CN107272091A - White reflection film - Google Patents

White reflection film Download PDF

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Publication number
CN107272091A
CN107272091A CN201710367396.7A CN201710367396A CN107272091A CN 107272091 A CN107272091 A CN 107272091A CN 201710367396 A CN201710367396 A CN 201710367396A CN 107272091 A CN107272091 A CN 107272091A
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CN
China
Prior art keywords
particle
reflection film
layer
white reflection
film
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CN201710367396.7A
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Chinese (zh)
Inventor
楠目博
浅井真人
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Toyobo Film Solutions Ltd
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Teijin DuPont Films Japan Ltd
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Application filed by Teijin DuPont Films Japan Ltd filed Critical Teijin DuPont Films Japan Ltd
Publication of CN107272091A publication Critical patent/CN107272091A/en
Pending legal-status Critical Current

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/08Mirrors
    • G02B5/0816Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/0825Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
    • G02B5/0841Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0273Diffusing elements; Afocal elements characterized by the use
    • G02B5/0284Diffusing elements; Afocal elements characterized by the use used in reflection
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0013Means for improving the coupling-in of light from the light source into the light guide
    • G02B6/0023Means for improving the coupling-in of light from the light source into the light guide provided by one optical element, or plurality thereof, placed between the light guide and the light source, or around the light source
    • G02B6/0031Reflecting element, sheet or layer
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336Illuminating devices
    • G02F1/133615Edge-illuminating devices, i.e. illuminating from the side
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/12Reflex reflectors
    • G02B5/126Reflex reflectors including curved refracting surface
    • G02B5/128Reflex reflectors including curved refracting surface transparent spheres being embedded in matrix
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033Means for improving the coupling-out of light from the light guide
    • G02B6/005Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
    • G02B6/0055Reflecting element, sheet or layer
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0065Manufacturing aspects; Material aspects

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Planar Illumination Modules (AREA)
  • Optical Elements Other Than Lenses (AREA)

Abstract

White reflection film, it has reflecting layer A and the superficial layer B comprising the resin combination containing particle, and it is 10 to have on superficial layer B and reflecting layer A opposite side surface in the projection formed by above-mentioned particle, the surface highly for more than 5 μm of projection number4~1010Individual/m2, above-mentioned particle is the non-spherical particle that average grain diameter is 3~100 μm, 10% compressive strength is 0.1~15MPa.The film can fully suppress stickup with light guide plate, while can fully suppress the damage of light guide plate.

Description

White reflection film
Technical field
The application is the applying date for August in 2014 4 days, Application No. " 201480002946.X ", entitled " white The divisional application of the application of reflectance coating ".The present invention relates to white reflection film.More particularly to it is used for the white of liquid crystal display device Reflectance coating.
Background technology
Liquid crystal display device(LCD)Back light unit have at the back side of liquid crystal display panel and there is light source and further at it The back side has the full run-down type of reflectance coating and has the light guide plate of reflecting plate at the back side configuration back side of liquid crystal display panel, led at this The side of tabula rasa has the edge lighting-type of light source(エ ッ ジ ラ イ ト types).Back light unit used is from picture in conventional large LCD In the brightness in face and picture mainly full run-down type is used from the viewpoint of the excellent in uniformity of brightness(Mainly full run-down type CCFL), side Edge light emitting-type is frequently used in the more small-sized LCD such as notebook type PC, still, in recent years, due to the development of light source or light guide plate, It is not only more small-sized LCD even the uniformity in the brightness and picture of edge lighting-type back light unit is also improved, it is large-scale The back light unit using edge lighting-type is also begun in LCD.Because having the advantages that LCD can be made thinning.
It is the structure that light guide plate and reflectance coating are directly contacted in edge lighting-type back light unit.Therefore, in this structure In, if there is light guide plate and reflectance coating is pasted, the brightness for the part pasted becomes abnormal, occurs in the face of brightness The problem of deviation.Therefore, it is necessary to make that there is gap between light guide plate and reflectance coating, and keep the clearance constant.For example, by making There is pearl can make the gap remained constant between light guide plate and reflectance coating on the surface of reflectance coating, so as to prevent them from gluing Patch.But, if the light guide plate now formed by softer material is contacted with reflectance coating, the pearl that there is reflectance coating or surface The problem of son can damage light guide plate.As its countermeasure, there is such as patent document 1~3 like that, painting to be passed through on the surface of reflectance coating Cloth forms the report of the antisitic defect layer containing elastic system pearl.
But, although antisitic defect layer has light guide plate injury inhibitory effect to a certain degree as patent document 1~3, The purpose of its script, ensure gap(Suppress to paste)Aspect has the tendency of variation.The present inventor is learnt by research, as conventional If being only conceived to the number of projection like that, can not fully meet sometimes in recent years required suppression and the stickup of light guide plate and Suppress two aspects of damage of light guide plate.
(Patent document 1)Japanese Unexamined Patent Publication 2003-92018 publications
(Patent document 2)Japanese Unexamined Patent Application Publication 2008-512719 publications
(Patent document 3)Japanese Unexamined Patent Publication 2009-244509 publications.
The content of the invention
It is an object of the invention to provide the stickup that can fully suppress with light guide plate, while can fully suppress light guide plate The white reflection film of damage.
The present invention uses following composition to solve above-mentioned problem.
1. white reflection film, it has the reflecting layer A and superficial layer B by the resin combination manufacture containing particle,
Highly it is during there is the projection formed by above-mentioned particle, the surface on superficial layer B and reflecting layer A opposite side surface More than 5 μm of projection number is 104~1010Individual/m2,
Above-mentioned particle is the non-spherical particle that average grain diameter is 3~100 μm, 10% compressive strength is 0.1~15MPa.
2. the white reflection film described in above-mentioned 1, wherein above-mentioned particle is polymerize by the way that polymer to be crushed to obtained crushing Thing particle.
3. the white reflection film described in above-mentioned 2, wherein above-mentioned polymer is polyester.
4. the white reflection film in above-mentioned 1~3 described in any one, wherein above-mentioned particle is length-width ratio(Major diameter/minor axis) Average out to more than 1.31, less than 1.80, and length-width ratio standard deviation be 0.15~0.50 non-spherical particle.
5. the content of above-mentioned particle is with table in the white reflection film in above-mentioned 1~3 described in any one, wherein superficial layer B It is 1~70 mass % on the basis of surface layer B quality.
