WO2014129673A1 - 白色反射フィルム - Google Patents

白色反射フィルム Download PDF

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Publication number
WO2014129673A1
WO2014129673A1 PCT/JP2014/054988 JP2014054988W WO2014129673A1 WO 2014129673 A1 WO2014129673 A1 WO 2014129673A1 JP 2014054988 W JP2014054988 W JP 2014054988W WO 2014129673 A1 WO2014129673 A1 WO 2014129673A1
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WIPO (PCT)
Prior art keywords
particles
reflective film
white reflective
layer
surface layer
Prior art date
Application number
PCT/JP2014/054988
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English (en)
French (fr)
Japanese (ja)
Inventor
倉垣　雅弘
浅井　真人
博 楠目
Original Assignee
帝人デュポンフィルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2013034587A external-priority patent/JP5722937B2/ja
Priority claimed from JP2013034586A external-priority patent/JP5785202B2/ja
Application filed by 帝人デュポンフィルム株式会社 filed Critical 帝人デュポンフィルム株式会社
Priority to KR1020157013430A priority Critical patent/KR101587393B1/ko
Priority to KR1020157026779A priority patent/KR101599684B1/ko
Priority to CN201480003213.8A priority patent/CN105190371B/zh
Publication of WO2014129673A1 publication Critical patent/WO2014129673A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0284—Diffusing elements; Afocal elements characterized by the use used in reflection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

Definitions

  • the present invention relates to a white reflective film.
  • it is related with the white reflective film used for a liquid crystal display device.
  • a backlight unit of a liquid crystal display device includes a direct type having a light source on the back of the liquid crystal display panel and a reflective film on the back, and a light guide plate having a reflector on the back of the liquid crystal display panel.
  • a direct type (mainly direct type CCFL) is mainly used from the viewpoint of excellent brightness of a screen and uniformity of brightness in the screen.
  • the type was often used for relatively small LCDs such as notebook PCs, but in recent years, with the development of light sources and light guide plates, the brightness and uniformity of brightness within the screen have been improved even in edge-light type backlight units.
  • edge-light type backlight units have been used not only in relatively small but large LCDs. This is because there is a merit that the LCD can be thinned.
  • the edge light type backlight unit the light guide plate and the reflective film are in direct contact with each other. Therefore, if the light guide plate and the reflective film are attached in such a structure, there is a problem that the luminance of the attached portion becomes abnormal and in-plane variation in luminance occurs. Therefore, it is necessary to have a gap between the light guide plate and the reflective film and keep this gap constant. For example, by having beads on the surface of the reflective film, the gap between the light guide plate and the reflective film can be kept constant, and sticking of these can be prevented.
  • the objective of this invention is providing the white reflective film which can fully suppress the damage
  • the second object of the present invention is to provide a white reflection that can sufficiently suppress the sticking to the light guide plate, and can sufficiently prevent the light guide plate from being scratched, and has excellent film-forming properties.
  • the present invention adopts the following configuration in order to achieve the above-described problems. 1. It has a reflection layer A and a surface layer B made of a thermoplastic resin composition containing particles, and has protrusions formed by the particles on the surface of the surface layer B opposite to the reflection layer A.
  • a white reflective film in which the number of protrusions having a height of 5 ⁇ m or more on the surface is 10 4 to 10 10 / m 2 , a.
  • the surface layer B is an oriented layer, and the white reflective film a having a compressibility of 40% or more when compressed with a load of 0.3 gf of the particles.
  • the particle is a white reflective film b having a 10% compressive strength of 0.1 to 10 MPa when compressed with a load of 3 gf and a Vickers hardness of the protrusion of 5 to 30.
  • the agglomerated particles are at least selected from the group consisting of polyester agglomerated particles, acrylic agglomerated particles, polyurethane agglomerated particles and polyethylene agglomerated particles, and silica agglomerated particles, alumina agglomerated particles and ceramic agglomerated inorganic particles.
  • the white reflective film as described in 2 above which is one type. 4). 2. The white reflective film as described in 1 above, wherein the average particle diameter d of the particles is 5 ⁇ m or more and 100 ⁇ m or less. 5. 3. The white reflective film as described in 2 above, wherein the aggregated particles have a secondary particle size ds of 5 ⁇ m or more and 100 ⁇ m or less. 6).
  • the white reflective film b wherein the content of the particles in the surface layer B is 1% by volume or more and 50% by volume or less based on the volume of the surface layer B.
  • the white reflective film as described in any one of 1 to 5 above which is used as a surface light source reflector provided with a light guide plate. 15. 6.
  • FIG. 1 is a schematic diagram showing a method for evaluating damage of a light guide plate and evaluation of particle dropout in the present invention.
  • FIG. 2 is a schematic diagram showing a structure used for adhesion spot evaluation in the present invention.
  • the white reflective film of the present invention has a reflective layer A and a surface layer B both in the white reflective film a and the white reflective film b.
  • each structural component which comprises this invention is demonstrated in detail.
  • the reflective layer A of the white reflective film a and the white reflective film b in the present invention is composed of a thermoplastic resin and a void forming agent. By being contained, the layer contains voids and exhibits a white color.
  • the void forming agent will be described in detail later.
  • inorganic particles and a resin that is incompatible with the thermoplastic resin that constitutes the reflective layer A hereinafter may be referred to as an incompatible resin).
  • the reflectance of the reflective layer A at a wavelength of 550 nm is preferably 95% or higher, more preferably 96% or higher, and particularly preferably 97% or higher. Thereby, it becomes easy to make the reflectance of a white reflective film into a preferable range.
  • the reflection layer A has voids in the layer as described above, and the proportion of the void volume to the volume of the reflection layer A (void volume ratio) is 15% by volume or more and 70% by volume or less. Preferably there is. By setting it as such a range, the improvement effect of a reflectance can be made high, and it becomes easy to obtain the above reflectances. Moreover, the improvement effect of film forming property can be made high.
