WO2014084361A1 - 異方性光学フィルム - Google Patents
異方性光学フィルム Download PDFInfo
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- WO2014084361A1 WO2014084361A1 PCT/JP2013/082204 JP2013082204W WO2014084361A1 WO 2014084361 A1 WO2014084361 A1 WO 2014084361A1 JP 2013082204 W JP2013082204 W JP 2013082204W WO 2014084361 A1 WO2014084361 A1 WO 2014084361A1
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- light
- optical film
- anisotropic optical
- linear transmittance
- region
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0257—Diffusing elements; Afocal elements characterised by the diffusing properties creating an anisotropic diffusion characteristic, i.e. distributing output differently in two perpendicular axes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133504—Diffusing, scattering, diffracting elements
Definitions
- the present invention relates to an anisotropic optical film having a prismatic structure inside.
- the light diffusing member is used not only in lighting fixtures and building materials but also in display devices.
- Examples of the display device include a liquid crystal display device (LCD) and an organic electroluminescence element (organic EL).
- LCD liquid crystal display device
- organic EL organic electroluminescence element
- scattering due to unevenness formed on the surface surface scattering
- scattering due to a refractive index difference between the matrix resin and fine particles dispersed therein internal scattering
- surface scattering scattering due to a refractive index difference between the matrix resin and fine particles dispersed therein
- surface scattering This is due to both internal scattering.
- these light diffusing members generally have isotropic diffusion performance, and even if the incident angle is slightly changed, the diffusion characteristics of the transmitted light are not greatly different.
- an anisotropic optical film in which incident light in a certain angle region is strongly diffused and incident light at other angles is transmitted (for example, Patent Document 1).
- This anisotropic optical film is cured by irradiating light from above the sheet-like photosensitive composition layer using a linear light source. Then, in the sheet-like substrate, as shown in FIG. 10, the peripheral region and the refractive index coincide with the length direction of the linear light source 51 disposed above when the anisotropic optical film 50 is produced. It is considered that different plate-like structures 40 are formed in parallel to each other. As shown in FIG.
- a sample 1 anisotropic optical film
- a light source not shown
- a light receiver 3 a light receiver 3
- the sample is transmitted straight through while changing the angle around the straight line L of the sample surface as a central axis.
- the linear transmittance entering the light receiver 3 can be measured.
- FIG. 11 shows the incident angle dependence of the scattering characteristics of the anisotropic optical film 50 shown in FIG. 10 measured using the method shown in FIG.
- FIG. 11 shows an evaluation of an anisotropic optical film having a plate-like structure as in Comparative Examples 2 and 3 described later.
- the vertical axis indicates the linear transmittance (an amount of parallel light emitted in the same direction as the incident direction when a predetermined amount of parallel light is incident), which is an index indicating the degree of scattering, and the horizontal axis indicates the incident angle. Indicates.
- the solid line and the broken line in FIG. 11 respectively rotate the anisotropic optical film 50 about the AA axis (through the plate-like structure) and the BB axis (parallel to the plate-like structure) in FIG.
- the sign of the incident angle indicates that the direction in which the anisotropic optical film 50 is rotated is opposite.
- the solid line in FIG. 11 shows that the linear transmittance remains small both in the front direction and in the oblique direction. This is because the optical film 50 is scattered regardless of the incident angle when rotated about the AA axis. It means a state.
- the broken line in FIG. 11 shows that the linear transmittance is small in the direction near 0 °. This is also true when the optical film is rotated with respect to the light in the front direction when rotated about the BB axis. Means that it is in a scattering state.
- the linear transmittance increases in the direction where the incident angle is large.
- the anisotropic optical film transmits light in an oblique direction. It means that. Thanks to this structure, for example, although the transmissivity varies depending on the incident angle in the horizontal direction, the transmissivity does not change even if the incident angle is changed in the vertical direction.
- the curve indicating the incident angle dependence of the scattering characteristics as shown in FIG. 11 is hereinafter referred to as “optical profile”.
- the optical profile does not directly represent the scattering characteristics, but if it is interpreted that the diffuse transmittance is increased due to the decrease of the linear transmittance, the diffusion profile is generally indicated. I can say that.
- the anisotropic optical film 50 has optical characteristics defined by the inclination of the plate-like structure 40 with respect to the film normal. In this case, the incident light from a direction substantially parallel to the plate-like structure 40 is strongly diffused, and the incident light passing through the plate-like structure is transmitted without being diffused. It can be said.
- the anisotropic optical film 50 Since the properties of the anisotropic optical film 50 depend on the inclination of the plate-like structure and the inclination of incident light, the incident angle range when light is strongly diffused is limited. In addition, since the anisotropic optical film 50 has a very steep change in diffusivity when the incident angle is changed, when it is applied to a display device, it appears as a sudden change in visibility, giving an unnatural impression. There was something to hold me. In order to solve this problem, there is a method of laminating a plurality of anisotropic optical films in which the inclination of the plate-like structure is changed. However, there is a problem that the cost is high, and improvement is required. In addition, the anisotropic optical film having a plate-like structure is likely to cause light interference (rainbow), and improvement in visibility has been demanded.
- drainbow light interference
- An object is to provide an anisotropic optical film in which interference (rainbow) hardly occurs.
- the present invention has solved the above problems by the following technical configuration.
- An anisotropic optical film whose diffusivity changes according to the incident angle of light, which has a plurality of prismatic regions and a matrix region, and has a maximum linear transmittance at an incident angle at which the linear transmittance is maximum.
- An anisotropic optical film characterized in that the minimum linear transmittance at an incident angle at which the linear transmittance is minimum is 20% or less.
- the angle range of the diffusion range of incident light with respect to the linear transmittance at which the difference between the maximum linear transmittance and the minimum linear transmittance is 1 ⁇ 2 or less is 50 ° to 80 °.
- a display device comprising the anisotropic optical film.
- a step of obtaining parallel light from a light source a step of obtaining the light having directivity by causing the parallel light to enter the directional diffusion element, and the light having directivity in the photocurable composition layer And a step of allowing the photocurable composition layer to enter and curing the photocurable composition layer.
- FIG. 2 is an optical profile of an anisotropic optical film of Example 1.
- FIG. 2 is an optical profile of an anisotropic optical film of Example 2.
- 2 is an optical profile of an anisotropic optical film of Example 3.
- FIG. 4 is an optical profile of an anisotropic optical film of Example 4.
- 2 is an optical profile of an anisotropic optical film of Comparative Example 1.
- 5 is an optical profile of an anisotropic optical film of Comparative Example 2.
- 10 is an optical profile of an anisotropic optical film of Comparative Example 3.
- the “low refractive index region” and the “high refractive index region” are regions formed by a difference in local refractive index of the material constituting the anisotropic optical film and have a lower refractive index than the other. It is a relative one indicating whether it is expensive. These regions are formed when the material forming the anisotropic optical film is cured.
- “Diffusion center axis” means a direction in which the scattering characteristic coincides with the incident angle of light having a substantially target property with the incident angle as a boundary when the incident angle is changed. The reason for having “substantially target” is because it does not strictly have the target of optical characteristics.
- the diffusion center axis can be found by observing the inclination of the film cross section with an optical microscope or by observing the projection shape of light through the anisotropic optical film while changing the incident angle.
- Linear transmittance is the ratio of the amount of transmitted light in the linear direction and the amount of incident light when incident from an incident angle, with respect to the linear transmittance of the incident light on the anisotropic optical film. It is expressed by a formula.
- Linear transmittance (%) (Linear transmitted light amount / incident light amount) ⁇ 100
- FIG. 1 is a schematic view of an anisotropic optical film 5 of the present invention.
- 1A is a plan view of the anisotropic optical film 5
- FIG. 1B is a cross-sectional view of the anisotropic optical film 5 cut along the line CC in FIG. 1A.
- the anisotropic optical film 5 has a plurality of prismatic regions 6 and a matrix region 4.
- the plurality of prismatic regions 6 and the matrix regions 4 have an irregular distribution and shape, but are formed over the entire surface of the anisotropic optical film, so that the obtained optical properties (for example, linear transmittance described later) are The measurement is the same regardless of the location. Since the plurality of prismatic regions 6 and the matrix region 4 have an irregular distribution or shape, the anisotropic optical film 5 of the present invention is less likely to cause light interference (rainbow).
- the surface shape of the prismatic region 6 has a short diameter SA and a long diameter LA as shown in FIG.
- the short diameter SA and the long diameter LA can be confirmed by observing the anisotropic optical film with an optical microscope (plan view).
- the surface shape of the prismatic column region 6 is not particularly limited as long as it satisfies the diffusion range described later, and may be linear or wavy, or a mixture of both.
