connection with a frame or a hinge or adhesion.
  • the mirror with an image display function of the present invention can be manufactured by adhering a half mirror to the image display surface of the image display device. Adhesion is performed so that the front plate, the circularly polarized light reflection layer, and the image display device are in this order.
  • the half mirror of the present invention may be provided as a half mirror with a polarizer. You may manufacture the mirror with an image display function using the half mirror with a polarizer. That is, in an image display device having a polarizing plate on the image display surface side, which is an image display device that emits linearly polarized light and forms an image, an image display function is achieved by using a half mirror with a polarizer instead of the polarizing plate.
  • a mirror can be manufactured.
  • the polarizer, the circularly polarized light reflection layer, and the front plate may be arranged in this order.
  • the polarizer may be bonded to, for example, a circularly polarized light reflection layer or a quarter wave plate.
  • the polarizer examples include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer.
  • the iodine-based polarizer and the dye-based polarizer are generally produced using a polyvinyl alcohol film.
  • a polarizer can be composed of modified or unmodified polyvinyl alcohol and dichroic molecules.
  • a polarizer composed of modified or unmodified polyvinyl alcohol and a dichroic molecule reference can be made to, for example, the description in JP-A-2009-237376.
  • the film thickness of a polarizer should just be 50 micrometers or less, 30 micrometers or less are preferable and 20 micrometers or less are more preferable. Moreover, the film thickness of a polarizer should just be 1.0 micrometer or more, 5.0 micrometers or more, or 10 micrometers or more normally.
  • the polarizer preferably has a polarizer protective layer on one or both main surfaces. In the case of having a polarizer protective layer on one of the main surfaces, the surface may be bonded to the circularly polarized light reflecting layer or the quarter-wave plate, or the opposite surface, but the opposite surface Preferably there is.
  • a cellulose acylate polymer film As the polarizer protective layer, a cellulose acylate polymer film, an acrylic polymer film, or a cycloolefin polymer film can be used.
  • cellulose acylate polymer reference can be made to the description of the cellulose acylate resin in JP2011-237474A.
  • the cycloolefin-based polymer film the descriptions in JP2009-175222A and JP2009-237376A can be referred to.
  • the polarizer protective layer may contain one or more of the above polymers as a main component, for example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 99% by mass or more. Or 100% by mass.
  • the film thickness of the polarizer protective layer may be 100 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, or 1.0 ⁇ m or more, 5.0 ⁇ m or more, and 10 ⁇ m or more.
  • the polarizer protective layer may be provided by a method such as directly applying and drying the protective layer forming composition on the surface on which the protective layer is provided, or may be adhered via an adhesive layer.
  • the use of the mirror with an image display function is not particularly limited. For example, it can be used as a security mirror, a beauty salon or a barber mirror, and can display images such as character information, still images, and moving images. Further, the mirror with an image display function of the present invention may be a vehicle rearview mirror, and may be used as a television, a personal computer, a smartphone, or a mobile phone.
  • the mirror with an image display function is particularly preferably used as a vehicle rearview mirror.
  • the mirror with an image display function may have a frame, a housing, a support arm for attaching to the vehicle body, and the like for use as a rearview mirror.
  • the vehicle image display function-equipped mirror may be formed for incorporation into a room mirror. In the vehicle-mounted image display function-equipped mirror having the above shape, it is possible to specify the vertical and horizontal directions during normal use.
  • the mirror By curving the mirror with an image display function so that the convex curved surface is on the front side, it is possible to make a wide mirror that can visually recognize the rear visual field and the like in a wide angle.
  • a curved front surface can be produced using a curved half mirror.
  • the curve may be in the vertical direction, the horizontal direction, or both the vertical direction and the horizontal direction.
  • the curvature may be a curvature radius of 500 mm to 3000 mm. More preferably, it is 1000 mm to 2500 mm.
  • the radius of curvature is the radius of the circumscribed circle when the circumscribed circle of the curved portion is assumed in the cross section.