  • the void volume ratio in the reflective layer A is more preferably 30% by volume or more, and particularly preferably 40% by volume or more.
  • the void volume ratio in the reflective layer A is more preferably 65% by volume or less, and particularly preferably 60% by volume or less. The void volume ratio can be achieved by adjusting the type, size, and amount of the void forming agent in the reflective layer A.
  • thermoplastic resin examples include thermoplastic resins made of polyester, polyolefin, polystyrene, and acrylic. Among these, polyester is preferable from the viewpoint of obtaining a white reflective film excellent in mechanical properties and thermal stability. As such a polyester, it is preferable to use a polyester comprising a dicarboxylic acid component and a diol component. Examples of the dicarboxylic acid component include components derived from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, adipic acid, sebacic acid, and the like.
  • diol component examples include components derived from ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, and the like.
  • aromatic polyesters are preferable, and polyethylene terephthalate is particularly preferable.
  • Polyethylene terephthalate may be a homopolymer, but is preferably a copolymer because the crystallization is suppressed when the film is stretched uniaxially or biaxially and the effect of improving stretchability and film-forming property is enhanced. .
  • the copolymer component examples include the dicarboxylic acid component and the diol component described above, and isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of high heat resistance and a high effect of improving the film forming property.
  • the proportion of the copolymerization component is, for example, 1 to 20 mol%, preferably 2 to 18 mol%, more preferably 3 to 15 mol%, particularly preferably 7 to 11 based on 100 mol% of the total dicarboxylic acid component of the polyester. Mol%.
  • the inorganic particles are preferably white inorganic particles.
  • the white inorganic particles include barium sulfate, titanium dioxide, silicon dioxide, and calcium carbonate particles. These inorganic particles should just select an average particle diameter and content so that a white reflective film may have an appropriate reflectance, and these are not specifically limited.
  • the reflectance of the reflective layer A or the white reflective film may be within a preferable range in the present invention. Moreover, what is necessary is just to make it the void volume ratio in the reflection layer A become the preferable range in this invention.
  • the average particle diameter of the inorganic particles is, for example, 0.2 to 3.0 ⁇ m, preferably 0.3 to 2.5 ⁇ m, and more preferably 0.4 to 2.0 ⁇ m.
  • the content thereof is preferably 20 to 60% by mass based on the mass of the reflective layer A, more preferably 25 to 55% by mass, and most preferably 31 to 53% by mass.
  • the inorganic particles may have any particle shape, for example, a plate shape or a spherical shape.
  • the inorganic particles may be subjected to a surface treatment for improving dispersibility.
  • the incompatible resin is not particularly limited as long as it is incompatible with the thermoplastic resin constituting the layer.
  • the thermoplastic resin is polyester, polyolefin, polystyrene, or the like is preferable. These may be in the form of particles.
  • the content should just select an average particle diameter and content so that a white reflective film may have a suitable reflectance similarly to the case of an inorganic particle, These are not specifically limited.
  • the reflectance of the reflective layer A or the white reflective film may be within a preferable range in the present invention.
  • the content is preferably 10 to 50% by mass, more preferably 12 to 40% by mass, and most preferably 13 to 35% by mass based on the mass of the reflective layer A.
  • the reflective layer A is made of other components such as UV absorbers, antioxidants, antistatic agents, fluorescent brighteners, waxes, particles and resins different from the void forming agents. Can be contained.
  • the surface layer B made of the thermoplastic resin composition containing particles forms at least one outermost layer of the white reflective film.
  • the surface layer B that forms the outermost layer has protrusions formed of the particles on the surface opposite to the reflective layer A (hereinafter sometimes referred to as the outermost layer surface).
  • Such protrusions need to have protrusions with an appropriate height at an appropriate frequency on the outermost layer surface from the viewpoint of securing a gap between the light guide plate and the film. Therefore, in the present invention, the number of protrusions having a height of 5 ⁇ m or more (protrusion frequency) is 10 on the outermost layer surface. 4 ⁇ 10 10 Pieces / m 2 Usually it is necessary. Thereby, the gap between the light guide plate and the film can be sufficiently secured, and the sticking suppression effect is excellent. If the projection frequency is too low, the sticking suppression effect is poor.
  • the ten-point average roughness (Rz) on the surface of the outermost layer and the average particle diameter d of the particles constituting the surface layer B (the secondary particle diameter ds when the particles are aggregated particles) and
  • Rz the ten-point average roughness
  • the effect of improving the gap can be increased.
  • the value of Rz when the value of Rz is smaller than the value on the left side, it represents an aspect in which the particles are buried too much in the surface layer B, and thus the effect of improving the gap tends to be reduced. From such a viewpoint, it is more preferable that 0.2 ⁇ d ( ⁇ m) ⁇ Rz ( ⁇ m), and still more preferably 0.3 ⁇ d ( ⁇ m) ⁇ Rz ( ⁇ m).
  • the value of Rz is larger than the value on the right side, it represents an aspect in which the particles protrude too much from the surface layer B, and the effect of suppressing particle dropout at the time of contact with the light guide plate tends to be low.
  • the thickness of the surface layer B can be adjusted by taking into consideration the average particle diameter d of the particles used (or the secondary particle diameter ds when the particles are aggregated particles described later). Good. For example, in a particle having a certain average particle diameter, when the thickness of the surface layer B is reduced, the value of Rz tends to increase. On the other hand, when the thickness of the surface layer B is increased, the value of Rz tends to decrease. Adjustments can be made in consideration of such trends.
  • the present invention employs soft particles having a high compressibility or a low 10% compressive strength (S10 strength) as the particles of the surface layer B.
  • the surface layer B is formed into an oriented layer or a hard protrusion. By doing so, sticking to the light guide plate is suppressed, and at the same time, scratching of the light guide plate is suppressed.
  • the surface layer in each aspect of the white reflective film a which comprises the particles having a high compressibility and the oriented surface layer B, and the white reflective film b which comprises particles having a low S10 strength and hard protrusions The aspect of B is demonstrated.