6. the white reflection film in above-mentioned 1~3 described in any one, wherein volatile organic solvent amount are below 10ppm.
7. the white reflection film in above-mentioned 1~3 described in any one, wherein reflecting layer A contains hole, its pore volume rate For more than 15 volume %, below 70 volume %.
8. the white reflection film described in above-mentioned 7, it is 0 volume % less than 15 volume %'s that it, which also has pore volume rate, Supporting layer C.
9. the white reflection film described in above-mentioned 7, wherein superficial layer B are the layers formed by the coating of masking liquid.
10. the white reflection film in above-mentioned 1~3 described in any one, it is used as the area source reflecting plate with light guide plate.
Brief description of the drawings
Fig. 1,2 be the projection formed by non-spherical particle in the present invention electron micrograph example.
Fig. 3 is the schematic diagram for representing the evaluation method that comes off of the Damage Evaluation of light guide plate and particle in the present invention.
Fig. 4 is the schematic diagram of structure used during closely sealed inequality of the invention is evaluated.
The preferred forms of invention
The white reflection film of the present invention has reflecting layer A and superficial layer B.
Each constituent described further below for constituting the present invention.
[ reflecting layer A ]
The reflecting layer A of the present invention contains thermoplastic resin and pore former, by making it contain pore former in layer Comprising hole, make its white.The pore former will be described in more detail below, and can use such as inorganic particulate, is somebody's turn to do with constituting The immiscible resin of reflecting layer A thermoplastic resin(Hereinafter sometimes referred to immiscible resin).In addition, reflecting layer A is in wavelength Reflectivity under 550nm is preferably more than 95%, more preferably more than 96%, particularly preferably more than 97%.Thus white reflection film Reflectivity more easily reach preferred scope.
Reflecting layer A has hole in layer as described above, and the volume of the hole is relative to the ratio shared by reflecting layer A volume Example(Pore volume rate)Preferably more than 15 volume %, below 70 volume %.By that can improve reflectivity in such scope Effect is improved, and is readily available above-mentioned reflectivity.Improved furthermore it is also possible to make film draftability improve effect.Pore volume rate When too low, have the tendency of to be difficult to obtain preferred reflectivity.Consider from above-mentioned viewpoint, the pore volume rate in the A of reflecting layer is more excellent Elect as more than 30 volume %, be particularly preferably more than 40 volume %.On the other hand, when pore volume rate is too high, there is film draftability Raising effect reduction tendency.Consider from above-mentioned viewpoint, the pore volume rate in the A of reflecting layer is more preferably below 65 volume %, Particularly preferably below 60 volume %.
Pore volume rate can be reached by adjusting the species or size of the pore former in the A of reflecting layer, amount.
(Thermoplastic resin)
Constituting reflecting layer A thermoplastic resin can enumerate for example by polyester, polyolefin, polystyrene, acrylic compounds(アクリ ル)Manufactured thermoplastic resin.Wherein, the viewpoint from the white reflection film for obtaining mechanical property and excellent heat stability is examined Consider, preferably polyester.
The polyester preferably uses the polyester by dicarboxylic acid component and diol component manufacture.The dicarboxylic acid component can enumerate Derived from terephthalic acid (TPA), M-phthalic acid, 2,6- naphthalenedicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid, adipic acid, decanedioic acid etc. into Point.Diol component can enumerate derived from ethylene glycol, 1,4- butanediols, 1,4 cyclohexane dimethanol, 1,6-HD etc. into Point.Optimization aromatic polyester in these polyester, particularly preferred polyethylene terephthalate.Polyethylene terephthalate Can be homopolymer, but from crystallization is suppressed when film is uniaxially or biaxially stretched so that what the raising effect of film draftability was improved Viewpoint consideration, preferred copolymer.Copolymer composition can enumerate above-mentioned dicarboxylic acid component, diol component, but from heat resistance is high, system From the viewpoint of the raising effect of film stretching is high, preferably M-phthalic acid composition, NDA composition.Copolymer composition Ratio be on the basis of 100 moles of % of whole dicarboxylic acid components of polyester, for example, 1~20 mole %, be preferably 2~18 moles of %, More preferably 3~15 moles %, particularly preferably 7~11 moles of %.By making the ratio of copolymer composition in the scope, film stretching The raising excellent effect of property.In addition, dimensional stability is also excellent.
(Pore former)
In the A of reflecting layer, during using inorganic particulate as pore former, inorganic particulate preferred white inorganic particulate.The white nothing Machine particle can enumerate the particle of barium sulfate, titanium dioxide, silica, calcium carbonate.As long as selected for these inorganic particulates Average grain diameter, content are selected so that white reflection film has suitable reflectivity, is not particularly limited.Preferably make reflecting layer A, the reflectivity of white reflection film reach the preferred scope of the present invention.In addition, making reflecting layer A pore volume rate reach this The preferred scope of invention.In view of these, the average grain diameter of inorganic particulate is such as 0.2~3.0 μm, be preferably 0.3~ 2.5 μm, more preferably 0.4~2.0 μm.Its content is preferably 20~60 mass % on the basis of reflecting layer A quality, more preferably For 25~55 mass %, most preferably 31~53 mass %.By using such particle shape, particle can be made to fit in the polyester Degree is scattered, it is difficult to occur the aggegation of particle, so as to obtain the film without thick projection.In addition, with oversize grain during stretching Disrumpent feelings for starting point is also inhibited.Inorganic particulate can be any shape of particle, for example, can be tabular, spherical.Inorganic grain Son can carry out the surface treatment for improving dispersiveness.
During using immiscible resin as pore former, as long as thermoplastic resin not phase of the immiscible resin with constituting layer It is molten, it is not particularly limited.For example when described thermoplastic resin is polyester, preferred polyolefm, polystyrene etc..These resins can To be particle shape.Its content is in the same manner as the situation of inorganic particulate, as long as selection average grain diameter, content are so that white reflection film With suitable reflectivity, it is not particularly limited.The reflectivity of reflecting layer A, white reflection film is preferably set to reach this hair Bright preferred scope.In addition, making reflecting layer A pore volume rate reach the preferred scope of the present invention.In view of this A bit, content is preferably 10~50 mass %, more preferably 12~40 mass %, most preferably 13 on the basis of reflecting layer A quality ~35 mass %.
(Other compositions)
In the A of reflecting layer, as long as not damaging the purpose of the present invention, other compositions, such as ultra-violet absorber, antioxygen can also be contained Agent, antistatic additive, fluorescent whitening agent, wax, the particle different from pore former, resin etc..