  • a coating solution for forming a cholesteric liquid crystal layer having the following composition.
  • Compound 1 80 parts by mass Compound 2 20 parts by mass Fluorine-based horizontal alignment agent 1 0.1 part by mass Fluorine-based horizontal alignment agent 2 0.007 parts by mass Right-turning chiral agent LC756 (manufactured by BASF) Target Adjusted according to the reflection wavelength of the polymerization initiator IRGACURE OXE01 (manufactured by BASF) 3.0 parts by mass Solvent (methyl ethyl ketone) Amount that the solute concentration is 30% by mass
  • Coating solutions 1 to 3 were prepared by adjusting the prescription amount of the chiral agent LC-756 having the above coating solution composition. Using each coating solution, a single cholesteric liquid crystal layer was prepared on a temporary support in the same manner as in the preparation of the following circularly polarized reflective layer, and the reflection characteristics were confirmed. The prepared cholesteric liquid crystal layers were all right circularly polarized light reflecting layers, and the central reflection wavelength was as shown in Table 1 below.
  • a quarter-wave plate forming coating solution having the following composition.
  • Compound 1 80 parts by mass Compound 2 20 parts by mass Fluorine-based horizontal alignment agent 1 0.1 part by mass Fluorine-based horizontal alignment agent 2 0.007 parts by mass Polymerization initiator IRGACURE OXE01 (manufactured by BASF) 3.0 Part by mass / solvent (methyl ethyl ketone) Amount of solute concentration of 30% by mass
  • Coating liquid for barrier layer formation A coating solution having the following composition was prepared. About each coating liquid, Tg was obtained by DSC in the above-mentioned procedure.
  • (C) Coating liquid for forming a barrier layer containing a plurality of acrylate monomers (Example 5) ⁇ Urethane (meth) acrylate monomer U-6LPA (made by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass ⁇ Urethane acrylate resin UA122P (made by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass ⁇ Polymer surfactant B1176 (Dainippon Chemical) Manufactured by Kogyo Co., Ltd.) 0.05 parts by mass / polymerization initiator IRGACURE OXE01 (manufactured by BASF) 1.0 parts by mass / solvent (methyl ethyl ketone) Amount at which the solute concentration is 40% by mass
  • (D) Coating liquid for forming a barrier layer containing an epoxy monomer (Examples 6 to 10) -Epoxy monomer listed in Table 2 100 parts by mass-Polymer surfactant B1176 (Dainippon Chemical Co., Ltd.) 0.05 part by mass-Polymerization initiator PAG-1 1.0 part by mass-Solvent (methyl ethyl ketone and methyl (A mixture of isobutyl ketone at 3: 7) Amount at which the solute concentration is 40% by mass
  • the monomers in Table 2 show the following.
  • U6LPA Urethane (meth) acrylate monomer U-6LPA (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • U4HA Urethane (meth) acrylate monomer U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • EBECRY220 Aromatic urethane acrylate EBECRYL220 (manufactured by Daicel Ornex Co., Ltd.)
  • ⁇ 8BR-600 Urethane polymer 8BR-600 (manufactured by Taisei Fine Chemical Co., Ltd.)
  • UA122P Urethane acrylate resin UA122P (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • CEL2021P bifunctional alicyclic epoxy resin ceroxide 2021P (manufactured by Daicel Corporation)
  • CEL8000 Alicyclic epoxy resin Celoxide 8000 (manufactured
  • PET30 Pentaerythritol (tri / tetra) acrylate KAYARAD PET-30 (Nippon Kayaku Co., Ltd.)
  • DPCA20 caprolactone-modified dipentaerythritol hexaacrylate DPCA20 (manufactured by Nippon Kayaku Co., Ltd.)
  • DPCA120 caprolactone-modified dipentaerythritol hexaacrylate DPCA120 (manufactured by Nippon Kayaku Co., Ltd.)