- the cross-sectional shape of the prismatic region 6 is formed such that the prismatic regions 6 and the matrix regions 4 are alternated.
- FIG. 1B shows a shape in which the prismatic region 6 extends linearly in the direction of the thickness T, it may be linear, wavy or bent, or these may enter. It may be mixed.
- region 4 should just differ from the refractive index of the prismatic area
- the matrix region 4 becomes a low refractive index region.
- the matrix region 4 becomes a high refractive index region.
- the refractive index at the interface between the matrix region 4 and the prismatic region 6 preferably changes gradually.
- the diffusive change when the incident angle is changed becomes very steep, and the problem of easily giving an unnatural impression is less likely to occur.
- the refractive index of the interface between the matrix region 4 and the prismatic region 6 can be gradually increased.
- the lower limit of the aspect ratio of the minor axis SA and the major axis LA is preferably 2, more preferably 4, and even more preferably 6. As the aspect ratio becomes smaller, there is a problem that the maximum linear transmittance at the incident angle at which the linear transmittance becomes maximum becomes lower.
- the upper limit of the aspect ratio of the minor axis SA and the major axis LA is preferably 40, more preferably 25, and even more preferably 15. As the aspect ratio increases, there is a problem in that the light diffusion range becomes narrower. Further, there is a problem that light interference (rainbow) is more likely to occur as the aspect ratio increases.
- These lower limit value and upper limit value of the aspect ratio can be appropriately combined. For example, by setting the aspect ratio of the prismatic region 6 to 2 to 40, the diffusion range can be widened, and the change in diffusivity when the incident angle is changed becomes extremely steep and it is easy to give an unnatural impression. Problems are less likely to occur.
- the lower limit of the length of the minor axis SA of the prismatic region 6 is preferably 0.5 ⁇ m, and more preferably 1.0 ⁇ m. As the minor axis SA becomes shorter, there is a problem that light diffusibility and light condensing properties become insufficient.
- the upper limit of the length of the minor axis SA of the prismatic region 6 is preferably 5.0 ⁇ m, more preferably 3.0 ⁇ m, and even more preferably 2.0 ⁇ m. There is a problem that the diffusion range becomes narrow as the minor axis SA becomes longer.
- These lower limit value and upper limit value of the minor axis SA of the prismatic region 6 can be appropriately combined. For example, by setting the short axis SA of the prismatic region 6 to 0.5 ⁇ m to 5.0 ⁇ m, the diffusion range can be widened and the light diffusibility and light condensing properties are sufficient.
- the lower limit of the length of the major axis LA of the prismatic region 6 is preferably 3.0 ⁇ m, and more preferably 5 ⁇ m. There is a problem that the diffusion range becomes narrower as the major axis LA becomes smaller.
- the upper limit of the length of the major axis LA of the prismatic region 6 is preferably 40 ⁇ m, more preferably 20 ⁇ m, and even more preferably 10 ⁇ m. There is a problem that the diffusion range becomes narrower as the major axis LA becomes larger, and a change in diffusibility when the incident angle is changed becomes extremely steep and an unnatural impression is easily given. There is also a problem that light interference (rainbow) tends to occur when the major axis LA becomes large.
- the thickness T of the prismatic region 6 By setting the thickness T of the prismatic region 6 to 30 ⁇ m to 200 ⁇ m, the problem of cost is reduced and the contrast of the image is sufficient.
- the lower limit value of the thickness T of the prismatic region 6 is preferably 30 ⁇ m, and more preferably 50 ⁇ m. As the thickness T decreases, there is a problem that light diffusibility and light condensing properties become insufficient.
- the upper limit value of the thickness T of the prismatic region 6 is preferably 200 ⁇ m, more preferably 150 ⁇ m, and even more preferably 100 ⁇ m. As the thickness T increases, the cost of materials increases and the time required for manufacturing increases, and blurring tends to occur in the image due to increased diffusion in the thickness T direction. There is a problem that the contrast tends to decrease. These lower limit value and upper limit value of the thickness T of the prismatic region 6 can be appropriately combined.
- the aspect ratio, the length of the minor axis SA, the length of the major axis LA, and the thickness T of the prismatic region 6 can be appropriately combined with the above numerical ranges.
- the upper surface 5a and the lower surface 5b of the anisotropic optical film 5 are illustrated.
- the upper surface 5a and the lower surface 5b are provided for the sake of convenience. If the anisotropic optical film 5 is turned upside down, it is reversed (lower surface and upper surface).
- the surface shapes of the upper surface 5a and the lower surface 5b of the anisotropic diffusion layer 5 are preferably different. Thereby, the anisotropic optical film 5 of the present invention can reduce the occurrence of light interference (rainbow).
- the surface shapes of the upper surface 5a and the lower surface 5b can be made different.
- the prismatic region 6 is gradually formed in the thickness T direction from the light-irradiated surface, but after the prismatic region 6 reaches the other surface (the opposite surface of the light-irradiated surface), the prismatic region 6 is further increased. This is because of stretching. In such a case, the prismatic region 6 can be easily confirmed by observing the other surface with an optical microscope.
- the interface between the prismatic column region 4 and the matrix region 6 may be continuously present without being interrupted over the thickness T direction (Z direction) of the single anisotropic diffusion layer 7.
- the interface between the prismatic region 4 and the matrix region 6 is connected, light diffusion and condensing easily occur continuously while passing through the anisotropic optical film 5, Increases efficiency.
- the prismatic region and the matrix region are mainly mottled like spots, because it is difficult to obtain the light collecting property that is the effect of the present invention.
- the maximum linear transmittance at an incident angle at which the linear transmittance of the anisotropic optical film is maximized is preferably 30% or more and less than 95%.
- the upper limit value of the maximum linear transmittance is more preferably 80% or less, and further preferably 70% or less.
- the lower limit value of the maximum linear transmittance is more preferably 40% or more, and further preferably 50% or more.
- the anisotropic optical film of the present invention has the above-mentioned maximum linear transmittance, and while maintaining excellent light diffusion / condensation in the horizontal direction, light diffusion / condensation in the vertical direction Is provided sufficiently.
- the minimum linear transmittance at an incident angle at which the linear transmittance of the anisotropic optical film is minimized is preferably 20% or less. It shows that the amount of linear transmitted light decreases (the haze value increases) as the minimum linear transmittance decreases. Therefore, the amount of diffused light increases as the minimum linear transmittance decreases.
- a lower minimum linear transmittance is preferred. It is preferably 10% or less, and more preferably 5% or less. Although a lower limit is not limited, For example, it is 0%.
- the linear transmitted light amount and the linear transmittance can be measured by the method shown in FIG. That is, the linear transmitted light amount and the linear transmittance are measured at each incident angle so that the rotation axis L shown in FIG.
- the maximum linear transmittance and the minimum linear transmittance of the anisotropic optical film are obtained, and the difference between the maximum linear transmittance and the minimum linear transmittance is obtained.
- a straight line that is 1 ⁇ 2 of the difference is created on the optical profile, two intersections where the straight line and the optical profile intersect are obtained, and an incident angle corresponding to the intersection is read.
- the normal direction is set to zero degrees, and the incident angle is shown in the minus direction and the plus direction. Therefore, the incident angle corresponding to the incident angle and the intersection may have a negative value.
- the value of the two intersections has a positive incident angle value and a negative incident angle value
- the sum of the absolute value of the negative incident angle value and the positive incident angle value is the angular range of the incident light diffusion range. It becomes.
- the values of the two intersection points are both positive, the difference obtained by subtracting the smaller value from the larger value is the angular range of the diffusion range of the incident light.
- the values of the two intersections are both negative, the absolute value of each is taken, and the difference obtained by subtracting the smaller value from the larger value is the angular range of the incident light diffusion range.
- the angle range of the diffusion range of incident light with respect to the linear transmittance where the difference between the maximum linear transmittance and the minimum linear transmittance is 1 ⁇ 2 or less is preferably 50 ° to 80 °.
- the angle range of the incident light diffusion range is smaller than 50 °, there is no great difference from the conventional anisotropic optical film.
- a more preferable angle range of the diffusion range is 60 to 80 °, and an angle range of 50 ° or more can be given by having a prismatic region.
- the angle range of the diffusion range of incident light exceeds 80 °, the light collecting property is impaired, which is not preferable.
- the angle at which one prismatic region extending straightly strongly scatters the light is approximately ⁇ 10 ° in the difference between the inclination of the prismatic region and the light traveling direction. When it is in range.
- the inclination of the prismatic region means a direction in which the scattering characteristic coincides with the incident angle of light having substantially target property with the incident angle as a boundary when the incident angle is changed.
- the reason for having “substantially target” is because it does not strictly have the target of optical characteristics.