[ superficial layer B ]
The superficial layer B of the present invention, by the resin combination manufacture containing particle in resin, is to be formed by the particle on surface There is the layer of projection.The resin preferred thermoplastic resin.Furthermore it is possible to have cross-linked structure by crosslinking agent.In this feelings Under condition, can use has and can pass through crosslinking agent with the thermoplastic resin formation of the functional group of the reaction-ity group reaction of crosslinking agent With thermoplastic resin formation cross-linked structure or using without can be with the reaction-ity group reaction of crosslinking agent functional group Thermoplastic resin, the form of the matrix of the cross-linked structure of the matrix with thermoplastic resin and cross-linking agents.Have During cross-linked structure, the intensity for having the tendency of superficial layer B is improved.On the other hand, too much with cross-linked structure when, by film reclaim again When raw, there is non-fused mass and become many etc. to make the recyclability of film be deteriorated, consider from above-mentioned viewpoint, preferably cross-linked structure is only It is many.
Superficial layer B can be formed by coating masking liquid in the manufacturing process of film or after manufacture, it would however also be possible to employ for example Coetrusion etc. is formed simultaneously with reflecting layer A.In order to which superficial layer B as described above has cross-linked structure, preferably pass through the painting of masking liquid Cloth is formed.Consider that the content of crosslinking agent is on the basis of the solid constituent for constituting masking liquid, preferably 35 mass % from above-mentioned viewpoint Below, below 30 mass %, more preferably below 25 mass %, particularly preferably below 20 mass % are more preferably.In addition, Preferably more than 1 mass %, more preferably more than 2 mass %, more preferably more than 3 mass %, particularly preferably 5 mass % with On.
(Thermoplastic resin)
The thermoplasticity same with above-mentioned composition reflecting layer A thermoplastic resin can be used by constituting superficial layer B thermoplastic resin Resin.Wherein, preferably acrylic compounds, polyester, particularly from the white reflection film for obtaining mechanical property and excellent heat stability Viewpoint consideration, preferably polyester.
The polyester can use the polyester same with the polyester in above-mentioned reflecting layer A.In these polyester, from obtaining machinery From the viewpoint of the white reflection film of characteristic and excellent heat stability, optimization aromatic polyester, particularly preferred poly terephthalic acid Glycol ester.Polyethylene terephthalate can be homopolymer, but be taken off from obtaining appropriateness softening superficial layer B, suppressing particle From the aspect of the effect fallen, preferred copolymer, particularly preferred copolymerization polyethylene terephthalate.Even if thus having and leaded light The external force such as plate friction apply, and particle is also difficult to come off.The copolymer composition can enumerate above-mentioned dicarboxylic acid component, glycol into Point, from heat resistance height, it is film-made from the viewpoint of the raising effect of draftability height, preferably M-phthalic acid composition, 2,6- naphthalene diformazans Sour composition.The ratio of copolymer composition is for example, 1~20 mole %, excellent on the basis of 100 moles of % of whole dicarboxylic acid components of polyester Elect 2~18 moles of %, more preferably 3~17 moles %, particularly preferably 12~16 moles of % as.By the ratio for making copolymer composition In above range, the raising excellent effect of draftability is film-made.In addition, dimensional stability is also excellent.
Formed by coating masking liquid in the manufacturing process of film or after manufacture during superficial layer B, in order to obtain the effect above, In addition to improving the stability of masking liquid, the preferably side chain or main chain of these polyester is carried with the function of improving said solvophilic Group.Here the group with the function of improving said solvophilic preferably enumerates the group of metal organic sulfonate(Preferably sodium sulfonate Salt), hydroxyl, the group of alkyl ether, the group of carboxylate etc..In the present invention particularly preferably relative to polyester all acid into 100 moles of % are divided to include M-phthalic acid composition preferably 3~30 moles %, more preferably 5~20 of the group with metal organic sulfonate Mole %, further preferred 5~15 moles of % embodiment.In addition, from the same viewpoint it is also preferred that comprising diethylene glycol (DEG) into Point, relative to 100 moles of % of all acid composition of polyester, preferably comprise the composition 3~30 moles of %, more preferably 5~20 moles %, Further preferred 5~15 moles of % embodiment.
(Non-spherical particle)
In the present invention, the particle in superficial layer B must be the non-spherical particle that average grain diameter is 3~100 μm.By making average grain Footpath easily forms the mode of aftermentioned projection number, it is easier to ensure that gap in above range.If average grain diameter is excessive, hold Easily occur particle to come off, cause the defect on picture.On the other hand, if average grain diameter is too small, it is used as ensuring for original purpose Become difficult with the gap of light guide plate.Consider from above-mentioned viewpoint, more preferably more than 5 μm, more preferably more than 7 μm, spy You Xuanwei not be more than 8 μm, also, more preferably less than 80 μm, more preferably less than 70 μm, be particularly preferably 50 μm with Under.
In addition, being that non-spherical particle may insure between light guide plate by the particle for making to form projection in outermost surface Gap, while the effect for suppressing guide-lighting dash-board injury can be improved.In the present invention, non-spherical particle refers to the maximum dimension D x of particle (It is designated as x directions)And the direction vertical with x directions(It is designated as y directions and z directions.Z directions are directions also vertical with y directions) Middle maximum dimension D y and Dz(Dy≧Dz)The difference of maximum gauge in these all directions(Dx-Dy、Dx-Dz、Dy-Dz)In at least Any 1 20% particle more than Dx.
Think that it is due to following mechanism to obtain the effect above by such non-spherical particle.I.e., it is believed that by making Particle is shaped as non-spherical, becomes big with the contact area of light guide plate, causes pressure dissipation, be thus not easy to cause damage.Grain When the shape of son is the non-spherical being specified as above, particle has maximum gauge in one direction, included in superficial layer B When, easily become and be direction that be substantially parallel with superficial layer B face direction from the probability maximum gauge direction.Therefore, by institute State the projection of particle formation and the contact area of light guide plate becomes big, pressure is disperseed.On the contrary, when particle is spherical, with light guide plate The area of the part of contact narrows, therefore pressure is concentrated easily to cause damage.Accordingly even when be the particle using softness, Become easily to damage light guide plate due to being spherical.