  • the quarter wavelength plate forming coating solution was applied to the rubbed surface of the PET film using a wire bar and then dried. Next, this was placed on a hot plate at 30 ° C., and UV irradiation was performed for 6 seconds with an electrodeless lamp “D bulb” (60 mW / cm 2 ) manufactured by Fusion UV Systems Co., Ltd. A retardation layer (1 ⁇ 4 wavelength plate) of 8 ⁇ m was obtained. The coating liquid 1 was applied to the surface of the obtained retardation layer using a wire bar and then dried.
  • the laminated body A which consists of a quarter wavelength plate and a circularly-polarized light reflection layer (three cholesteric liquid crystal layers) was obtained.
  • the barrier layer forming coating solution is applied to the surface of the laminate A on the cholesteric liquid crystal layer side at room temperature so that the dry film thickness after drying is 3.0 ⁇ m. Further application was performed using a wire bar.
  • the coating layer was dried at room temperature for 10 seconds, heated in an atmosphere of 85 ° C. for 1 minute, and then irradiated with UV at 70 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 80% for 5 seconds.
  • an OCA tape (MHM-FWD25, film thickness 25 ⁇ m, manufactured by Nichiei Kako Co., Ltd.) was bonded to a 50 mm square glass plate, and then the protective film of the OCA tape was peeled off.
  • bonding was performed on the glass plate with the adhesive layer of OCA and the surface of the laminate A on the side of the circularly polarized light reflecting layer, or on the surface of the laminate A with the barrier layer on the side of the barrier layer. Thereafter, the temporary support (PET) was peeled off to produce a 50 mm square half mirror.
  • the half mirror of Example 17 was produced by the procedure described above.
  • a triacetyl cellulose film (Fujitack, thickness 80 ⁇ m) manufactured by Fuji Film Co., Ltd. was used as a support (150 mm ⁇ 100 mm).
  • a predetermined amount of a 2% by mass solution of long-chain alkyl-modified bhopal (MP-203, manufactured by Kuraray Co., Ltd.) was applied on the support, and then dried to form an alignment film resin layer.
  • One side was subjected to rubbing treatment (rayon cloth, pressure: 0.5 kgf (4.9 N), rotation speed: 1000 rpm, conveyance speed: 10 m / min, number of times: 1 reciprocation), and a support with an alignment layer was obtained. .
  • Triacetylcellulose (Fujitack, manufactured by Fuji Film Co., Ltd.) was used as a support (150 mm ⁇ 100 mm).
  • a rubbing treatment (rayon cloth, pressure: 0.5 kgf (4.9 N), rotation speed: 1000 rpm, conveyance speed: 10 m / min, number of times: 1 reciprocation) was performed on one surface.
  • the coating solution 1 was applied to the rubbed surface using a wire bar and then dried.
  • Hard coat composition / acrylate monomer DPHA (manufactured by Shin-Nakamura Chemical Co., Ltd.) 76.5 parts by mass / methacrylate monomer Cyclomer M-100 (manufactured by Daicel) 23.5 parts by mass / antifouling agent RS-90 (DIC) 0.7 parts by mass, inorganic particles MEK-AC-2140Z (manufactured by Nissan Chemical Industries) 15.0 parts by mass, polymerization initiator IRGACURE 184 (manufactured by BASF) 4.0 parts by mass, polymerization initiator PAG-1. 5 parts by mass / solvent (methyl ethyl ketone) 40.0 parts by mass / solvent (methyl isobutyl ketone) 60.0 parts by mass
  • One side was subjected to rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), rotation speed: 1000 rpm, conveyance speed: 10 m / min, number of times: 1 reciprocation).
  • the quarter-wave plate forming coating solution was applied to the rubbed surface of the PET film using a wire bar and then dried.
  • a 80 ⁇ m thick triacetyl cellulose film (Fujitac, manufactured by Fuji Film Co., Ltd.) was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes, and then neutralized and washed with water. Iodine was adsorbed on a polyvinyl alcohol film and stretched to produce a polarizer. A triacetyl cellulose film after washing with water was bonded to one side of the produced polarizer. On the other surface of the polarizer, a UV adhesive composition A having the following composition was applied and applied using a wire bar so that the film thickness after curing was 2.5 ⁇ m.