- the inclination of the prismatic region can be found by observing the inclination of the film cross section with an optical microscope or by observing the projected shape of light through the anisotropic optical film while changing the incident angle.
- the angle (bending angle) when the prismatic region is bent is preferably 10 to 40 °. More preferably, efficient diffusion can be obtained at 15 to 25 °. As a result, the region where light is strongly scattered can be further expanded. In addition, since the region that strongly scatters light can be formed continuously, the light condensing property can be further enhanced in a state where the light intensity is kept substantially constant.
- the inclinations are preferably in the range of ⁇ 70 ° when the normal direction is zero °. If it is smaller than -70 ° or larger than + 70 °, depending on the material forming the anisotropic optical film, light exceeding these upper limits tends to be reflected on the surface of the anisotropic optical film. This is because it is difficult to be incident on the conductive optical film.
- the number of slopes is not limited, but is preferably between 2 and 5. This is because as the number of inclinations increases, the thickness of the anisotropic optical film increases and the productivity decreases.
- At least one of the inclinations is preferably within a range of ⁇ 5 ° (when the normal direction is zero °), and the inclination of another diffusion center axis is ⁇ 15 ° to ⁇ 5 ° or + 5 °. It is preferably in the range of + 15 °.
- the region where light is strongly scattered can be further expanded.
- the region that strongly scatters light can be formed continuously, the light condensing property can be further enhanced in a state where the light intensity is kept substantially constant.
- the shape where the inclination is bent may be such that the bent portion bends in a substantially straight line, may gradually change (for example, a curved shape), or may change sharply (for example, Linear). This makes it easier to obtain the effects of the present invention.
- the bending direction it is preferable that the bending direction gradually changes without interruption in the extending direction. By gradually changing without interruption, light can be efficiently diffused and collected.
- Such a structure in which the inclination is bent can be adjusted by the aspect ratio of the minor axis SA and the major axis LA of the prismatic structure, the thickness T, and the like.
- An anisotropic optical film in which another layer is provided on one surface of the anisotropic diffusion layer may be used.
- other layers include an adhesive layer, a polarizing layer, a light diffusion layer, a low reflection layer, an antifouling layer, an antistatic layer, an ultraviolet / near infrared (NIR) absorption layer, a neon cut layer, and an electromagnetic wave shielding layer. be able to.
- Other layers may be sequentially stacked.
- Other layers may be laminated on both surfaces of the anisotropic diffusion layer. The other layer laminated on both surfaces may be a layer having the same function or a layer having another function.
- the anisotropic optical film of the present invention can be produced by subjecting a specific photocurable composition layer to UV irradiation under special conditions.
- the raw material of the anisotropic optical film will be described first, and then the manufacturing process will be described.
- the material for forming the anisotropic optical film of the present invention is a photocurable compound selected from a macromonomer, polymer, oligomer or monomer having a radical polymerizable or cationic polymerizable functional group. It is a material composed of a photoinitiator and polymerized and solidified by irradiation with ultraviolet rays and / or visible rays.
- a difference in refractive index occurs due to the difference in density.
- (meth) acrylate means that either acrylate or methacrylate may be sufficient.
- the radically polymerizable compound mainly contains one or more unsaturated double bonds in the molecule, and specifically includes epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polybutadiene acrylate, silicone acrylate, and the like.
- a compound having at least one epoxy group, vinyl ether group or oxetane group in the molecule can be used.
- the compounds having an epoxy group include 2-ethylhexyl diglycol glycidyl ether, glycidyl ether of biphenyl, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrachloro Diglycidyl ethers of bisphenols such as bisphenol A and tetrabromobisphenol A, polyglycidyl ethers of novolac resins such as phenol novolak, cresol novolak, brominated phenol novolak, orthocresol novolak, ethylene glycol, polyethylene glycol, polypropylene glycol, Butanediol, 1,6-hexanediol, neopentyl glycol, trimethyl Diglycidyl ethers of
- Examples of the compound having a vinyl ether group include diethylene glycol divinyl ether, triethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, dodecyl vinyl ether, and trimethylolpropane trivinyl ether. , Propenyl ether propylene carbonate and the like, but are not limited thereto. Vinyl ether compounds are generally cationically polymerizable, but radical polymerization is also possible by combining with acrylates.
- the above cationic polymerizable compounds may be used alone or in combination.
- the photopolymerizable compound is not limited to the above.
- fluorine atoms (F) may be introduced into the photopolymerizable compound in order to reduce the refractive index, and in order to increase the refractive index, Sulfur atoms (S), bromine atoms (Br), and various metal atoms may be introduced.
- ultrafine particles made of a metal oxide having a high refractive index such as titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), tin oxide (SnOx)
- a photopolymerizable functional group such as an acryl group, a methacryl group, or an epoxy group is introduced to the above-described photopolymerizable compound.
- Photo-curable compound having a silicone skeleton It is preferable to use a photocurable compound having a silicone skeleton as the photocurable compound.
- a photocurable compound having a silicone skeleton is oriented and polymerized and solidified along with its structure (mainly ether bonds), and has a low refractive index region, a high refractive index region, or a low refractive index region and a high refractive index region. Form.
- the prismatic region is easily bent, and the light condensing property in the front direction is improved.
- the low refractive index region corresponds to either a prismatic region or a matrix region, and the other corresponds to a high refractive index region.
- the silicone resin which is a cured product of the photocurable compound having a silicone skeleton, is relatively increased. This makes it easier to bend the diffusion center axis, thereby improving the light condensing property in the front direction. Since a silicone resin contains more silica (Si) than a compound having no silicone skeleton, the relative use of the silicone resin can be achieved by using an EDS (energy dispersive X-ray spectrometer) with this silica as an index. The amount can be confirmed.
- EDS energy dispersive X-ray spectrometer
- the photocurable compound having a silicone skeleton is a monomer, oligomer, prepolymer or macromonomer having a radical polymerizable or cationic polymerizable functional group.
- the radical polymerizable functional group include an acryloyl group, a methacryloyl group, and an allyl group.
- the cationic polymerizable functional group include an epoxy group and an oxetane group. There are no particular restrictions on the type and number of these functional groups, but it is preferable to have a polyfunctional acryloyl group or methacryloyl group because the higher the functional groups, the higher the crosslink density and the greater the difference in refractive index. .
- skeleton may be inadequate in compatibility with another compound from the structure, in such a case, it can urethanize and can improve compatibility.
- silicone, urethane, (meth) acrylate having an acryloyl group or a methacryloyl group at the terminal is preferably used.
- the weight average molecular weight (Mw) of the photocurable compound having a silicone skeleton is preferably in the range of 500 to 50,000. More preferably, it is in the range of 2,000 to 20,000.
- Mw weight average molecular weight
- a sufficient photocuring reaction occurs, and the silicone resin present in the anisotropic optical film is easily oriented. With the orientation of the silicone resin, the diffusion center axis is easily bent.
- silicone skeleton examples include those represented by the following general formula (1).
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently a methyl group, an alkyl group, a fluoroalkyl group, a phenyl group, an epoxy group, an amino group, a carboxyl group.
- a functional group such as a polyether group, an acryloyl group, and a methacryloyl group.
- n is preferably an integer of 1 to 500.
- thermoplastic resin examples include polyester, polyether, polyurethane, polyamide, polystyrene, polycarbonate, polyacetal, polyvinyl acetate, acrylic resin, and a copolymer or modified product thereof.
- thermoplastic resin it is dissolved using a solvent in which the thermoplastic resin dissolves, and after application and drying, the photocurable compound having a silicone skeleton is cured with ultraviolet rays to form an anisotropic optical film.
- thermosetting resin examples include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyesters, copolymers thereof, and modified products.
- thermosetting resin an anisotropic optical film is formed by curing the photocurable compound having a silicone skeleton with ultraviolet rays and then appropriately heating to cure the thermosetting resin.
- the most preferable compound that does not have a silicone skeleton is a photo-curing compound, which easily separates a low refractive index region from a high refractive index region, and does not require a solvent and a drying process when using a thermoplastic resin. It is excellent in productivity, such as being unnecessary and a thermosetting process like a thermosetting resin is unnecessary.
- the refractive index difference (absolute value) between the low refractive index region and the high refractive index region is preferably 0.02 or more. More preferably, it is 0.03 or more, More preferably, it is 0.04 or more. As the refractive index difference increases, the degree of anisotropy increases, and it becomes easier to confirm whether a plate-like structure is formed with an optical microscope or the like.
- Photoinitiators that can polymerize radically polymerizable compounds include benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- Diethoxyacetophenone, benzyldimethyl ketal, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -On, bis (cyclo Nt
- the photoinitiator of a cationic polymerizable compound is a compound that generates an acid by light irradiation and can polymerize the above-mentioned cationic polymerizable compound with the generated acid.