  • the surface layer B of the white reflective film a in the present invention is an oriented layer made of a thermoplastic resin composition containing particles.
  • the “oriented layer” is not a layer formed by applying a coating solution to a film that has been stretched, but is subjected to, for example, a coextrusion method as described in the preferred production method described below, and then stretched. Indicates that the layer is formed.
  • the surface layer B is preferably an oriented polyester film layer, and more preferably an oriented polyethylene terephthalate film layer.
  • a biaxially oriented polyester film layer is more preferred, and a biaxially oriented polyethylene terephthalate film layer is particularly preferred. Thereby, the improvement effect of film forming property can be made high.
  • Thermoplastic resin The aspect of the thermoplastic resin of the white reflective film a will be described later.
  • the particles contained in the surface layer B of the white reflective film a are particles having a compressibility of 40% or more when compressed with a load of 0.3 gf determined by a measurement method described later.
  • the above-described particles are used as the particles forming the surface irregularities for securing the gap and suppressing the sticking to the light guide plate, thereby simultaneously suppressing the scratches on the light guide plate. Can do.
  • the present invention in order to secure a gap, the surface of the surface layer B has a specific projection mode, and in order to obtain such a projection mode, particles having a relatively large particle size are preferably employed.
  • the present invention has the above-described specific compression ratio because the film breakage usually starts from the particles.
  • the compression ratio when compressed with a particle load of 0.3 gf is preferably 42% or more, more preferably 44% or more, and further preferably 45% or more.
  • the compression ratio when compressed with a particle load of 0.3 gf is preferably 95% or less, more preferably 90% or less, and further preferably 85% or less.
  • the particles in the surface layer B of the white reflective film a can satisfy the aspect of the protrusion on the surface layer B surface defined by the present invention, and are not particularly limited as long as the aspect of the compression ratio is satisfied. It may be organic particles, inorganic particles, or organic-inorganic composite particles.
  • the shape of the particles is not particularly limited, and examples thereof include spherical particles, tabular particles, aggregated particles, and hollow particles. Among these, agglomerated particles are preferable, and a preferable agglomerated particle mode of the white reflective film a will be described later.
  • the surface layer B of the white reflective film b in the present invention is made of a thermoplastic resin composition containing particles.
  • thermoplastic resin The aspect of the thermoplastic resin of the white reflective film b will be described later.
  • the surface layer B containing the particles forms at least one outermost layer of the white reflective film, and the surface of the surface layer B that forms the outermost layer is the surface opposite to the reflective layer A. And having protrusions formed by the particles.
  • the 10% compressive strength (S10 strength) when the particles are compressed with a load of 3 gf determined by the measurement method described later is 0.1 MPa or more and 10 MPa or less. It is necessary that the Vickers hardness when measured with a weight of 500 N determined by the above is 5 or more and 30 or less.
  • the present invention employs relatively soft particles as described above as particles forming surface irregularities to secure a gap and suppress sticking to the light guide plate, and at the same time, the hardness of the protrusions as described above.
  • the effect of suppressing sticking to the light guide plate and the effect of suppressing damage to the light guide plate can be achieved at the same time. This is thought to be due to the following mechanism. That is, first, the sticking between the reflection plate and the light guide plate is an operation of pressing the light guide plate and the reflection plate, and thus the direction parallel to the height direction of the protrusion (perpendicular to the film surface). It is considered that the Vickers hardness in the height direction of the projection can be suppressed by making it a relatively hard region as in the above numerical range.
  • the operation is such that the light guide plate and the reflective plate are rubbed together, and therefore stress applied in a direction perpendicular to the height direction of the protrusion (direction parallel to the film surface) with respect to the protrusion. Since it is related, the protrusion can be slightly deformed and distorted in the direction perpendicular to the height direction, or it can be suppressed by making the S10 intensity of the particles forming the protrusion a relatively soft region as in the above numerical range. it is conceivable that.
  • the S10 strength of the particles is too high, deformation tends to be difficult to occur when stress is applied in a direction perpendicular to the height direction of the protrusion, and the effect of suppressing damage to the light guide plate is poor. It is 0 MPa or less, more preferably 2.0 MPa or less, further preferably 1.0 MPa or less, and particularly preferably 0.8 MPa or less. If the S10 strength of the particles is too high, the Vickers hardness of the protrusions may become too high.
  • the S10 strength of the particles tends to make it difficult to increase the Vickers hardness of the protrusion if it is too low, it is preferably at least 0.12 MPa, more preferably at least 0.13 MPa, even more preferably at least 0.14 MPa. Especially preferably, it is 0.15 MPa or more.
  • the effect of suppressing sticking to the light guide plate is inferior, and is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more.
  • the Vickers hardness of the protrusion is preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the particles in the surface layer B of the white reflective film b can satisfy the aspect of the projection on the surface layer B surface defined by the present invention, and are not particularly limited as long as the aspect of the S10 strength is satisfied. It may be organic particles, inorganic particles, or organic-inorganic composite particles.
  • the shape of the particles is not particularly limited, and examples thereof include spherical particles, tabular particles, aggregated particles, and hollow particles. Among these, agglomerated particles are preferred, and a preferred agglomerated particle aspect of the white reflective film b will be described later.
  • the surface layer B of the white reflective film b in the present invention may be formed by any method as long as it satisfies the above requirements. For example, the sheet can be melted at the same time as the material of the reflective layer A and extruded from the same or adjacent die, and a sheet formed by stretching and crystallization (melt coextrusion method) can be used.
  • a coating method in which a coating solution dissolved in a solvent or water is applied and then dried.
  • a melt coextrusion method and formation from a coating solution using water as a solvent are preferable.
  • the resin added with particles is melted simultaneously with the material of the reflective layer A.
  • the most preferable method is to stretch and crystallize sheets formed by extrusion from the same or adjacent die.