  • UV adhesive composition A ⁇ Denacol EX-211 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass. WPBG-056 (manufactured by Daicel Corporation) 7.5 parts by mass. Composition A was applied. The laminate C and the polarizer were bonded so that the surfaces coated with the UV adhesive composition A were not bubbled, and an electrodeless lamp “D bulb” (60 mW / cm) manufactured by Fusion UV Systems Co., Ltd. 2 ) UV irradiation was performed for 10 seconds. Thus, the half mirror with a polarizer was produced.
  • Esterification reaction In a first esterification reaction tank, 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol were mixed for 90 minutes to form a slurry, and continuously at a flow rate of 3800 kg / h. It supplied to the esterification reaction tank. Further, an ethylene glycol solution of antimony trioxide was continuously supplied, and the reaction was carried out at a reaction vessel temperature of 250 ° C. with stirring and an average residence time of about 4.3 hours. At this time, antimony trioxide was continuously added so that the amount of Sb added was 150 ppm in terms of element.
  • the reaction product was transferred to a second esterification reaction vessel, and reacted with stirring at a temperature in the reaction vessel of 250 ° C. and an average residence time of 1.2 hours.
  • an ethylene glycol solution of magnesium acetate and an ethylene glycol solution of trimethyl phosphate are continuously supplied so that the added amount of Mg and the added amount of P are 65 ppm and 35 ppm in terms of element, respectively. did.
  • the esterification reaction product obtained above is continuously supplied to the first polycondensation reaction tank, and with stirring, the reaction temperature is 270 ° C. and the pressure in the reaction tank is 20 torr (2.67 ⁇ 10 ⁇ 3 MPa). The polycondensation was carried out with an average residence time of about 1.8 hours.
  • reaction tank temperature was 276 ° C.
  • reaction tank pressure was 5 torr (6.67 ⁇ 10 ⁇ 4 MPa)
  • residence time was about 1.2 hours.
  • the reaction (polycondensation) was performed under the conditions.
  • the reaction tank temperature was 278 ° C.
  • the reaction tank pressure was 1.5 torr (2.0 ⁇ 10 ⁇ 4 MPa)
  • the residence time was 1.5 hours.
  • the reaction product polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • polyester pellets cross section: major axis: about 4 mm, minor axis: about 2 mm, length: about 3 mm).
  • This polymer was designated as raw material polyester 1 (hereinafter abbreviated as PET1).
  • the molten resin was extruded from the die under the conditions that the pressure fluctuation was 1% and the temperature distribution of the molten resin was 2%. Specifically, the back pressure was increased by 1% with respect to the average pressure in the barrel of the extruder, and the piping temperature of the extruder was heated at a temperature 2% higher than the average temperature in the barrel of the extruder.
  • the molten resin extruded from the die was extruded onto a cooling cast drum set at a temperature of 25 ° C., and was brought into close contact with the cooling cast drum using an electrostatic application method. It peeled using the peeling roll arrange
  • the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the I layer, the II layer, and the III layer was 10:80:10. Moreover, the unstretched polyester film from which thickness differs was changed by changing the conditions which extrude molten resin from die
  • a coating solution H was prepared with the composition shown below.
  • (Coating liquid H) Water 56.6 parts by mass acrylic resin (A1, solid content 28% by mass) 21.4 parts by mass carbodiimide compound: (B1, solid content 40% by mass) 2.9 parts by mass surfactant (E1, solid content 1% by mass) 8.1 parts by weight surfactant (E2, solid content 1% by weight aqueous solution) 9.6 parts by weight particles (F1, solid content 40% by weight) 0.4 parts by weight lubricant (G, solid content 30% by weight) 1.0 part by weight
  • the polyester film was divided into 1.4 m widths in the width direction, and the chuck portion was trimmed. Then, after extruding (knurling) at a width of 10 mm on both ends of each divided roll, it was wound up 2000 m at a tension of 18 kg / m.