- an onium salt or a metallocene complex is used.
- the onium salt a diazonium salt, a sulfonium salt, an iodonium salt, a phosphonium salt, a selenium salt, or the like is used, and these counter ions include anions such as BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ and the like. Used.
- Specific examples include 4-chlorobenzenediazonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenyl.
- the photoinitiator is about 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. Blended. This is because when less than 0.01 parts by weight, the photo-curing property decreases, and when it exceeds 10 parts by weight, only the surface is cured and the internal curability is deteriorated. This is because it inhibits the formation of.
- photoinitiators are usually used by directly dissolving powder in a photopolymerizable compound, but if the solubility is poor, a photoinitiator dissolved beforehand in a very small amount of solvent at a high concentration is used. It can also be used.
- a solvent is more preferably photopolymerizable, and specific examples thereof include propylene carbonate and ⁇ -butyrolactone. It is also possible to add various known dyes and sensitizers in order to improve the photopolymerizability.
- a thermosetting initiator capable of curing the photopolymerizable compound by heating can be used in combination with the photoinitiator. In this case, by heating after photocuring, it can be expected to further accelerate the polymerization and curing of the photopolymerizable compound to complete it.
- an anisotropic optical film can be formed by curing the above-mentioned photo-curable compound alone or a mixture of a plurality of them.
- the anisotropic optical film of the present invention can also be formed by curing a mixture of a photocurable compound and a polymer resin that does not have photocurability.
- Polymer resins that can be used here include acrylic resin, styrene resin, styrene-acrylic copolymer, polyurethane resin, polyester resin, epoxy resin, cellulose resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyvinyl Examples include butyral resin.
- polymer resins and photo-curable compounds must have sufficient compatibility before photo-curing, but various organic solvents, plasticizers, etc. are used to ensure this compatibility. It is also possible.
- an acrylate as a photocurable compound, it is preferable from a compatible point to select as a polymer resin from an acrylic resin.
- the ratio of the photocurable compound having a silicone skeleton to the compound having no silicone skeleton is preferably in the range of 15:85 to 85:15 by mass ratio. More preferably, it is in the range of 30:70 to 70:30. By setting it in this range, the phase separation between the low refractive index region and the high refractive index region can easily proceed, and the prismatic region can be easily bent.
- the ratio of the photocurable compound having a silicone skeleton is less than the lower limit value or exceeds the upper limit value, the phase separation is difficult to proceed, and the prismatic region is hardly bent.
- silicone / urethane / (meth) acrylate is used as the photocurable compound having a silicone skeleton, the compatibility with a compound having no silicone skeleton is improved. Accordingly, the prismatic region can be bent even if the mixing ratio of the materials is widened.
- FIG. 2 [process] Next, the manufacturing method (process) of the anisotropic optical film of this invention is demonstrated using FIG.
- the anisotropic optical film of the present invention can be obtained by sequentially performing the following steps. (1) Step of obtaining the parallel light D from the light source 30 (2) Step of obtaining the light E having directivity by making the parallel light D incident on the directional diffusion element 60 (3) Light with the light E having directivity The process of making it enter into the curable composition layer 20, and hardening a photocurable composition layer In any of FIG. 2 (a), (b), the anisotropic optical film of this invention can be obtained.
- the difference between FIGS. 2A and 2B is that the spread of the light E with directivity is large in (a) but small in (b). Depending on the size of the spread of the light E having directivity, the size of the prismatic region is different.
- the spread of the light E having directivity mainly depends on the distance between the directional diffusion element 60 and the photocurable composition layer 20 and the type of the directional diffusion element 60. As the distance is shortened, the size of the prismatic region is reduced, and as the distance is increased, the size of the prismatic region is increased. Therefore, the size of the prismatic region can be adjusted by adjusting the distance.
- a short arc ultraviolet light source As a light source for irradiating a composition containing a photocurable compound, a short arc ultraviolet light source is usually used, and specifically, a high pressure mercury lamp, a low pressure mercury lamp, a metahalide lamp, a xenon lamp or the like is used. Is possible.
- the light beam applied to the composition containing the photocurable compound needs to include a wavelength capable of curing the photocurable compound. Usually, light having a wavelength centered at 365 nm of a mercury lamp is used. Any lamp can be used as long as the light source includes a wavelength close to the absorption wavelength of the photopolymerization initiator to be used.
- An anisotropic optical film is formed by curing the photocurable composition layer.
- a reflecting mirror is arranged behind the light source so that the light is emitted as a point light source in a predetermined direction. Obtainable. If a point light source is used, parallel rays can be easily obtained.
- the directivity diffusing element 60 only needs to provide directivity to the incident parallel light beam D.
- FIG. 2 shows a mode in which light E having directivity is diffused much in the X direction and hardly diffused in the Y direction.
- a needle-like filler having a high aspect ratio is contained in the directivity diffusing element 60 and the major axis of the needle-like filler extends in the Y direction.
- a method of aligning can be employed.
- Various methods can be used for the directional diffusion element in addition to the method using the needle-like filler.
- the diffusibility of light may vary depending on the incident part of the directional diffusing element.
- the parallel light D passes through the directional diffusing element 60 to generate the light E having directivity. What is necessary is just to arrange
- the aspect ratio of the light E having directivity is preferably 5 to 40.
- the aspect ratio of the prismatic region is formed substantially corresponding to the aspect ratio.
- the lower limit of the aspect ratio is preferably 5, more preferably 8, and even more preferably 10.
- the upper limit of the aspect ratio is preferably 40, more preferably 40, and even more preferably 30. As the aspect ratio increases, there is a problem that light diffusibility and light condensing properties become insufficient.
- the anisotropic optical film of the present invention can be obtained by making light E having directivity incident on the photocurable composition layer 20 and curing the photocurable composition layer.
- the photocurable composition layer 20 is coated on a suitable substrate 10 such as a transparent polyethylene terephthalate (PET) film to provide a coating film (photocurable composition layer).
- PET transparent polyethylene terephthalate
- the solvent is evaporated by drying as necessary, but the dry film thickness is preferably 30 to 200 ⁇ m.
- the lower limit of the dry film thickness is more preferably 50 ⁇ m. Increasing the film thickness tends to cause bending.
- the upper limit of the dry film thickness is more preferably 150 ⁇ m, still more preferably 100 ⁇ m. Productivity improves as the film thickness decreases.
- a preferable value, a more preferable value, and a still more preferable value can be combined suitably.
- a dry film thickness of less than 30 ⁇ m is not preferable because light diffusibility is poor.
- the dry film thickness exceeds 200 ⁇ m the overall diffusibility is too strong and it becomes difficult to obtain the characteristic anisotropy of the present invention, and it is not preferable because it is not suitable for thinning applications.
- a release film or a mask described later is laminated on the coated film or cured film to form a photosensitive laminate.
- a normal coating method or printing method is applied. Specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating Coating such as die coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.
- a weir having a certain height can be provided around the substrate, and the composition can be cast in the area surrounded by the weir.
- a mask can be laminated in order to prevent oxygen inhibition of the photocurable composition layer.
- the material of the mask is not particularly limited, but it is necessary to use a sheet that transmits at least part of incident ultraviolet rays.
- Examples of such sheets include transparent plastic sheets such as PET, TAC, PVAc, PVA, acrylic, and polyethylene, inorganic sheets such as glass and quartz, and patterning and ultraviolet rays for controlling the amount of ultraviolet rays transmitted to these sheets. It may also contain pigments that absorb water.
- the illuminance of UV light applied to the photocurable composition layer is preferably in the range of 0.01 to 100 mW / cm 2 , more preferably in the range of 0.1 to 20 mW / cm 2 . If the illuminance is 0.01 mW / cm 2 or less, it takes a long time to cure, resulting in poor production efficiency. If the illuminance is 100 mW / cm 2 or more, the photo-curing compound is cured too quickly to form a structure, This is because the desired anisotropic diffusion characteristic cannot be expressed.
- the UV irradiation time is not particularly limited, but is 10 to 180 seconds, more preferably 30 to 120 seconds. Then, the anisotropic optical film of this invention can be obtained by peeling a release film.
- the anisotropic optical film of the present invention is obtained by forming a specific internal structure in the photocurable composition layer by irradiating low-illuminance UV light for a relatively long time as described above. For this reason, unreacted monomer components remain by such UV irradiation alone, and stickiness may occur, which may cause problems in handling properties and durability.
- the residual monomer can be polymerized by additional irradiation with UV light having a high illuminance of 1000 mW / cm 2 or more.