The present invention is in superficial layer B by the way that with specific particle shape as described above, projection summit is concentrated on it Narrow range contact light guide plate, not as take keep projection quantity while increase projection and light guide plate contact area, by This makes the embodiment of pressure dissipation, because the quantity with the contact point of light guide plate is suitable, while realization ensures gap, makes Each projection reduces to the pressure of light guide plate, thus suppresses the damage of light guide plate.If not in above range, as only concentrating Narrow range on such as projection summit contacts the form of light guide plate, and the pressure rise applied to the part becomes easily to be cut.
In the present invention, in order to further improve the effect that the effect for suppressing guide-lighting dash-board injury and suppression are pasted with light guide plate, The length-width ratio of preferred particle(Major diameter/minor axis)Average out to more than 1.31, less than 1.80.The length-width ratio be more preferably 1.35 with Above, less than 1.75 are more preferably in addition.In order to obtain the effect above, preferably length-width ratio is big, but if excessive, is difficult to maintain Highly it is the tendency of more than 5 μm of projection number in outermost surface.Here length-width ratio is by using electron microscopic described later Mirror is observed what is tried to achieve.In the observation, the maximum gauge of particle is regard as major diameter, the direction vertical with the maximum gauge On maximum gauge be used as minor axis.
Simultaneously, thus it is speculated that when the shape of particle has the deviation of appropriateness, i.e. the shape of particle becomes moderately inconsistent, thus It is difficult to apply pressure to specific particle, so as to be difficult to damage light guide plate.
Therefore, the standard deviation of the preferred length-width ratio of the particle is 0.15~0.50.That is, this represents that the shape of each particle has The deviation of appropriateness.There is appropriate deviation by the shape for the particle for forming projection, it can be ensured that while gap with light guide plate, Further improve the effect for suppressing guide-lighting dash-board injury.Deviation hour, it is ensured that the raising effect reduction that gap and damage suppress.It is another , when deviation is excessive, easily there is bad problem in aspect when being added to superficial layer B, there is inclining for the projection frequency for being difficult to obtain imagination To result is to be difficult to play the raising effect for ensuring that gap, damage suppress.Consider from above-mentioned viewpoint, the mark of the length-width ratio of particle Quasi- deviation is more preferably more than 0.16, more preferably more than 0.17, in addition more preferably less than 0.45, more preferably Less than 0.43.
In the present invention, 10% compressive strength of above-mentioned particle is necessary for 0.1~15MPa.It may thereby be ensured that gap, also The damage to light guide plate can be suppressed.When compressive strength is too low, can stress and excessive deformation, therefore as original purpose really The gap protected with light guide plate becomes difficult.On the other hand, when compressive strength is too high, even non-spherical particle also easily lead by damage Tabula rasa.Consider from above-mentioned viewpoint, 10% compressive strength is preferably more than 0.2MPa, is more preferably more than 0.3MPa, further preferably For more than 3MPa, particularly preferably more than 8MPa, it is additionally preferred to for below 14MPa, more preferably below 13MPa, more excellent Elect below 12MPa as.
The content of non-spherical particle in the present invention in superficial layer B can use the particle of average grain diameter as described above, Progress is suitably adjusted in the way of meeting aftermentioned projection number.For example, there is the average grain diameter superficial layer B thickness of thin relative to particle Tendency when, have the tendency of easily to form projection, therefore content can be with more less;When opposite, preferred content is more, can be with Consider that such tendency is suitably adjusted.Specifically, on the basis of superficial layer B quality, preferably 1~70 mass %, more preferably For more than 5 mass %, more preferably more than 10 mass %, more than 20 mass % are particularly preferably, in addition more preferably 60 matter Measure below %, more preferably below 50 mass %, particularly preferably below 30 mass %.
Particle in the present invention contained by superficial layer B, regardless of its species, can be organic filler or inorganic Particle, can also be organo-mineral complexing particle.From the viewpoint of the mode for readily satisfying above-mentioned particle, preferably by acrylic acid The polymer particle of the polymer such as class, polyester, polyurethane, nylon, polyolefin, polyethers manufacture.More preferably polyester, nylon, this Sample is readily available more suitably 10% compressive strength.Particularly preferably polyester(Wherein more preferably polyethylene terephthalate), It has the advantages that recovery Film making properties are excellent.
In the present invention, to realizing that the method for above-mentioned shape of particle is not particularly limited, but from being readily available with especially excellent The viewpoint of the particle of form slection shape and from the viewpoint of manufacturing cost, productivity, solid polymer is preferably crushed obtain particle Method.The particle obtained by the process is referred to as crushing polymer particle.Will for example after the process more specifically preferred polymeric The polymer sheet granulated preferably crystallizes it by heat treatment, the side crushed in a low temperature of normal temperature or less than normal temperature Method.From being easier from the viewpoint of crushing, preferably crushed in a low temperature of less than normal temperature, be used as the side for obtaining the low temperature Method, can preferably enumerate the method cooled down by liquid nitrogen.
In addition to the above-mentioned polymer sheet granulated, by the polymer composition being molded, the polymer being film-made Film, polymer fiber of throwing etc. are crushed and can also prepare purpose and crush polymer particle.By so selecting polymerization to be comminuted The form of thing(Changing size during including being, for example, particle, changing thickness when being film, changing diameter when being fiber), can be had There are various non-spherical forms(Length-width ratio)Particle, furthermore it is also possible to adjust the deviation of shape of particle(Standard deviation).
The polymer for crushing polymer particle can be the blend of copolymerization or 2 kinds of polymer, crush polymer particle Inside can also be comprising the smaller inorganic particulate of diameter, organic filler, or contains ultra-violet absorber, lubricant etc..
(Superficial layer B form)
In the present invention, white reflection film is formed extremely by the superficial layer B of the resin combination manufacture containing particle as described above The outermost layer of a few side.Also, on the outermost superficial layer B of the formation surface with reflecting layer A opposite side(Below sometimes Referred to as outermost surface)With the projection formed by above-mentioned particle.The projection is examined from the viewpoint in the gap for ensuring light guide plate and film Consider, it is necessary to there is the projection of proper height with appropriate frequency in outermost surface.
Therefore, in the present invention, in outermost surface, it is often necessary to be the projection number that height is more than 5 μm(Projection frequency Rate)For 104~1010Individual/m2.It is possible thereby to substantially ensure that the gap of light guide plate and film, ensure to paste inhibition.Projection frequency Inhibition is pasted when too low poor.On the other hand, when projection frequency is too high, the probability for having particle to come off rises or reflectivity drop Low tendency.