  • the divided samples were designated as an end A, a center B, and an end C from one end side, and the center B was used.
  • the obtained retardation film had a film thickness of 80 ⁇ m, and the front phase difference measured by Axoscan was 8060 nm.
  • Laminate F (Half Mirror) Using a laminator, an OCA tape (MHM-FWD25 film thickness 25 ⁇ m, manufactured by Niei Kaiko Co., Ltd.) is bonded to the barrier layer side of the laminate D, and then the OCA tape is protected. The film was peeled off. A laminate F was obtained by laminating a surface opposite to the hard coat application surface of the laminate E on the release surface using a laminator.
  • the UV adhesive composition A was applied to the triacetyl cellulose surface of the laminate F.
  • Laminate F and the above polarizer were bonded so that the surfaces coated with UV adhesive composition A were not bubbled, and an electrodeless lamp “D bulb” (60 mW / cm) manufactured by Fusion UV Systems Co., Ltd. 2 ) UV irradiation was performed for 10 seconds.
  • an electrodeless lamp “D bulb” 60 mW / cm manufactured by Fusion UV Systems Co., Ltd. 2
  • a laminate G of a quarter-wave plate and a circularly polarizing reflective layer is obtained in the same manner as in the production of the laminate A, except that the same amount of IRGACURE 819 (manufactured by BASF) is used as a polymerization initiator instead of IRGACURE OXE01. It was.
  • An OCA tape (MHM-FWD25, film thickness 25 ⁇ m, manufactured by Nichiei Kako Co., Ltd.) was bonded to the surface of the circularly polarized reflective layer of the laminate G. Thereafter, the temporary support was peeled off to obtain Sample 1.
  • the horizontal axis represents the cutting time and corresponds to the depth
  • the vertical axis represents the observed signal intensity of the ions (corresponding to the amount of substance).
  • “Fresh” is the analysis result before the environmental test
  • “wet” is the analysis result after the environmental test at 85 ° C. and 85% relative humidity 85%
  • “Dry” is an analysis result after an environmental test at 110 ° C. for 160 hours.
  • the polymerization initiator IRGACURE819 C 26 H 27 PO 3 ⁇
  • its decomposition product PO 2 ⁇
  • Sample 2 was produced in the same procedure except that the laminate A was used instead of the laminate G. The same analysis by TOF-SIMS was performed on this sample 2. As a result, a result showing that the polymerization initiator IRGACURE OXE01 and the decomposition product were transferred as in the case of sample 1 was obtained.
  • a coating solution for forming a barrier layer having the following composition was applied to the surface of the circularly polarized light reflecting layer of the laminate G using a wire bar at room temperature so that the dry film thickness after drying was 3.0 ⁇ m. .
  • the coating layer was dried at room temperature for 10 seconds, and then heated at 85 ° C. for 1 minute. Thereafter, UV irradiation was performed at 70 ° C. with a fusion D bulb (lamp 90 mW / cm) at an output of 80% for 5 seconds to obtain a barrier layer.
  • OCA MHM-FWD25 film thickness 25 ⁇ m, manufactured by Niei Kaiko Co., Ltd.
  • Sample 3 was similarly analyzed by TOF-SIMS, and no data indicating that the chiral agent, the polymerizable liquid crystal compound, the polymerization initiator, or any of the decomposition products thereof had moved was obtained.