- the UV irradiation at this time is preferably performed from the opposite side of the mask side.
- the means for obtaining the internal bending structure in the anisotropic optical film of the present invention is not limited, but in the thickness direction of the photocurable composition layer when the composition containing the photocurable compound is cured.
- a method obtained by giving a temperature distribution is effective.
- the photocurable composition layer here refers to the state before the anisotropic diffusion layer is formed. That is, the photocurable composition layer refers to a state before the composition containing the photocurable compound is cured.
- it is possible to generate a temperature distribution in the thickness direction of the composition layer by applying cool air to the surface side on which ultraviolet rays are incident to cool the substrate and heating the substrate side with various temperature control plates.
- the refractive index of the photocurable composition changes with temperature, and the photocurable composition bends as the irradiated ultraviolet rays pass through the interior.
- the bending angle, position, and direction can be changed by the refractive index of the composition, the reaction rate, the temperature gradient, and the like. Further, the number of the main bends can be adjusted by adjusting the film thickness.
- the reaction rate is appropriately adjusted depending on the reactivity of the composition itself, the viscosity, the intensity of ultraviolet rays, the type and amount of initiator, and the like.
- the anisotropic optical film of the present invention is a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a surface electric field display (SED), an electronic paper. It can be applied to such a display device. It is particularly preferably used for a liquid crystal display (LCD).
- the anisotropic optical film of the present invention is formed by curing a photocurable compound having a silicone skeleton, but there are few problems of adhesive strength, and it can be placed at a desired place via an adhesive layer or an adhesive layer. Can be used together.
- the anisotropic optical film of the present invention can be preferably used for a transmissive, reflective, or transflective liquid crystal display device.
- the anisotropic optical film of the present invention and the anisotropic optical film of the comparative example were produced.
- Example 1 A partition wall having a height of 0.1 mm was formed with a curable resin using a dispenser on the entire periphery of a PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 ⁇ m and a size of 76 ⁇ 26 mm. This was filled with the following photocurable resin composition and covered with another PET film.
- a PET film trade name: A4300, manufactured by Toyobo Co., Ltd.
- Silicone urethane acrylate (refractive index: 1.460, weight average molecular weight: 5,890) 20 parts by weight (trade name: 00-225 / TM18, manufactured by RAHN) 30 parts by weight of neopentyl glycol diacrylate (refractive index: 1.450) (manufactured by Daicel Cytec Co., Ltd., trade name Ebecryl 145) Bisphenol A EO adduct diacrylate (refractive index: 1.536) 15 parts by weight (manufactured by Daicel Cytec, trade name: Ebecyl 150) ⁇ Phenoxyethyl acrylate (refractive index: 1.518) 40 parts by weight (Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PO-A) ⁇ 2,2-dimethoxy-1,2-diphenylethane-1-one 4 parts by weight (manufactured by BASF, trade name: Irgacure 651) A 0.1mm-th
- Example 2 An anisotropic optical film of Example 2 was obtained in the same manner as in Example 1 except that a directional diffusion element having an aspect ratio of transmitted UV light of 20 was used as the directional diffusion element.
- Example 3 An anisotropic optical film of Example 3 was obtained in the same manner as in Example 1 except that a directional diffusion element having an aspect ratio of transmitted UV light of 10 was used as the directional diffusion element.
- Example 4 The manufacturing conditions were changed so that the thickness of the liquid film was 60 ⁇ m, and the directional diffusion element having an aspect ratio of transmitted UV light of 10 was used as the directional diffusion element in the same manner as in Example 1, An anisotropic optical film of Example 4 was obtained.
- Comparative Example 1 An anisotropic optical film of Comparative Example 1 was obtained in the same manner as Example 1 except that the directional diffusion element was not used.
- the anisotropic optical film of Comparative Example 1 had a plurality of columnar structures formed from the upper surface to the lower surface of the anisotropic optical film.
- Comparative Example 2 An anisotropic optical film of Comparative Example 2 was obtained in the same manner as in Example 1 except that a directional diffusion element having an aspect ratio of transmitted UV light of 50 was used as the directional diffusion element.
- the anisotropic optical film of Comparative Example 2 had a plate-like structure shown in FIG. 10 (however, the diffusion center axis is different from that in FIG. 10).
- Comparative Example 3 The manufacturing conditions were changed so that the thickness of the liquid film was 60 ⁇ m, and a directional diffusion element having an aspect ratio of transmitted UV light of 50 was used as the directional diffusion element in the same manner as in Example 1, An anisotropic optical film of Comparative Example 3 was obtained.
- the anisotropic optical film of Comparative Example 3 had a plate-like structure shown in FIG. 10 (however, the diffusion center axis is different from that in FIG. 10).
- the weight average molecular weight (Mw) of the silicone, urethane, and acrylate used in Examples 1 to 3 was measured as a polystyrene-equivalent molecular weight using the GPC method under the following conditions.
- Degasser DG-980-51 (manufactured by JASCO Corporation) Pump: PU-980-51 (manufactured by JASCO Corporation)
- Autosampler AS-950 (manufactured by JASCO Corporation)
- Thermostatic chamber C-965 (manufactured by JASCO Corporation)
- Temperature 40 ° C Eluent: THF Injection volume: 150 ⁇ l Flow rate: 1.0ml / min Sample concentration: 0.2%
- the anisotropic optical films of Examples and Comparative Examples were evaluated using a variable angle photometer goniophotometer (manufactured by Genesia Co., Ltd.) that can arbitrarily change the light projecting angle of the light source and the light receiving angle of the light receiver.
- the light receiving part was fixed at a position where the light traveling straight from the light source was received, and the anisotropic optical films obtained in Examples and Comparative Examples were set in the sample holder therebetween. As shown in FIG. 12, the sample was rotated as the rotation axis (L), and the amount of linear transmitted light corresponding to each incident angle was measured. By this evaluation method, it is possible to evaluate in which angle range the incident light is diffused.
- This rotation axis (L) is the same axis as the BB axis in the sample structure shown in FIG. 10 or the CC axis in the sample structure shown in FIG.
- the linear transmitted light amount was measured by measuring the wavelength in the visible light region using a visibility filter.
- the interference (rainbow) of the anisotropic optical film the transmitted light was visually observed from various angles, and the degree of interference was evaluated.
- FIGS. 3 to 6 show the results of Examples obtained by the above measurement.
- FIGS. 3 is Example 1
- FIG. 4 is Example 2
- FIG. 5 is Example 3
- FIG. 6 is Example 4
- FIG. 7 is Comparative Example 1
- FIG. 8 is Comparative Example 2
- FIG. show the dependence on incident light by measuring the amount of linear transmitted light.
- Example 3 (Section observation of anisotropic optical film) As a representative example, the cross section of Example 3 was observed with an optical microscope, and the result of confirming the bent state of the prismatic structure was shown in FIG.
- Table 1 summarizes the prism shape, optical characteristics, etc.
- the value of the angle range of the diffusion range of incident light with respect to the linear transmittance where the difference between the maximum linear transmittance and the minimum linear transmittance is 1 ⁇ 2 or less correlates with the aspect ratio of the prismatic region.
- the angle range of the incident light diffusion range can be set to 53 ° to 70 ° by using a prismatic region having an aspect ratio of 6 to 35. It was.
- the aspect ratios of the prisms are almost the same, and the thickness of the anisotropic diffusion layer is different. However, even if the thickness of the anisotropic diffusion layer is about 60 ⁇ m, the above-mentioned input is sufficiently practical.
- an angular range of the diffusion range of incident light could be achieved. That is, the anisotropic optical films of Examples 1 to 4 were able to diffuse and collect light over a wide incident angle range, and did not give an unnatural impression.
- the angle range of the diffusion range of the incident light can be 50 ° or more. could not. That is, the anisotropic optical films of Comparative Examples 1 to 3 could not diffuse and collect light over a wide incident angle range, and gave an unnatural impression.
- the aspect ratio of the prismatic region generally reflects the aspect ratio of the directional diffusion element.
- Those skilled in the art who have seen this can adjust the distance between the directional diffusion element and the photocurable resin composition (before curing of the anisotropic optical film) while considering the aspect ratio of the directional diffusion element.
- the values of the minor axis SA and the major axis LA can be adjusted, and an anisotropic optical film having a prismatic region defined in the present invention can be produced.
- FIG. 13 in order to realize such a wide diffusion range, it plays the role of adjusting the bending of the prismatic structure by adjusting the aspect ratio and film thickness, and has a plurality of scattering central axes continuously. It is considered to obtain the same effect as.
- the prism structure was bent as shown in FIG.