(Other compositions)
It can also contain the composition beyond above-mentioned constituent in the range table surface layer B for not damaging the object of the invention.The composition Such as ultra-violet absorber, antioxidant, antistatic additive, fluorescent whitening agent, wax, surfactant and above-mentioned grain can be enumerated Son different particle, resin etc..
[ Rotating fields ]
Reflecting layer A thickness is preferably 80~350 μm in the present invention.It is possible thereby to improve the effect of raising reflectivity.If The reflecting layer A excessively thin effect for then improving reflectivity of thickness is low, and blocked up, is non-efficient.From the viewpoint, instead The thickness for penetrating layer A is more preferably 80~300 μm, more preferably 100~320 μm, particularly preferably 150~250 μm.
Superficial layer B thickness is preferably 5~100 μm in the present invention.More preferably 5~80 μm.Now superficial layer B thickness The thickness sum of the particle diameter for referring to particle and the resin portion for being coated to its surface.
In addition, the thickness for maintaining the resin portion of superficial layer B particle is preferably 0.2~50 μm.Thus projection frequency is held Mutability is into preferred embodiment, it is easy to ensure that the gap with light guide plate.If the thickness mistake of superficial layer B above-mentioned resin portion Thin, then the particle having the tendency of in the projection that superficial layer B surface is formed easily is fallen off.And it is blocked up if, have and be difficult to Obtain the tendency of preferred projection frequency.From above-mentioned viewpoint consider, more preferably more than 0.3 μm, be more preferably 0.5 μm with Above, particularly preferably more than 1 μm, most preferably more than 2 μm, and more preferably less than 40 μm.Further, if it is considered that If deciduous, preferably more than 1 μm, preferably more than 2 μm.
When reflecting layer A being expressed as into A, superficial layer B being expressed as B, the laminated construction of white reflection film can enumerate the 2 of B/A B is configured outermost more than 4 layers of the sandwich construction at least any one party by Rotating fields, B/A/B 3-tier architecture.Especially Preferably further there is the supporting layer C for being used for making Film making properties stable(It is expressed as C), B/C/A or B/A/C 3-tier architecture, B/C/ A/C 4 Rotating fields.Most preferably B/C/A/C 4 Rotating fields, film draftability is more excellent.And it is difficult to generation curling etc. to ask Topic.In the present invention, the preferred embodiment with such supporting layer C.The supporting layer C is preferably by same with reflecting layer A Polyester manufacture, pore volume rate are than relatively low(Preferably 0 volume % is less than 15 volume %, more preferably below 5 volume %, spy You Xuanwei not below 3 volume %)Embodiment.In addition, the thickness of the supporting layer C(Refer to during with multiple supporting layer C total Thickness)Preferably 5~140 μm, more preferably 20~140 μm.
In the present invention, in addition to reflecting layer A, superficial layer B and supporting layer C, may be used also as long as not damaging the purpose of the present invention With with other layers.Can also for example have and assign easy-adhesion, windability(Slickness), it is antistatic behaviour, electric conductivity, ultraviolet The layer of the functions such as line durability, the layer for adjusting optical characteristics.
[ manufacture method of film ]
Explanation manufactures one of method of white reflection film of the present invention example below.
, can be on the reflecting layer A obtained by extrusion by melting etc. by molten when manufacturing the white reflection film of the present invention Melt resin rubbing method(Including melting extrusion resin rubbing method), coetrusion and lay-up method and using being used to form superficial layer B Masking liquid pass through masking liquid rubbing method formation superficial layer B.Wherein, reflecting layer A and supporting layer C are particularly preferably being passed through into coetrusion By masking liquid rubbing method come laminate surface layer B method in the manufactured laminated body of stacking.It is laminated by using masking liquid rubbing method Superficial layer B can easily control the distribution of particle by changing drying condition etc., so as to cheap and easy The predetermined projection number of ground volume production.Even in addition, the less particle of 10% compressive strength, processing also becomes easy.Further Ground, keeps the specified particle shape in the present invention to become easy, and the form for easily making projection is preferred form.
Below to using polyester as the thermoplastic resin and composition supporting layer C thermoplastic resin for constituting reflecting layer A, adopting With coetrusion as reflecting layer A and supporting layer C laminating method, using laminating method of the masking liquid rubbing method as superficial layer B When manufacture method illustrate, but the invention is not restricted to the manufacture method, with reference to it is following otherwise also can be similarly Manufacture.When now, not comprising extrusion operation, following " melting extrusion temperature " can be separately read as such as " melting temperature ".Here The fusing point of polyester used is designated as Tm(Unit:℃), glass transition temperature be designated as Tg(Unit:℃).
First, as the polymer blend for forming reflecting layer A, prepare polyester, pore former and other Hank point mixture mixed.In addition, as the polymer blend for forming supporting layer C, preparation is by polyester and optionally Pore former and the mixture that mixes of other optional members.These polymer blends are dried, fully remove moisture Use.
Then, the polymer blend dried is put into respectively and melting extrusion is carried out in different extruders.Melting is squeezed It must be more than Tm to go out temperature, be set in Tm+40 DEG C or so.
Now, preferably used for making the polymer blend of film, the polymer blend particularly for reflecting layer A by line Footpath is that the average pore size that less than 15 μm of stainless steel fine rule is constituted is that 10~100 μm of non-woven cloth type filter is filtered. By carrying out the filtering, the aggegation for the particle that can suppress to be typically easy to aggegation and become thick agglutination particle, so as to obtain thick The film of big few foreign.The average pore size of non-woven cloth is preferably 20~50 μm, more preferably 15~40 μm.Polyester group after filtering Compound is in the molten state by using multilayer extrusion method while supply head(Coetrusion)Extruded from die head with multilayered state, So as to manufacture non-stretched laminated sheet.Non-stretched lamination is made with curtain coating drum cooling and solidifying in the non-stretched laminated sheet extruded from die head Film.
Then, the non-stretched stack membrane is heated by roller, the heating such as infrared heating, along the mechanical direction of principal axis of film(With Longitudinal direction or length direction or MD are sometimes referred to as down)Progress, which is stretched, obtains longitudinal stretching film.The stretching is preferably by the roller of more than 2 Difference carry out.Film after longitudinal stretching is then imported into stenter, vertical with longitudinal direction and thickness direction Direction(Hereinafter sometimes referred to transverse direction or width or TD)Stretching obtains biaxially-stretched film.