  • the surface layer B of the white reflective film b is preferably an oriented polyester film layer, and more preferably an oriented polyethylene terephthalate film layer.
  • a biaxially oriented polyester film layer is more preferred, and a biaxially oriented polyethylene terephthalate film layer is particularly preferred. This makes it easy to obtain a suitable Vickers hardness of the protrusion.
  • thermoplastic resin As the thermoplastic resin of the thermoplastic resin composition constituting the surface layer B, the same thermoplastic resin as the thermoplastic resin constituting the reflective layer A described above can be used. Among these, polyester is preferable from the viewpoint of obtaining a white reflective film excellent in mechanical properties and thermal stability, and from the viewpoint of easily obtaining the oriented surface layer B or obtaining a suitable Vickers hardness of the protrusion. As this polyester, the same polyester as the polyester in the reflective layer A described above can be used.
  • polyesters aromatic polyesters are preferable, and polyethylene terephthalate is particularly preferable from the viewpoint of obtaining a white reflective film excellent in mechanical properties and thermal stability.
  • Polyethylene terephthalate may be a homopolymer, but a copolymer is preferred from the viewpoint that crystallization is suppressed when the film is stretched uniaxially or biaxially and the effect of improving stretchability and film-forming property is enhanced.
  • the copolymer component include the dicarboxylic acid component and the diol component described above, and isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of high heat resistance and a high effect of improving the film forming property.
  • the ratio of the copolymerization component is, for example, 1 to 20 mol%, preferably 2 to 18 mol%, more preferably 3 to 17 mol%, particularly preferably 12 to 16 mol% based on 100 mol% of the total dicarboxylic acid component of the polyester. Mol%.
  • the ratio of the copolymer component is within this range, the effect of improving the film forming property is excellent. Further, it is easy to achieve the Vickers hardness of the protrusion. Furthermore, it has excellent thermal dimensional stability.
  • the particles suitably used for the surface layer B of the white reflective film a and the surface layer B of the white reflective film b described above are preferably aggregated particles.
  • Such aggregated particles may be organic aggregated particles or inorganic aggregated particles.
  • the organic aggregated particles include polyester aggregated particles, acrylic aggregated particles, polyurethane aggregated particles, and polyethylene aggregated particles from the viewpoint of easily obtaining a suitable compressibility and S10 strength and from the viewpoints of heat resistance and surface protrusion formation.
  • polyester agglomerated particles are preferable because they have good compatibility with the main raw material polyester and have little influence on film forming properties.
  • an inorganic aggregated particle a silica aggregated particle, an alumina aggregated particle, and a ceramic aggregated particle are mentioned preferably from a viewpoint with which a suitable compressibility and S10 intensity
  • the particles of the surface layer B are preferably inorganic agglomerated particles from the viewpoint that a suitable compressibility and S10 strength can be easily obtained, and excellent heat resistance and easy formation of surface protrusions. Particles are particularly preferred.
  • the aggregated particles in the surface layer B preferably have a secondary particle size (ds) of 5 ⁇ m or more and 100 ⁇ m or less.
  • the aspect of the protrusion on the surface layer B surface defined by the present invention can be easily satisfied, the distance between the light guide plate and the film can be kept constant, and the sticking of these can be further suppressed, and the film can be formed.
  • the effect of improving the property is increased.
  • the secondary particle size is more preferably 6 ⁇ m or more, further preferably 8 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
  • the effect of improving the film forming property tends to be low.
  • the secondary particle diameter of the white reflective film a is preferably 90 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 70 ⁇ m or less, particularly preferably 60 ⁇ m or less, and most preferably 50 ⁇ m or less.
  • the secondary particle size is preferably 95 ⁇ m or less, more preferably 90 ⁇ m or less, still more preferably 80 ⁇ m or less, particularly preferably 30 ⁇ m or less, and most preferably 25 ⁇ m or less.
  • the average particle diameter d of the particles is preferably in the same range as the secondary particle diameter ds from the same viewpoint as described above.
  • the primary particle size (dp) of the aggregated particles is preferably 0.01 ⁇ m or more, and preferably 5 ⁇ m or less.
  • the primary particle diameter is more preferably 0.02 ⁇ m or more, further preferably 0.03 ⁇ m or more, and particularly preferably 0.05 ⁇ m or more.
  • the surface is more preferably 4 ⁇ m or less, further preferably 3 ⁇ m or less, particularly preferably 2 ⁇ m or less, and most preferably 1 ⁇ m or less.
  • the content of the particles in the surface layer B is preferably 30% by volume or less based on the volume of the surface layer B. By setting it as this range, it is excellent in film forming property. Moreover, it is preferable that it is 1 volume% or more and 30 volume% or less, and it becomes easy to set it as the aspect of the surface layer B surface suitable in this invention. If the amount is too small, surface irregularities tend to be reduced, and it tends to be difficult to keep the distance from the light guide plate constant. Therefore, it is more preferably 2% by volume or more, particularly preferably 3% by volume or more.
  • the amount is more preferably 25% by volume or less, further preferably 20% by volume or less, and particularly preferably 15% by volume or less.
  • the content of the particles in the surface layer B is preferably 1% by volume or more and 50% by volume or less based on the volume of the surface layer B.
  • the amount is more preferably 2% by volume or more, particularly preferably 3% by volume or more.
  • the amount is more preferably 45% by volume or less, further preferably 40% by volume or less, and particularly preferably 30% by volume or less.
  • the volume fraction of particles can be determined from the mass fraction and density of the thermoplastic resin constituting the surface layer B and the mass fraction and density of the particles.
  • the surface layer B may contain components other than the above-described constituent components as long as the object of the present invention is not impaired. Examples of such components include ultraviolet absorbers, antioxidants, antistatic agents, fluorescent brighteners, waxes, particles and resins that are different from the aggregated particles. Further, the surface layer B may contain the void forming agent mentioned in the reflective layer A within a range not impairing the object of the present invention, and by making such an aspect, the effect of improving the reflectance is enhanced. be able to.