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Abstract
Description
(2)前記角柱領域の短径と長径のアスペクト比が2~40の範囲内にあることを特徴とする前記(1)に記載の異方性光学フィルム。
(3)前記角柱領域の厚さが30μm~200μmの範囲内にあることを特徴とする前記(1)に記載の異方性光学フィルム。
(4)前記最大直線透過率と前記最小直線透過率との差が1/2以下となる直線透過率に対する入射光の拡散範囲の角度範囲が50°~80°であることを特徴とする前記(1)に記載の異方性光学フィルム。
(5)前記短径の長さが0.5μm~5.0μmの範囲内にあることを特徴とする前記(2)に記載の異方性光学フィルム。
(6)前記長径の長さが3.0μm~50μmの範囲内にあることを特徴とする前記(2)に記載の異方性光学フィルム。
(7)前記異方性光学フィルムを備えたことを特徴とする表示装置。
(8)光源から平行光線を得る工程と、上記平行光線を指向性拡散要素に入射させ、指向性をもった光を得る工程と、上記指向性をもった光を光硬化性組成物層に入射させ、光硬化性組成物層を硬化させる工程と、を有することを特徴とする異方性光学フィルムの製造方法。
(9)前記指向性をもった光のアスペクト比が2~40の範囲内にあることを特徴とする前記(8)に記載の異方性光学フィルムの製造方法。
直線透過率(%)=(直線透過光量/入射光量)×100
図1は本発明の異方性光学フィルム5の模式図である。図1(a)は異方性光学フィルム5の平面図、図1(b)は図1(a)のC-C線で切断した異方性光学フィルム5の断面図である。
図1に示すように異方性光学フィルム5は、複数の角柱領域6とマトリックス領域4を有する。複数の角柱領域6およびマトリックス領域4は、不規則な分布や形状を有するが、異方性光学フィルムの全面にわたって形成されることから、得られる光学特性(例えば、後述する直線透過率等)はどの部位で測定しても略同じである。複数の角柱領域6およびマトリックス領域4が不規則な分布や形状を有するため、本発明の異方性光学フィルム5は光の干渉(虹)が発生することが少ない。
角柱領域6の断面形状は図1(b)に示すように、角柱領域6とマトリックス領域4が交互になるように形成されている。図1(b)においては角柱領域6が厚さTの方向に直線状に延存している形を示しているが、直線状、波打ち状もしくは屈曲していてもよいし、またはこれらが入り混じっているものであってもよい。
マトリックス領域4と角柱領域6の界面における屈折率は漸増的に変化するものであることが好ましい。漸増的に変化させることで、入射角度を変えた場合の拡散性の変化が極めて急峻となり不自然な印象を与えやすくなる問題が発生し難くなる。マトリックス領域4と角柱領域6を光照射に伴う相分離によって形成することで、マトリックス領域4と角柱領域6の界面の屈折率を漸増的に変化させることができる。
短径SAと長径LAのアスペクト比の上限値は40であることが好ましく、25であることがより好ましく、15であることがさらに好ましい。アスペクト比が大きくなるにつれ、光の拡散範囲が狭くなる問題がある。また、アスペクト比が大きくなるほど、光の干渉(虹)が生じやすくなる問題がある。
これらアスペクト比の下限値および上限値は、適宜組み合わせることができる。例えば、角柱領域6のアスペクト比を2~40とすることで、拡散範囲を広くすることができるとともに、入射角度を変えた場合の拡散性の変化が極めて急峻となり不自然な印象を与えやすくなる問題が発生し難くなる。
角柱領域6の短径SAの長さの上限値は5.0μmであることが好ましく、3.0μmであることがより好ましく、2.0μmであることがさらに好ましい。短径SAが長くなるにつれ、拡散範囲が狭くなる問題がある。
これら角柱領域6の短径SAの下限値および上限値は、適宜組み合わせることができる。例えば、角柱領域6の短径SAを0.5μm~5.0μmとすることで、拡散範囲を広くすることができるとともに、光の拡散性・集光性が十分なものとなる。
角柱領域6の長径LAの長さの上限値は40μmであることが好ましく、20μmであることがより好ましく、10μmであることがさらに好ましい。長径LAが大きくなるにつれ、拡散範囲が狭くなる問題や入射角度を変えた場合の拡散性の変化が極めて急峻となり不自然な印象を与えやすくなる問題がある。また、長径LAが大きくなると光の干渉(虹)が発生しやすくなる問題もある。
これら角柱領域6の短径SAの下限値および上限値は、適宜組み合わせることができる。例えば、角柱領域6の長径LAを3.0μm~40μmとすることで、拡散範囲を広くすることができるとともに、入射角度を変えた場合の拡散性の変化が極めて急峻となり不自然な印象を与えやすくなる問題を解消することができる。
角柱領域6の厚さTの下限値は30μmであることが好ましく、50μmであることがより好ましい。厚さTが小さくなるにつれ、光の拡散性・集光性が不十分になる問題がある。
角柱領域6の厚さTの上限値は200μmであることが好ましく、150μmであることがより好ましく、100μmであることがさらに好ましい。厚さTが大きくなるにつれ、材料費が多くかかることや製造に時間を要すること等のコストが高くなる問題と、厚さT方向での拡散が多くなることにより画像にボケが発生しやすくなりコントラストが低下しやすくなる問題がある。
これら角柱領域6の厚さTの下限値および上限値は、適宜組み合わせることができる。
相分離により異方性光学フィルムを作成すると、上面5aまたは下面5bのいずれか一方が光学顕微鏡で観察し難くなる場合がある。光を照射した面から厚さT方向に向けて徐々に角柱領域6が形成されていくが、その他面(光を照射した面の反対面)にまで角柱領域6が達した後にさらに角柱領域6が伸長するためである。このような場合はもう一方の面を光学顕微鏡で観察することによって角柱領域6を確認しやすくなる。
最大直線透過率を当該範囲にすることによって、拡散範囲が広くなるとともに、入射角度を変えた場合の拡散性の変化が極めて急峻となり不自然な印象を与えやすくなる問題が発生し難くなる。また、最大直線透過率を低くするにつれ、光の干渉(虹)が生じにくくなる点で好ましいが、最大直線透過率が低すぎると拡散範囲が狭くなる問題がある。
加えて、適度な異方性とすることができるため、異方性光学フィルムの適用範囲を広くすることができる。例えば表示装置に異方性光学フィルムを使用する場合、異方性が強すぎると、水平方向への光の拡散・集光性に極めて優れるものの、垂直方向への光の拡散・集光性が不十分となりやすい問題がある。本願発明の異方性光学フィルムは上記の最大直線透過率を有することで、水平方向への優れた光の拡散・集光性を維持した上で、垂直方向への光の拡散・集光性を十分に備えるものである。
ここで、直線透過光量および直線透過率は図12に示す方法によって測定することができる。すなわち、図12に示す回転軸Lと、図1(a)に示すC-C軸を一致させるようにして、入射角毎に直線透過光量及び直線透過率を測定する(法線方向をゼロ°とする)。得られたデータより光学プロファイルが得られ、この光学プロファイルから最大直線透過率および最小透過率を求める。
なお、C-C軸と直交する軸を図12に示す回転軸Lと一致させるようにして、入射角毎に直線透過光量及び直線透過率を測定した場合、図11に示すように入射角によらずゼロ付近の直線透過率を示す。
2つの交点の値が両方ともプラスである場合、より大きい値からより小さい値を引いた差が入射光の拡散範囲の角度範囲となる。2つの交点の値が両方ともマイナスである場合、それぞれの絶対値をとり、より大きい値からより小さい値を引いた差が入射光の拡散範囲の角度範囲となる。
角柱領域の傾きとは、入射角を変化させた際に散乱特性がその入射角を境に略対象性を有する光の入射角と一致する方向を意味する。「略対象性を有する」としたのは、厳密に光学特性の対象性を有しないためである。角柱領域の傾きは、フィルム断面の傾きを光学顕微鏡によって観察することや、異方性光学フィルムを介した光の投影形状を入射角を変化させて観察することにより見出せる。
この傾きのうち少なくとも一つは±5°の範囲にあることが好ましく(法線方向をゼロ°としたとき)、且つ、別の拡散中心軸の傾きは-15°~-5°または+5°~+15°の範囲にあることが好ましい。これによって光を強く散乱する領域をより広げることができる。また、光を強く散乱する領域を連続して形成することができるため、光の強さを略一定に保った状態でより集光性を高めることができる。
このような傾きが屈曲する構造は、角柱構造の短径SAと長径LAのアスペクト比、および、厚さTなどによって調整することが可能である。
異方性拡散層の両方の面に、他の層を積層してもよい。両方の面に積層される他の層は、同一の機能を有する層であってもよいし、別の機能を有する層であってもよい。