As draft temperature, preferably in polyester(Preferably constitute reflecting layer A polyester)More than Tg, less than Tg+30 DEG C At a temperature of carry out, it is more excellent to be so film-made draftability, and easily satisfactorily forms hole.As stretching ratio, indulge To, laterally preferably 2.5~4.3 times, more preferably 2.7~4.2 times.When stretching ratio is too low, the uneven thickness of film has change The tendency of difference, and have the tendency of to be difficult to be formed hole, and stretching ratio it is too high when, have in film and easily occur disrumpent feelings to incline To.Implement longitudinal stretching after carry out cross directional stretch it is progressively biaxial stretch-formed when, the 2nd stage(It is now cross directional stretch)It is preferred that compare High 10~50 DEG C or so of the draft temperature in the 1st stage.This is due to the stretching orientation in the 1st stage so that the Tg of uniaxial film is elevated Reason.
In addition, preferably film is preheated before each stretching.The pre-heat treatment of such as cross directional stretch can be from than polyester(It is preferred that To constitute reflecting layer A polyester)Temperature Tg+5 DEG C high start slow heating.Heating during cross directional stretch can be It is continuous or interim(Progressively), but be typically progressively to heat up.For example by the regions of lateral stretch edge of stenter Film moving direction is divided into several regions, and each region flows through the heating medium of predetermined temperature to heat up.
Film after biaxial stretch-formed then carries out heat fixation, hot wire-CVD successively(Hot relaxations Slow)Biaxially oriented film is made in processing, but Can then it be stretched by melting extrusion, these processing can also be carried out while film is moved.
Film after biaxial stretch-formed can be in the state of two ends be held with clip, by polyester(Preferably constitute reflecting layer A Polyester)Fusing point when being designated as Tm,(Tm-20℃)~(Tm-100℃)Under, enter in the case where constant-breadth or less than 10% Kuan Du Minus are few Row heat treatment, heat fixation, reduce percent thermal shrinkage.When the heat treatment temperature is too high, the flatness of film has the tendency of variation, thick Degree inequality has the tendency of to become big;And it is too low, there is percent thermal shrinkage and become big.
In addition, in order to adjust thermal shrinking quantity, the two ends of the film of holding can be cut away, the hauling speed of adjustment film longitudinal direction, Relaxed in the vertical.Loose method is the speed for the roller group for adjusting tenter outlet side.As loose ratio, relatively The speed for making roller group in the film linear velocity of stenter is reduced, implement preferably 0.1~2.5%, further preferred 0.2~2.3%, especially It is preferred that 0.3~2.0% reduction of speed relaxes film(The value is referred to as " relaxation rate "), longitudinal heat is adjusted by controlling relaxation rate Shrinkage factor.In addition, it is horizontal for film, it can reduce width during before cutting away two ends, so as to obtain desired heat Shrinkage factor.
It is in addition to longitudinal direction as described above-horizontal progressively biaxial stretching process or horizontal when carrying out biaxial stretch-formed To-longitudinal direction progressively biaxial stretching process.Furthermore it is also possible to be film-made using simultaneously biaxial drawing method.Using simultaneously biaxial drawing method When, it is all longitudinally, laterally such as 2.7~4.3 times that stretching ratio, which is, be preferably 2.8~4.2 times.
Superficial layer B can be formed preferably by so-called online rubbing method, i.e. after the longitudinal stretching of above-mentioned operation, The masking liquid for forming superficial layer B on longitudinal stretching film is coated with, in preheating procedure, cross directional stretch process, heat fixation process etc. It is middle to be dried, solidify using described heat.Masking liquid can constitute superficial layer B composition, in order that it is easily applied by mixing Cloth and optionally obtained with solvent dilution.Now, solvent is preferably water, can so reduce aftermentioned volatile organic solvent amount. The coating method of masking liquid is not particularly limited, method preferably can enumerate reverse roll coating method, gravure method, die head painting Cloth method, spraying process etc..In addition, superficial layer B can also be on the Biaxially oriented film obtained in biaxial stretch-formed, heat fixation by so-called Offline rubbing method formed.In offline rubbing method, it is difficult to apply hyperpyrexia when causing to dry due to reasons such as film deformations, thus it is logical Easily dry organic solvent is often used as solvent.But like this have the tendency of aftermentioned volatile organic solvent amount and increase, Therefore particularly preferably online rubbing method in the present invention.
The white reflection film of the present invention can so be obtained.
[ characteristic of white reflection film ]
(Reflectivity, brightness)
The reflectivity that the white reflection film of the present invention is determined from superficial layer B sides(Reflectivity under wavelength 550nm)Preferably 95% More than, more preferably more than 96%, more preferably more than 97%, still more preferably for more than 97.5%, particularly preferably More than 98%.It is more than 95% or more than 96% by reflectivity, during for liquid crystal display device or illumination etc., can obtains highlighted Degree.The reflectivity can be by being such as issued to:Take the preferred configurations such as the pore volume rate for improving reflecting layer A, increase reflecting layer A's Thickness or reduction superficial layer B thickness etc. makes the form of each layer be preferred form etc..
In addition, the brightness determined from superficial layer B sides is tried to achieve by assay method described later, preferably 5400cd/m2With Upper, more preferably 5450cd/m2Above, particularly preferably 5500cd/m2More than.
Above-mentioned reflectivity and brightness are in white reflection film, when light guide plate is used together, and are the faces of light guide plate side Value.
(Volatile organic solvent amount)
The volatile organic solvent amount that the white reflection film of the present invention is determined by aftermentioned method is preferably below 10ppm.This can be with Represent that superficial layer B is formed by using the rubbing method of organic solvent.In addition, obtaining from recovery raw material and using it During being film-made, it is difficult to produce air marks(ガスマーク), it is film-made draftability(Reclaim Film making properties)Improve.Consider from above-mentioned viewpoint, More preferably below 5ppm, more preferably below 3ppm, it is generally desirable to 0ppm.In the present invention, in order that volatilization is organic molten Dosage is few, when forming superficial layer B, does not preferably use and is adopted with the aforedescribed process using the solution coating method of organic solvent.
Embodiment
Describe the present invention in detail by the following examples.Wherein, each characteristic value is determined by following method.
(1)Light reflectance
In spectrophotometer(The UV-3101PC of Shimadzu Seisakusho Ltd.'s manufacture)Upper installation integrating sphere, determined under wavelength 550nm with BaSO4Reflectivity when blank is 100%, regard the value as reflectivity.Determine and carried out on the surface of superficial layer B sides.Have in table When having different superficial layer B, the superficial layer B surface in light guide plate side is measured.