  • the void volume ratio in the surface layer B (ratio of the volume of voids in the surface layer B to the volume of the surface layer B) is preferably 0% by volume or more and less than 15% by volume, more preferably 5%. It is not more than volume%, particularly preferably not more than 3 volume%.
  • the preferable void volume ratio in the reflective layer A and the preferable void volume ratio in the surface layer B described above are simultaneously adopted. Is particularly preferred.
  • the thickness of the reflective layer A in the present invention is preferably 80 to 300 ⁇ m. Thereby, the improvement effect of a reflectance can be made high. If it is too thin, the effect of improving the reflectance is low, while if it is too thick, it is inefficient. From such a viewpoint, the thickness is more preferably 150 to 250 ⁇ m.
  • the thickness of the surface layer B (when there are a plurality of layers, the thickness of one layer forming the outermost layer on the light guide plate side) is preferably 10 to 70 ⁇ m.
  • the relationship between the average particle diameter d of the particles or the secondary particle size ds of the aggregated particles and the ten-point average roughness Rz can be easily set to the preferred mode as described above. It is easy to secure the gap. Moreover, it becomes easy to make the aspect of Rz and protrusion frequency into the preferable aspect mentioned above. Furthermore, the improvement effect of a reflectance and the improvement effect of film forming property can be made high. If it is too thin, it is difficult to achieve a preferable Rz, and the effect of suppressing particle dropout tends to be reduced. In addition, the effect of improving the film forming property tends to be low.
  • the average particle diameter d of the particles in the surface layer B (secondary particle diameter ds in the case of aggregated particles) and the thickness t of the surface layer B satisfy the following formula. preferable. 0.05 ⁇ d ( ⁇ m) / t ( ⁇ m) ⁇ 20
  • d ( ⁇ m) / t ( ⁇ m) ⁇ 19 is preferable, d ( ⁇ m) / t ( ⁇ m) ⁇ 18 is more preferable, d ( ⁇ m) / t ( ⁇ m) ⁇ 10 is particularly preferable. Is an embodiment satisfying d ( ⁇ m) / t ( ⁇ m) ⁇ 2.
  • the average particle diameter d of the particles added to the surface layer B (secondary particle diameter ds when the particles are aggregated particles) from the viewpoint of facilitating appropriate hardness of the protrusions.
  • the thickness t of the surface layer B (the thickness of the portion of the surface layer B where no particles protrude from the surface) t is preferably in a relationship of 1.5d ⁇ t ⁇ 5.0d. More preferably, 2.0d ⁇ t ⁇ 4.0d, and most preferably 2.5d ⁇ t ⁇ 3.5d.
  • the laminated structure of the white reflective film is B / A two-layer configuration, B / A / B three-layer configuration, B / A / B ′ / A four-layer structure of A (where B ′ represents an inner layer B ′ having the same structure as the surface layer B), and a multilayer structure of five or more layers in which B is disposed on at least one of the outermost layers.
  • B ′ represents an inner layer B ′ having the same structure as the surface layer B
  • B multilayer structure of five or more layers in which B is disposed on at least one of the outermost layers.
  • Particularly preferred are a two-layer structure of B / A and a three-layer structure of B / A / B. Most preferably, it has a three-layer structure of B / A / B, and is excellent in film forming property. Further, problems such as curling are unlikely to occur.
  • the reflection layer A and the surface layer B have a thickness ratio of the reflection layer A of 50 to 90% and a thickness ratio of the surface layer B of 5 to 50% when the thickness of the entire white reflection film is 100%. Furthermore, the aspect which is 5 to 25% is preferable, and the balance of each characteristic such as the reflection characteristic and the film forming property can be improved.
  • the thickness ratio of each layer refers to the ratio between the integrated thicknesses when there are a plurality of layers.
  • other layers may be provided as long as the object of the present invention is not impaired. For example, you may have the layer for providing functions, such as antistatic property, electroconductivity, and ultraviolet durability.
  • the void volume ratio for improving the film formability of the film is relatively low (preferably 0% by volume or more and less than 15% by volume, more preferably 5% by volume or less, particularly preferably 3% by volume or less. )
  • a support layer C can also be provided.
  • the surface layer B can be easily oriented, and the desired Vickers hardness of the protrusion can be easily obtained.
  • the white reflective film of the present invention is produced by laminating the reflective layer A and the surface layer B by a coextrusion method.
  • the reflective layer A and the surface layer B are directly laminated by a coextrusion method.
  • polyester is employed as the thermoplastic resin constituting the reflective layer A and the thermoplastic resin constituting the surface layer B and a co-extrusion method is employed as a laminating method. It is not limited to this, and other embodiments can be produced in the same manner with reference to the following.
  • the following “melt extrusion temperature” may be read as, for example, “melt temperature”.
  • the melting point of the polyester used is Tm (unit: ° C.), and the glass transition temperature is Tg (unit: ° C.).
  • a polyester composition for forming the reflective layer A is prepared by mixing polyester, a void forming agent, and other optional components.
  • polyester composition for forming the surface layer B is prepared. These polyester compositions are used after drying to sufficiently remove moisture. Next, the dried polyester composition is put into separate extruders and melt-extruded. The melt extrusion temperature needs to be Tm or higher, and may be about Tm + 40 ° C. At this time, the polyester composition used for the production of the film, particularly the polyester composition used for the reflective layer A, is filtered using a nonwoven fabric type filter having an average aperture of 10 to 100 ⁇ m made of stainless steel fine wires having a wire diameter of 15 ⁇ m or less. It is preferable.
  • the average opening of the nonwoven fabric is preferably 20 to 50 ⁇ m, more preferably 15 to 40 ⁇ m.
  • the filtered polyester composition is extruded in a multilayer state from a die by a simultaneous multilayer extrusion method (coextrusion method) using a feed block in a molten state, and an unstretched laminated sheet is produced.