本発明の異方性光学フィルムは、特定の光硬化性組成物層に特殊な条件でUV照射を行うことにより作製することが出来る。以下、まず異方性光学フィルムの原料を説明し、次いで製造プロセスを説明する。
本発明の異方性光学フィルムを形成する材料は、ラジカル重合性又はカチオン重合性の官能基を有するマクロモノマー、ポリマー、オリゴマーまたはモノマーから選択される光硬化性化合物と光開始剤とから構成され、紫外線及び/又は可視光線を照射することにより重合固化する材料である。
ここで、異方性光学フィルムを形成する材料が1種類であっても、密度の高低差ができることによって屈折率差が生ずる。UVの照射強度が強い部分は硬化速度が早くなるため、その硬化領域周囲に硬化材料が移動し、結果として屈折率が高くなる領域と屈折率が低くなる領域が形成されるからである。
なお、(メタ)アクリレートとは、アクリレートまたはメタアクリレートのどちらであってもよいことを意味する。
光硬化性化合物として、シリコーン骨格を有する光硬化性化合物を使用することが好ましい。シリコーン骨格を有する光硬化性化合物は、その構造(主にエーテル結合)に伴い配向して重合・固化し、低屈折率領域、高屈折率領域、又は、低屈折率領域及び高屈折率領域を形成する。シリコーン骨格を有する光硬化性化合物を使用することによって、角柱領域を屈曲させやすくなり、正面方向への集光性が向上する。
低屈折率領域は角柱領域またはマトリックス領域のいずれかに相当するものであり、他方が高屈折率領域に相当する。
シリコーン樹脂はシリコーン骨格を有さない化合物に比べ、シリカ(Si)を多く含有するため、このシリカを指標として、EDS(エネルギー分散型X線分光器)を使用することによってシリコーン樹脂の相対的な量を確認することができる。
一般式(1)中、nは1~500の整数であることが好ましい。
シリコーン骨格を有する光硬化性化合物にシリコーン骨格を有さない化合物を配合して、異方性光学フィルムを形成すると、低屈折領域と高屈折率領域が分離して形成されやすくなり、異方性の程度が強くなり好ましい。シリコーン骨格を有さない化合物は、光硬化性化合物のほかに熱可塑性樹脂、熱硬化性樹脂を用いることができ、これらを併用することもできる。光硬化性化合物としては、ラジカル重合性又はカチオン重合性の官能基を有するポリマー、オリゴマー、モノマーを使用することができる(ただし、シリコーン骨格を有していないものである)。熱可塑性樹脂としては、ポリエステル、ポリエーテル、ポリウレタン、ポリアミド、ポリスチレン、ポリカーボネート、ポリアセタール、ポリ酢酸ビニル、アクリル樹脂とその共重合体や変性物が挙げられる。熱可塑性樹脂を用いる場合においては熱可塑性樹脂が溶解する溶剤を使用して溶解し、塗布、乾燥後に紫外線でシリコーン骨格を有する光硬化性化合物を硬化せしめて異方性光学フィルムを成形する。熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステルとその共重合体や変性物が挙げられる。熱硬化性樹脂を用いる場合においては、紫外線でシリコーン骨格を有する光硬化性化合物を硬化させた後に適宜過熱することで、熱硬化性樹脂を硬化せしめて異方性光学フィルムを成形する。シリコーン骨格を有さない化合物として最も好ましいのは光硬化性化合物であり、低屈折領域と高屈折率領域が分離しやすいことと、熱可塑性樹脂を用いる場合の溶剤が不要で乾燥過程が不要であること、熱硬化性樹脂のような熱硬化過程が不要であることとなど、生産性に優れている。
ラジカル重合性化合物を重合させることのできる光開始剤としては、ベンゾフェノン、ベンジル、ミヒラーズケトン、2-クロロチオキサントン、2,4-ジエチルチオキサントン、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、2,2-ジエトキシアセトフェノン、ベンジルジメチルケタール、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパノン-1、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、ビス(シクロペンタジエニル)-ビス(2,6-ジフルオロ-3-(ピル-1-イル)チタニウム、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド等が挙げられる。又、これらの化合物は、各単体で用いてもよく、複数混合して用いてもよい。
本発明において、上記光開始剤は、光重合性化合物100重量部に対して、0.01~10重量部、好ましくは0.1~7重量部、より好ましくは0.1~5重量部程度配合される。これは、0.01重量部未満では光硬化性が低下し、10重量部を超えて配合した場合には、表面だけが硬化して内部の硬化性が低下してしまう弊害、着色、角柱領域の形成の阻害を招くからである。これらの光開始剤は、通常粉体を光重合性化合物中に直接溶解して使用されるが、溶解性が悪い場合は光開始剤を予め極少量の溶剤に高濃度に溶解させたものを使用することもできる。このような溶剤としては光重合性であることが更に好ましく、具体的には炭酸プロピレン、γ-ブチロラクトン等が挙げられる。又、光重合性を向上させるために公知の各種染料や増感剤を添加することも可能である。更に光重合性化合物を加熱により硬化させることのできる熱硬化開始剤を光開始剤と共に併用することもできる。この場合、光硬化の後に加熱することにより光重合性化合物の重合硬化を更に促進し完全なものにすることが期待できる。
次に本発明の異方性光学フィルムの製造方法(プロセス)について、図2を用いて説明する。以下の工程を順次経ることで、本発明の異方性光学フィルムを得ることができる。
(1)光源30から平行光線Dを得る工程
(2)平行光線Dを指向性拡散要素60に入射させ、指向性をもった光Eを得る工程
(3)指向性をもった光Eを光硬化性組成物層20に入射させ、光硬化性組成物層を硬化させる工程
図2(a)、(b)のいずれにおいても、本発明の異方性光学フィルムを得ることができる。図2(a)と(b)で異なるのは、指向性をもった光Eの広がりが(a)では大きいのに対し(b)では小さいことである。指向性をもった光Eの広がりの大きさに依存して、角柱領域の大きさが異なることになる。
光硬化性化合物を含む組成物に光照射を行うための光源としては、通常はショートアークの紫外線発生光源が使用され、具体的には高圧水銀灯、低圧水銀灯、メタハライドランプ、キセノンランプ等が使用可能である。光硬化性化合物を含む組成物に照射する光線は、該光硬化性化合物を硬化可能な波長を含んでいることが必要で、通常は水銀灯の365nmを中心とする波長の光が利用されるが、使用する光重合開始剤の吸収波長に近い波長を含む光源であればいずれのランプも使用できる。光硬化性組成物層を硬化させることで、異方性光学フィルムを形成する。
指向性拡散要素60は、入射した平行光線Dに指向性を付与するものであればよい。図2においては指向性をもった光Eが、X方向に多く拡散し、Y方向にはほとんど拡散しない態様を記載している。このように指向性をもった光を得るためには、例えば、指向性拡散要素60内にアスペクト比の高い針状フィラーを含有させるとともに、当該針状フィラーをY方向に長軸方向が延存するように配向させる方法を採用することができる。指向性拡散要素は針状フィラーを使用する方法以外に種々の方法を使用することができる。指向性拡散要素の種類によっては、指向性拡散要素への入射部分によって光の拡散性が異なることがあるが、平行光線Dが指向性拡散要素60を介することで指向性をもった光Eを得るように配置すればよい。
上記アスペクト比の下限値は5であることが好ましく、8であることがより好ましく、10であることがさらに好ましい。アスペクト比が小さくなるにつれ拡散範囲が狭くなる問題がある。
上記アスペクト比の上限値は40であることが好ましく、40であることがより好ましく、30であることがさらに好ましい。アスペクト比が大きくなるにつれ、光の拡散性・集光性が不十分になる問題がある。
指向性を持った光Eを光硬化性組成物層20に入射させ、当該光硬化性組成物層を硬化させることで、本発明の異方性光学フィルムを得ることができる。
光硬化性組成物層20は、透明ポリエチレンテレフタレート(PET)フィルムのような適当な基体10上に塗工して塗工膜(光硬化性組成物層)を設ける。必要に応じて乾燥して溶剤を揮発させるが、その乾燥膜厚は30~200μmであることが好ましい。乾燥膜厚の下限値は、より好ましくは50μmである。膜厚を厚くするほど屈曲を生じさせやすくなる。乾燥膜厚の上限値は、より好ましくは150μm、更に好ましくは100μmである。膜厚を薄くするほど生産性が向上する。上記の乾燥膜厚の下限値および上限値について、好ましい値、より好ましい値、更に好ましい値を適宜組み合わせることができる。乾燥膜厚が30μm未満では、光拡散性が乏しいため好ましくない。一方乾燥膜厚が200μmを越えるような場合、全体の拡散性が強すぎて本発明の特徴的な異方性が得られ難くなると共に、コストアップ、薄型化用途に不適合といったことからも好ましくない。更に、この塗工膜あるいは硬化膜上には離型フィルムや後述するマスクをラミネートして感光性の積層体を作る。