(2)The average grain diameter of particle
With laser light scattering type particle size distribution machine(The SALD-7000 of Shimadzu Seisakusho Ltd.'s manufacture)Try to achieve the size distribution of particle (The standard deviation of particle diameter), by d50 particle diameter(The particle diameter of 50% distribution is reached since small side by volume distributed median benchmark) It is used as average grain diameter.
(3)Shape of particle
(3-1)Shape of particle 1
Particle powder is fixed on measure platform with conductive paste band, the S-4700 types electric field produced using Hitachi is launched SEM is observed under 1000 times of multiplying power, observes the shape of particle.To 30 particles selected at random, grain is obtained The maximum dimension D x of son(It is designated as x directions)And, the direction vertical with x directions(It is designated as y directions and z directions.Z directions are and y side To also vertical direction)On maximum dimension D y and Dz(Dy≧Dz), average value is calculated respectively, be designated as Dxave, Dyave, Dzave, obtains Dxave-Dyave, Dxave-Dzave, Dyave-Dzave, and at least one in them is exceeded into the 20% of Dx Particle is determined as non-spherical, not less than judgement to be spherical.
(3-2)Shape of particle 2(The standard deviation of length-width ratio and length-width ratio)
Particle is gently attached on conductive paste band using glass bar, be fixed on measure platform, use Hitachi The electric field emission scanning electron microscope of the S-4700 types of production is from front(Without inclination angle)Observed under 100 times of multiplying power, To 30 particles selected at random, using the maximum gauge of particle as major diameter, by the direction vertical with the maximum gauge most Major diameter obtains major diameter/minor axis respectively as minor axis to each particle(Length-width ratio), the average value averaged as length-width ratio. In addition, calculating the standard deviation of length-width ratio by the value of each length-width ratio.
The particle small to average grain diameter(Anticipation is such as less than 3 μm), improve multiplying power(For example bring up to 1000 times)To see Survey.
(4)The projection frequency on film surface(Projection number)
Device SE-3CKT is determined with three-dimensional roughness(Kosaka Laboratory Ltd. produces), in sample length(cut-off) The projection profile on film surface is determined under conditions of 0.25mm, measured length 1mm, 2 μm of sweep span, scan line 100, with height 1000 times of multiplying power, 200 times of record projection profiles of scanning direction multiplying power.By the projection profile of gained(Transverse axis:Rising height, the longitudinal axis: The projection profile of projection number)Try to achieve the projection number that height is more than 5 μm(Individual/m2)It is used as projection frequency.Parsing uses three Tie up roughness resolver SPA-11(Kosaka Laboratory Ltd. produces).
(5)10% compressive strength
The compression that the micro-hardness tester ENT-1100a produced using エ リ オ ニ Network ス societies determines each particle under load 3gf is strong Degree, compressive strength when being deformed using 10%(MPa).Use the average value of 5 measure.
(6)Volatile organic solvent amount
In room temperature(23℃)It is lower to be fitted into 1g membrane sample in the bag of 10L fluororesin, sealed after wherein being purged with purity nitrogen. Gathered respectively with TENAX-TA trap tubes toward 2 analyses with the flow of 0.2L/ minutes immediately followed by from the nitrogen in the bag 0.2L, 1.0L nitrogen, quality of the HPLC and GCMS to Elements in Organic Solvents contained in the nitrogen that is gathered is passed through using these pipes Quantified.The value of gained is scaled the amount in 10L nitrogen, the organic solvent being evaporate into by 1g membrane sample in 10L nitrogen is tried to achieve Quality, as volatile organic solvent amount(Unit:Ppm, on the basis of the quality of membrane sample).Wherein, aldehydes is to use second Nitrile dissolution from trap tube by aldehyde derivatives, is quantified by HPLC.It is many using detected level when HPLC is different with GCMS value Value.
(7)Film thickness and Rotating fields
White reflection film is cut into slices with slicer and exposes section, the S-4700 types electric field produced using Hitachi, which is launched, to be scanned Electron microscope observes the section under 500 times of multiplying power, and film entirety, reflecting layer A, superficial layer B, supporting layer C are obtained respectively Thickness.For superficial layer B, arbitrarily take particle to there is 10 points of the thickness of part, regard their average value as thickness.
(8)Pore volume rate is calculated
Meter is obtained by the density and compounding ratio of the polymer for the layer for seeking pore volume rate, addition particle and other each compositions Calculate density.The layer is separated by stripping etc. simultaneously, quality measurement and volume calculate actual density, by calculating by these Density and actual density try to achieve pore volume rate by following formula.
Pore volume rate=100 ×(1-(Actual density/calculating density))
M-phthalic acid copolymerization polyethylene terephthalate(After biaxial stretch-formed)Density be 1.39g/cm3, barium sulfate Density is 4.5g/cm3
In addition, only separating the layer for determining pore volume rate, the quality of unit volume is tried to achieve, so as to try to achieve actual close Degree.Volume is calculated as follows:Sample is cut out into 3cm2Area, use electric micrometer(The K-402B of ア Application リ Star production)Determine the chi Very little thickness, determines at 10 points and averages as thickness, volume is calculated in the form of area × thickness.Quality with electronic balance come Weigh.
Particle(Including agglutination particle)Proportion use the Bulk Specific Gravity value tried to achieve by following graduated cylinder method.It is toward volume The particle of absolute dry condition is filled in 1000ml graduated cylinder, overall weight is determined, the weight of graduated cylinder is subtracted from the overall weight The weight of the particle is tried to achieve, graduated cylinder Rong Plot are determined, with the weight of the particle(g)Divided by the volume(cm3)To try to achieve.
(9)Fusing point, glass transition temperature
Device is determined using means of differential scanning calorimetry(TA Instruments 2100 DSC), surveyed with 20 DEG C/min of programming rate Surely try to achieve.
(10)Brightness
The LED liquid crystal television produced from LG company(LG42LE5310AKR)Middle taking-up reflectance coating, will be various described in embodiment The superficial layer B sides of reflectance coating are arranged on picture side(The side contacted with light guide plate), luminance meter is used in the state of back light unit (The Model MC-940 of great mound electronics production)The brightness at backlight center is determined with 500mm mensuration distance from front.