  • the unstretched laminated sheet extruded from the die is cooled and solidified with a casting drum to obtain an unstretched laminated film.
  • this unstretched laminated film is heated by roll heating, infrared heating or the like, and stretched in the film forming machine axial direction (hereinafter sometimes referred to as the longitudinal direction or the longitudinal direction or MD) to obtain a longitudinally stretched film.
  • This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls.
  • the film after the longitudinal stretching is then guided to a tenter and stretched in a direction perpendicular to the longitudinal direction and the thickness direction (hereinafter sometimes referred to as a transverse direction or a width direction or TD) to be biaxially stretched.
  • As the stretching temperature it is preferably performed at a temperature of Tg or more and Tg + 30 ° C.
  • the polyester preferably the polyester constituting the reflective layer A
  • excellent in film forming properties and voids are preferably formed.
  • the stretching ratio is preferably 2.5 to 4.3 times, more preferably 2.7 to 4.2 times in both the vertical direction and the horizontal direction. If the draw ratio is too low, uneven thickness of the film tends to be worsened, and voids tend not to be formed. On the other hand, if it is too high, breakage tends to occur during film formation.
  • the second stage in this case, lateral stretching should be about 10 to 50 ° C. higher than the first stage stretching temperature. Is preferred.
  • the pre-heat treatment for transverse stretching may be performed by gradually increasing the temperature starting from a temperature higher than Tg + 5 ° C. of the polyester (preferably the polyester constituting the reflective layer A).
  • the temperature rise in the transverse stretching process may be continuous or stepwise (sequential), the temperature is usually raised sequentially.
  • the transverse stretching zone of the tenter is divided into a plurality along the film running direction, and the temperature is raised by flowing a heating medium having a predetermined temperature for each zone.
  • the biaxially stretched film is subsequently subjected to heat setting and heat relaxation treatment in order to make a biaxially oriented film, but these processes can also be performed while the film is running following melt extrusion to stretching. .
  • the film after biaxial stretching has a constant width or (Tm ⁇ 20 ° C.) to (Tm ⁇ 100 ° C.) with the melting point of the polyester (preferably the polyester constituting the reflective layer A) as Tm while holding both ends with clips. It is preferable to heat-treat under a width reduction of 10% or less and heat-set to lower the heat shrinkage rate. When the heat treatment temperature is too high, the flatness of the film tends to deteriorate, and the thickness unevenness tends to increase.
  • both ends of the film being held can be cut off, the take-up speed in the film vertical direction can be adjusted, and the film can be relaxed in the vertical direction.
  • the speed of the roll group on the tenter exit side is adjusted.
  • the rate of relaxation the speed of the roll group is reduced with respect to the film line speed of the tenter, preferably 0.1 to 2.5%, more preferably 0.2 to 2.3%, particularly preferably 0.3.
  • the film is relaxed by carrying out a speed reduction of ⁇ 2.0% (this value is referred to as “relaxation rate”), and the longitudinal heat shrinkage rate is adjusted by controlling the relaxation rate.
  • the width of the film in the horizontal direction can be reduced in the process until both ends are cut off, and a desired heat shrinkage rate can be obtained.
  • a lateral-longitudinal sequential biaxial stretching method may be used in addition to the longitudinal-lateral sequential biaxial stretching method as described above. Moreover, it can form into a film using a simultaneous biaxial stretching method.
  • the stretching ratio is, for example, 2.7 to 4.3 times, preferably 2.8 to 4.2 times in both the longitudinal direction and the transverse direction.
  • the white reflective film of the present invention can be obtained.
  • the reflectance measured from the surface layer B side of the white reflective film of the present invention is preferably 96% or more, more preferably 97% or more, and further preferably 97.5% or more. When the reflectance is 96% or more, high luminance can be obtained when used in a liquid crystal display device or illumination.
  • Such a reflectance may be a preferable aspect such as increasing the void volume ratio of the reflective layer A, or a preferable aspect of each layer such as increasing the thickness of the reflective layer A or reducing the thickness of the surface layer B. Can be achieved.
  • luminance measured from the surface layer B side is calculated
  • the reflectance and brightness are values on the surface on the side of the light guide plate when used with the light guide plate in the white reflective film.
  • the amount of volatile organic solvent measured by the method described later is preferably 10 ppm or less.
  • the surface layer B is not formed by a coating method using an organic solvent.
  • a gas mark is hardly generated, and the film forming property (collecting film forming property) is improved. From this viewpoint, it is more preferably 5 ppm or less, further preferably 3 ppm or less, and ideally 0 ppm.
  • the amount of the volatile organic solvent in order to reduce the amount of the volatile organic solvent, it is preferable to employ the above-described method without employing the solution coating method using the organic solvent in the formation of the surface layer B. Also, the amount of volatile organic solvent tends to increase with the use of organic particles.
  • Each characteristic value was measured by the following method.
  • the particle size of 100 primary particles was arbitrarily measured, and the primary particle size (dp) was determined from the average value.
  • the aggregated particles are also dissolved (for example, in the case of organic particles), the aggregated particles before blending are used, and the S-4700 field emission scan manufactured by Hitachi, Ltd. is used.
  • the S-4700 field emission scan manufactured by Hitachi, Ltd. is used.
  • observe at a magnification of 10,000 times observe the agglomeration state of primary particles on the surface of the secondary particles, measure the particle size of 100 primary particles arbitrarily, and determine the primary particle size from the average value ( dp) was determined.
  • the minor axis indicates the maximum diameter in the direction perpendicular to the major axis.
  • the resin component is dissolved with the solvent
  • the aggregated particles are also dissolved (for example, in the case of organic particles)
  • the aggregated particles before blending are used, and the S-4700 field emission scan manufactured by Hitachi, Ltd. is used.
  • observation was performed at a magnification of 1000 times, the particle size of 100 particles was arbitrarily measured, and the secondary particle size (ds) was obtained from the average value.