  • Circularly polarized reflective layer 2 Adhesive layer (adhesive layer in contact with the barrier layer) 3 Front plate 4 Barrier layer 5 1/4 wavelength plate 6 Polarizer 10 Support 11 Orientation layer 12 Other adhesive layer 16 Polarizer protective layer 21 Glass plate or plastic film 22 High Re retardation film 23 Optical functional layer

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

Abstract

La présente invention porte : sur un miroir ayant une fonction d'affichage d'image qui permet à un utilisateur d'observer une image d'affichage et une image de réflexion de miroir sans dépendance directionnelle même à travers des lunettes de soleil polarisées et est capable d'afficher une image claire et de bonne couleur; et sur un demi-miroir pour obtenir le miroir avec une fonction d'affichage d'image. Le demi-miroir comprend : une couche de réflexion de lumière polarisée de manière circulaire comprenant une couche de cristaux liquides cholestériques; une couche barrière; une couche adhésive; et une plaque de surface avant. La couche barrière est disposée entre la couche adhésive et la couche de réflexion de lumière polarisée de manière circulaire et est formée par durcissement d'une composition contenant, par exemple, un monomère (méth)acrylate d'uréthane.
PCT/JP2017/009980 2016-05-31 2017-03-13 Demi miroir et miroir ayant une fonction d'affichage d'image WO2017208559A1 (fr)

Priority Applications (1)

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US16/172,192 US20190072819A1 (en) 2016-05-31 2018-10-26 Half mirror and mirror with image display function

Applications Claiming Priority (4)

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JP2016108561 2016-05-31
JP2016-108561 2016-05-31
JP2016-122604 2016-06-21
JP2016122604A JP6632479B2 (ja) 2016-05-31 2016-06-21 ハーフミラーおよび画像表示機能付きミラー

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005055887A (ja) * 2003-07-22 2005-03-03 Dainippon Printing Co Ltd 投影スクリーン及びそれを備えた投影システム
JP2007334206A (ja) * 2006-06-19 2007-12-27 Dainippon Printing Co Ltd 光学素子およびその製造方法
JP2015072410A (ja) * 2013-10-04 2015-04-16 富士フイルム株式会社 コレステリック液晶層を含む熱圧着貼合用フィルムおよびその応用
JP2015125240A (ja) * 2013-12-26 2015-07-06 日本ゼオン株式会社 光制御素子及び車載用液晶表示装置
WO2015141818A1 (fr) * 2014-03-20 2015-09-24 富士フイルム株式会社 Composition, membrane de réflexion de lumière, film d'amélioration de luminosité, unité de rétroéclairage, et dispositif d'affichage à cristaux liquides
JP2015194675A (ja) * 2013-08-26 2015-11-05 富士フイルム株式会社 輝度向上フィルム、光学シート部材および液晶表示装置
JP2016071078A (ja) * 2014-09-29 2016-05-09 富士フイルム株式会社 投映像表示用部材および投映像表示システム
JP2016090993A (ja) * 2014-10-31 2016-05-23 富士フイルム株式会社 光学部材および光学部材を有する画像表示装置

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005055887A (ja) * 2003-07-22 2005-03-03 Dainippon Printing Co Ltd 投影スクリーン及びそれを備えた投影システム
JP2007334206A (ja) * 2006-06-19 2007-12-27 Dainippon Printing Co Ltd 光学素子およびその製造方法
JP2015194675A (ja) * 2013-08-26 2015-11-05 富士フイルム株式会社 輝度向上フィルム、光学シート部材および液晶表示装置
JP2015072410A (ja) * 2013-10-04 2015-04-16 富士フイルム株式会社 コレステリック液晶層を含む熱圧着貼合用フィルムおよびその応用
JP2015125240A (ja) * 2013-12-26 2015-07-06 日本ゼオン株式会社 光制御素子及び車載用液晶表示装置
WO2015141818A1 (fr) * 2014-03-20 2015-09-24 富士フイルム株式会社 Composition, membrane de réflexion de lumière, film d'amélioration de luminosité, unité de rétroéclairage, et dispositif d'affichage à cristaux liquides
JP2016071078A (ja) * 2014-09-29 2016-05-09 富士フイルム株式会社 投映像表示用部材および投映像表示システム
JP2016090993A (ja) * 2014-10-31 2016-05-23 富士フイルム株式会社 光学部材および光学部材を有する画像表示装置

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