本発明の異方性光学フィルムは、液晶表示装置(LCD)、プラズマディスプレイパネル(PDP)、エレクトロルミネッセンスディスプレイ(ELD)や陰極管表示装置(CRT)、表面電界ディスプレイ(SED)、電子ペーパーのような表示装置に適用することができる。特に好ましくは液晶表示装置(LCD)に用いられる。本発明の異方性光学フィルムは、シリコーン骨格を有する光硬化性化合物を硬化して形成されるものであるが、接着強度の問題は少なく、接着層や粘着層を介して、所望の場所に貼り合わせて使用することができる。
本発明の異方性光学フィルムは、透過型、反射型、または半透過型の液晶表示装置に好ましく用いることができる。
厚さ100μm、76×26mmサイズのPETフィルム(東洋紡社製、商品名:A4300)の縁部全周に、ディスペンサーを使い硬化性樹脂で高さ0.1mmの隔壁を形成した。この中に下記の光硬化性樹脂組成物を充填し、別のPETフィルムでカバーした。
・シリコーン・ウレタン・アクリレート(屈折率:1.460、重量平均分子量:5,890) 20重量部
(RAHN社製、商品名:00-225/TM18)
ネオペンチルグリコールジアクリレート(屈折率:1.450) 30重量部
(ダイセルサイテック社製、商品名Ebecryl145)
・ビスフェノールAのEO付加物ジアクリレート(屈折率:1.536) 15重量部
(ダイセルサイテック社製、商品名:Ebecyl150)
・フェノキシエチルアクリレート(屈折率:1.518) 40重量部
(共栄社化学製、商品名:ライトアクリレートPO-A)
・2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン 4重量部
(BASF社製、商品名:Irgacure651)
この両面をPETフィルムで挟まれた0.1mmの厚さの液膜を80℃に加熱したホットプレート載せ、表面からは送風機より風を送り冷やした状態にして、上部からUVスポット光源(浜松ホトニクス社製、商品名:L2859-01)の落射用照射ユニットから出射される平行光線を透過UV光線のアスペクト比が30となる指向性拡散要素を介して線状光線に変換した紫外線を垂直に、照射強度10mW/cm2として1分間照射して、図1に示すような角柱領域を多数有する実施例1の異方性光学フィルムを得た(ただし、図1とは拡散中心軸が異なる)。そこから、PETフィルムを剥がして本発明の異方性光学フィルムを得た。
指向性拡散要素として透過UV光線のアスペクト比が20となる指向性拡散要素を用いた
こと以外は実施例1と同様にして、実施例2の異方性光学フィルムを得た。
指向性拡散要素として透過UV光線のアスペクト比が10となる指向性拡散要素を用いたこと以外は実施例1と同様にして、実施例3の異方性光学フィルムを得た。
液膜の厚さを60μmになるように作製条件を変更し、指向性拡散要素として透過UV光線のアスペクト比が10となる指向性拡散要素を用いたこと意外は実施例1と同様にして、実施例4の異方性光学フィルムを得た。
指向性拡散要素を使用しないこと以外、実施例1と同様にして、比較例1の異方性光学フィルムを得た。
比較例1の異方性光学フィルムは、異方性光学フィルムの上面から下面にかけて、複数の柱状構造が形成されているものであった。
指向性拡散要素として透過UV光線のアスペクト比が50となる指向性拡散要素を用いたこと以外は実施例1と同様にして、比較例2の異方性光学フィルムを得た。
比較例2の異方性光学フィルムは、図10に示す板状構造が形成されているものであった(ただし、図10とは拡散中心軸が異なる)。
液膜の厚さを60μmになるように作製条件を変更し、指向性拡散要素として透過UV光線のアスペクト比が50となる指向性拡散要素を用いたこと以外は実施例1と同様にして、比較例3の異方性光学フィルムを得た。
比較例3の異方性光学フィルムは、図10に示す板状構造が形成されているものであった(ただし、図10とは拡散中心軸が異なる)。
デガッサー:DG-980-51(日本分光株式会社製)
ポンプ:PU-980-51(日本分光株式会社製)
オートサンプラー:AS-950(日本分光株式会社製)
恒温槽:C-965(日本分光株式会社製)
カラム:Shodex KF-806L × 2本 (昭和電工株式会社製)
検出器:RI (SHIMAMURA YDR-880)
温度:40℃
溶離液:THF
注入量:150μl
流量:1.0ml/min
サンプル濃度:0.2%
実施例および比較例の異方性光学フィルムの表面(紫外線照射時の照射光側)を光学顕微鏡で観察し、角柱構造の長径LA、短径SAを測定した。長径LAおよび短径SAの算出には、任意の20の構造の平均値とした。また、長径LA/短径SAをアスペクト比として算出した。
光源の投光角、受光器の受光角を任意に可変できる変角光度計ゴニオフォトメータ(ジェネシア社製)を用いて、実施例および比較例の異方性光学フィルムの評価を行った。光源からの直進光を受ける位置に受光部を固定し、その間のサンプルホルダーに実施例および比較例で得られた異方性光学フィルムをセットした。図12に示すように回転軸(L)としてサンプルを回転させてそれぞれの入射角に対応する直線透過光量を測定した。この評価方法によって、どの角度の範囲で入射される光が拡散するかを評価することができる。この回転軸(L)は、図10に示されるサンプルの構造におけるB-B軸または図1(a)に示されるサンプルの構造におけるC-C軸と同じ軸である。直線透過光量の測定は、視感度フィルターを用いて可視光領域の波長を測定した。
異方性光学フィルムの干渉(虹)については、透過光をさまざまな角度から目視で観察し、干渉の度合いを評価した。
代表例として、実施例3の断面を光学顕微鏡で観察し、角柱構造の屈曲状態を確認した結果を図13に示した。
一方、角柱領域のアスペクト比が小さすぎる比較例1と、アスペクト比が大きすぎる比較例2~3の異方性光学フィルムは、前記入射光の拡散範囲の角度範囲を50°以上にすることができなかった。すなわち、比較例1~3の異方性光学フィルムは、広い入射角度範囲で、光の拡散と集光を行うことができず、不自然な印象を抱かせるものであった。
一方、長径LAが大きすぎる比較例2と比較例3は、光の干渉(虹)が強く発生するため、実用上の問題を生じるものであった。なお、比較例1は長径LAが小さいことから光の干渉(虹)は発生しないものの、長径LAが小さすぎるため、最大直線透過率と最小直線透過率との差が1/2以下となる直線透過率に対する入射光の拡散範囲の角度範囲の値を50°以上にすることはできないものであった。
3 受光器
4 マトリックス領域
5、50 異方性光学フィルム
5a 上面
5b 下面
6 角柱領域
10 基体
20 光硬化性組成物層
30 光源
40 板状構造
51 線状光源
60 指向性拡散要素
Claims (9)
- 光の入射角により拡散性が変化する異方性光学フィルムであって、
複数の角柱領域とマトリックス領域とを有するものであり、
直線透過率が最大となる入射角における最大直線透過率が30%以上95%未満であり、
直線透過率が最小となる入射角における最小直線透過率が20%以下であることを特徴とする異方性光学フィルム。 - 前記角柱領域の短径と長径のアスペクト比が2~40の範囲内にあることを特徴とする請求項1に記載の異方性光学フィルム。
- 前記角柱領域の厚さが30μm~200μmの範囲内にあることを特徴とする請求項1に記載の異方性光学フィルム。
- 前記最大直線透過率と前記最小直線透過率との差が1/2以下となる直線透過率に対する入射光の拡散範囲の角度範囲が50°~80°であることを特徴とする請求項1に記載の異方性光学フィルム。
- 前記短径の長さが0.5μm~5.0μmの範囲内にあることを特徴とする請求項2に記載の異方性光学フィルム。
- 前記長径の長さが3.0μm~50μmの範囲内にあることを特徴とする請求項2に記載の異方性光学フィルム。
- 前記異方性光学フィルムを備えたことを特徴とする表示装置。
- 光源から平行光線を得る工程と、
上記平行光線を指向性拡散要素に入射させ、指向性をもった光を得る工程と、
上記指向性をもった光を光硬化性組成物層に入射させ、光硬化性組成物層を硬化させる工程と、を有することを特徴とする異方性光学フィルムの製造方法。 - 前記指向性をもった光のアスペクト比が2~40の範囲内にあることを特徴とする請求項8に記載の異方性光学フィルムの製造方法。
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