  • the volume was calculated as an area ⁇ thickness, where the sample was cut into an area of 3 cm 2 and the thickness at that size was measured at 10 points with an electric micrometer (K-402B manufactured by Anritsu). The mass was weighed with an electronic balance.
  • the specific gravity of the particles including aggregated particles
  • the value of bulk specific gravity obtained by the following graduated cylinder method was used. Fill a 1000 ml measuring cylinder with completely dry particles, measure the total weight, subtract the weight of the measuring cylinder from the total weight to obtain the weight of the particle, and measure the volume of the measuring cylinder. , By dividing the weight (g) of the particles by the volume (cm 3 ).
  • Luminance The reflective film is taken out from the LED liquid crystal television (LG42LE5310AKR) manufactured by LG, and the surface layer B side of the various reflective films described in the examples is installed on the screen side (side in contact with the light guide plate).
  • the luminance meter Model MC-940, manufactured by Otsuka Electronics Co., Ltd.
  • the luminance was measured at a measurement distance of 500 mm from the front of the center of the backlight.
  • Adhesion spot evaluation As shown in FIG. 2, take out the chassis (6) from the LED liquid crystal television (LG42LE5310AKR) manufactured by LG and place it on a horizontal desk so that the inside of the television is facing upward.
  • the film was placed with the surface layer surface facing upward, and further, the light guide plate and three optical sheets (two diffusing films and one prism) originally provided in the television were placed thereon (7).
  • an equilateral triangular base (801) having three columnar legs having a diameter of 5 mm as shown in FIG. 2 is placed in an area including the most severely uneven portion of the chassis within the plane, and a further 15 kg is placed thereon.
  • a region surrounded by the three legs was visually observed, and if there was no abnormally bright part, “no adhesion spots” (adhesion spots evaluation ⁇ ) was obtained. If there is an abnormally bright part, place the DBEF sheet originally provided on the television on the three optical sheets and observe it in the same manner.
  • Amount of volatile organic solvent At room temperature (23 ° C.), 1 g of a film sample was placed in a 10 L fluororesin bag, and the inside was purged with pure nitrogen and sealed. Next, immediately from the nitrogen in the bag, 0.2 L and 1.0 L of nitrogen were collected in two analytical TENAX-TA collection tubes at a flow rate of 0.2 L / min. The mass of the organic solvent component contained in nitrogen collected by HPLC and GCMS was quantified. The obtained value is converted into the amount in 10 L of nitrogen, and the mass of the organic solvent volatilized in 10 L of nitrogen is obtained from 1 g of the film sample, and the amount of volatile organic solvent (unit: ppm, based on the mass of the film sample) did.
  • Examples 1 to 10 and Comparative Examples 1 and 2 (16) Evaluation of scratches on light guide plate (evaluation of abrasion) and evaluation of dropout of particles (1) As shown in FIG. 1, an iron plate (2, weight about 200 g) of length 200 mm ⁇ width 200 mm ⁇ thickness 3 mm is firmly attached to the end of the handle portion (1), and the evaluation surface is 250 mm wide with the evaluation surface on top.
  • a reflective film (3) having a length of 200 mm was pasted so that each 25 mm portion protruded from the iron plate from both ends in the width direction (so that the central 200 mm ⁇ 200 mm portion overlapped the iron plate).
  • the evaluation surface (surface layer surface) of the reflective film was placed outside.
  • the remaining 25 mm at both ends in the width direction of the reflective film is folded back to the back side of the iron plate, eliminating the effect of the edge of the reflective film (the part where the blade is inserted with a knife during sampling) scraping the light guide plate. did.
  • a light guide plate (4, having a size of at least 400 mm ⁇ 200 mm) with a dot surface having dots (401) is fixed on a horizontal desk, and the reflection film fixed on the iron plate created above is evaluated.
  • the reflective film fixed to the iron plate is moved.
  • 15 reciprocations were performed at a speed of about 5 to 10 seconds per reciprocation.
  • the degree of shaving and the presence or absence of particles dropped from the reflective film were observed using a 20-fold magnifier and evaluated according to the following criteria.
  • the degree of shaving and the presence or absence of particles dropped from the reflective film were observed using a 20-fold magnifier and evaluated according to the following criteria.
  • “cannot be scraped” if there are no scratches that can be observed with a loupe after 15 reciprocating movements, it is determined that “cannot be scraped” (scraping evaluation ⁇ ), and scratches that can be observed after 10 reciprocating movements.
  • “scratch was difficult” scraping evaluation ⁇
  • when there were scratches that could be observed after 10 reciprocating movements “scraping” (scraping evaluation ⁇ ) was designated.
  • Example 1 Manufacture of white reflective film
  • Each layer was mixed so as to have the structure described in Table 1, and charged into an extruder.
  • Layer A was melt extrusion temperature 255 ° C
  • layer B was melt extrusion temperature 230 ° C
  • Table 1 was used.
  • the layers were combined using a three-layer feed block device so as to have a layer structure of B layer / A layer / B layer, and formed into a sheet shape from a die while maintaining the laminated state. At this time, it adjusted with the discharge amount of each extruder so that the thickness ratio of B layer / A layer / B layer might become 10/80/10 after biaxial stretching. Further, this sheet was an unstretched film cooled and solidified with a cooling drum having a surface temperature of 25 ° C. This unstretched film is led to a longitudinal stretching zone maintained at 92 ° C.
  • Example 2 After cooling, a film having a thickness of 250 ⁇ m was obtained as shown in Table 1.
  • the evaluation results of the obtained film are shown in Table 2.
  • Examples 2 to 10, Comparative Examples 1 and 2 A white reflective film was obtained in the same manner as in Example 1 except that the form of particles used for the surface layer was as shown in Table 1.
  • the evaluation results of the obtained film are shown in Table 2.
  • the types of particles used are as follows. Aggregated particles B: AY-601 (aggregated silica) manufactured by Tosoh Silica Co., Ltd. was air-classified to an average particle size (secondary particle size) of 15 ⁇ m.
  • Aggregated particles C C812 (aggregated silica) manufactured by Grace Japan KK was air-classified to obtain an average particle size (secondary particle size) of 15 ⁇ m.
  • Aggregated particles D Carriage P-10 (aggregated silica) manufactured by Fuji Silysia Chemical Co., Ltd. was air-classified to an average particle size (secondary particle size) of 15 ⁇ m.
  • Aggregated particles E: C622 (aggregated silica) manufactured by Grace Japan KK was air-classified to obtain an average particle size (secondary particle size) of 15 ⁇ m.
  • Aggregated particles F AY-601 manufactured by Tosoh Silica Co., Ltd. was air-classified to an average particle size (secondary particle size) of 20 ⁇ m.
  • Aggregated particles G AY-601 manufactured by Tosoh Silica Co., Ltd. was air-classified to an average particle size (secondary particle size) of 10 ⁇ m.
  • Cross-linked acrylic particles A BMX-30 (true spherical particles) manufactured by Sekisui Plastics
  • the isophthalic acid copolymerized polyethylene terephthalate 2 obtained above was mixed as agglomerated particles H with 8% by mass of Carrier Sirt P-10 manufactured by Fuji Silysia Chemical Co., Ltd. and extruded at a melting temperature of 235 ° C. Chip 3 was created.
  • Example 11 Manufacture of white reflective film
  • Each layer was mixed so as to have the structure described in Table 3, and charged into an extruder.
  • the A layer was melt extruded at a temperature of 255 ° C.
  • the B layer was melt extruded at a temperature of 230 ° C.
  • the layers were merged so as to have a layer configuration of layer A / layer B, and formed into a sheet from a die while maintaining the laminated state.
  • it adjusted with the discharge amount of each extruder so that the thickness ratio of B layer / A layer / B layer might become 10/80/10 after biaxial stretching.
  • this sheet was an unstretched film cooled and solidified with a cooling drum having a surface temperature of 25 ° C. This unstretched film is led to a longitudinal stretching zone maintained at 92 ° C.
  • Example 12 A white reflective film was obtained in the same manner as in Example 11 except that AY-603 manufactured by Tosoh Silica Co., Ltd. was used as the particles of the surface layer B. Table 4 shows the evaluation results of the obtained film.
  • Example 13 A white reflective film was obtained in the same manner as in Example 11 except that G0105 manufactured by Tosoh Silica Co., Ltd. was used as the particles of the surface layer B, and the lateral draw ratio was set to 4.0 times. Table 4 shows the evaluation results of the obtained film.
  • Example 3 A white reflective film was obtained in the same manner as in Example 11 except that cross-linked poly (methyl methacrylate) (PMMA) particles manufactured by Soken Chemical were used as the particles of the surface layer B.
  • Comparative Example 4 Adjustment of coating liquid
  • Water-soluble polyester binder Z565 (solid content 30%) manufactured by Kyodo Chemical Co., Ltd. is 60% by mass as a solid content
  • carrier ct P-10 manufactured by Fuji Silysia Chemical Co., Ltd. is 35% by mass as a solid content.
  • the coating liquid for forming the surface layer B was prepared by diluting 420 with 5% by mass as a solid content and diluting with water so that the total solid content concentration of the coating liquid was 30% by mass.
  • the above-obtained isophthalic acid copolymerized polyethylene terephthalate 1 and particle master chip 1 were used as the raw material for the reflective layer (A layer), and isophthalic acid copolymerized polyethylene terephthalate 2 was used as the raw material for the support layer (C layer).
  • the layer A has a melt extrusion temperature of 255 ° C.
  • the layer C has a melt extrusion temperature of 230 ° C.
  • the layer configuration of layer C / layer A were merged using a two-layer feed block device and formed into a sheet shape from a die while maintaining the laminated state.
  • this sheet was an unstretched film cooled and solidified with a cooling drum having a surface temperature of 25 ° C.
  • the coating liquid having the above-described composition is applied to the A layer side of this unstretched film with a roll coater so that the coating layer thickness after drying is 3 ⁇ m, and then passed through a preheating zone at 73 ° C., followed by a preheating zone at 75 ° C.
  • the film was led to a longitudinal stretching zone maintained at 92 ° C., stretched 2.9 times in the longitudinal direction, and cooled by a roll group at 25 ° C.
  • the film was led to a transverse stretching zone maintained at 130 ° C. through a preheating zone at 115 ° C., and stretched 3.8 times in the transverse direction.
  • the surface layer B can be formed simultaneously.
  • heat setting is performed at 185 ° C. in the tenter, the width is set to 2%, the width is set in the horizontal direction at a temperature of 130 ° C., then both ends of the film are cut off, and the film is thermally relaxed at a longitudinal relaxation rate of 2%.
  • a white reflective film was obtained in which a coating layer B having a thickness of 3 ⁇ m as a surface layer B was formed on a base material (A layer + C layer) having a thickness of 250 ⁇ m.
  • Table 4 shows the evaluation results of the obtained film.
  • a white reflective film was obtained in the same manner as in Comparative Example 4 except that the particles added to the coating liquid for forming the surface layer B were changed to AY-603 manufactured by Tosoh Silica Corporation. The evaluation results of the obtained film are shown in Table 4.
  • the white reflective film which can fully suppress the damage
  • it is excellent in the film forming property of a film, and is a white reflective film Can be provided.
  • the white reflective film of the present invention can sufficiently suppress sticking to the light guide plate and can sufficiently suppress scratches on the light guide plate
  • the surface light source reflector provided with the light guide plate among others, for example, It can be suitably used as a reflective film used for an edge light type backlight unit used in a liquid crystal display device or the like.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Planar Illumination Modules (AREA)
  • Nonlinear Science (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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KR20150118194A (ko) 2015-10-21
KR20150065904A (ko) 2015-06-15
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