(11)The Damage Evaluation of light guide plate(It is ploughing to evaluate)
(11-1)Damage Evaluation 1
As shown in figure 3, in handle portion(1)End stick wide 200mm × long 200mm × thickness 3mm iron plate securely(2, weight Amount is about 200g), face-up wide 250mm × long 200mm reflectance coating is evaluated in patch thereon(3), make reflectance coating(3)Width side Expose from iron plate the part for playing each 25mm to two ends(Central 200mm × 200mm part is overlapping with iron plate).Now make reflectance coating Evaluation face(Surface aspect)For outside.In addition, iron plate is gone back in reflectance coating width two ends 25mm more than needed part Inboard, eliminates the end of reflectance coating(The part that the sword of knife etc. is entered during sampling)Cut the influence of light guide plate.
Then, there will be point(401)The face-up light guide plate of point(4, size is at least 400mm × 200mm)It is fixed on On the table of level, the above-mentioned reflectance coating being fixed on iron plate being made is made into reflectance coating in the way of evaluating face and be contacted with light guide plate Side face-down and be placed on light guide plate, further loading 500g weight thereon(5), with 200mm distance( The reflectance coating being fixed on iron plate is moved in 400mm × 200mm region)By 1 back and forth about 5~10 seconds speed come and go fortune It is dynamic 15 times.Then, observe its scraping situation in light guide plate surface with 20 times of magnifying glass and whether have the grain come off from reflectance coating Son, is evaluated according to following benchmark.
Can not seen with magnifying glass after the 400mm × 200mm gamuts nuzzled up on light guide plate, back and forth movement 20 times It is designated as during the damage observed " without scraping "(Scraping evaluates zero), do not have after back and forth movement 10 times it is observed that damage but Have after back and forth movement 20 times it is observed that damage when be designated as " being difficult scraping "(△ is evaluated in scraping), have energy after back and forth movement 10 times It was observed that damage when be designated as " scraping "(Scraping evaluation ×).
When carrying out above-mentioned evaluation, in order to suppress the influence of spot size as much as possible, spot size is selected as far as possible in light guide plate Big region, each evaluation sample is set unanimously to be evaluated.
(11-2)Damage Evaluation 2
It is above-mentioned except making(11-1)Middle iron plate(2)Size be 400mm × 200mm(The size for correspondingly making reflectance coating is 400mm × 250mm, the size of light guide plate are at least 400mm × 400mm.Make to be fixed on iron plate in 400mm × 400mm region On reflectance coating motion, range of observation also becomes the scope), weight(5)Weight be 1000g(Pressure with it is above-mentioned(11-1)Phase Together)In addition, it is other similarly to be evaluated.
(12)White point is evaluated
(12-1)White point evaluates 1
Using above-mentioned(11-1)Evaluation in the reflectance coating and light guide plate that use, reflectance coating, which is placed on table, faces its superficial layer On, light guide plate is placed to put face-down mode thereon, each 300g weight and fixation are placed respectively on four sides of light guide plate, The LED liquid crystal television produced using LG company(LG42LE5310AKR)Back light, make light incident from the side of light guide plate, If range estimation it is observed that light guide plate point beyond bright spot be then evaluated as white point generation(Evaluate △)If do not estimated It is observed that abnormal bright spot be then evaluated as no white point and produce(Evaluate zero).
(12-2)White point evaluates 2
Except using above-mentioned(11-2)Evaluation in the reflectance coating and light guide plate that use, metewand be changed to it is following beyond, it is other With it is above-mentioned(12-1)Similarly evaluated.Metewand:If range estimation it is observed that light guide plate point beyond bright spot then It has been evaluated as white point generation(Evaluate ×), if without can visual observations to abnormal bright spot if be evaluated as no white point and produce (Evaluate zero)Although, have range estimation it is observed that light guide plate point beyond bright spot but very light, be evaluated as some white points and produced (Evaluate △).
(13)Closely sealed uneven evaluation(Paste and evaluate)
(13-1)Paste and evaluate 1
As shown in figure 4, the LED liquid crystal television produced from LG company(47 inches of sizes)Take out underframe(6), with television internal side Mode upward is placed on horizontal table, and the size reflectance coating roughly the same with underframe is being placed thereon, is making its superficial layer up, Light guide plate and optical sheet 3 that TV is carried originally are further placed thereon(7, diffusion barrier 2,1, prism).Then, exist In its face, the region of the concavo-convex the best part of underframe is being included, the circle with three a diameter of 5mm is placed as shown in Figure 4 The estrade of the equilateral triangle of column leg(801), 10kg weight is further being loaded thereon(802), visual observations this three Leg area defined, is evaluated as " without closely sealed uneven " if without abnormal bright part(Closely sealed uneven evaluation zero). When having abnormal bright part, the DBEF pieces that TV is carried originally are further placed on 3 optical sheets, similarly visual observations, Abnormal bright part is evaluated as " having closely sealed inequality " if not being corrected(Evaluate ×), extremely if bright partial disappearance It is evaluated as " almost without closely sealed inequality "(Evaluate △).Wherein, three leg area defined are that the length on each side is 10cm Substantially equilateral triangle.
(13-2)Paste and evaluate 2
Except above-mentioned(13-1)In make weight(802)Weight be 15kg beyond, it is other similarly to be evaluated.
(14)Reclaim Film making properties evaluation
The biaxially-stretched film of gained in embodiment is crushed, fragment is made in melting extrusion, be thus made from recovery raw material.Should be certainly Reclaim raw material to be added in the A of reflecting layer, addition is 35 mass % on the basis of reflecting layer A quality, makes other polyester and hole The quality ratio of gap forming agent is identical with original film, is made in the same manner as original film containing the biaxial stretch-formed of recovery raw material certainly Film, is evaluated according to following benchmark.
◎:More than 2000m length can be stably film-made.
○:Length of the 1000m more but less than 2000m can be stably film-made.
△:1 cut-out is there occurs in the length less than 1000m.
×:More than 2 times cut-outs are there occurs in the length less than 1000m.
< Production Examples 1:The synthesis > of M-phthalic acid copolymerization polyethylene terephthalate 1
By the mass parts of dimethyl terephthalate (DMT) 136.5, the mass parts of DMIP 13.5(Relative to gained polyester 100 moles of % of all acid composition reach 9 moles of %), the mass parts of ethylene glycol 98, the mass parts of diethylene glycol (DEG) 1.0, the mass of manganese acetate 0.05 Part, the mass parts of lithium acetate 0.012 be encased in in rectifying column, the flask of distiller condenser, being heated to 150 while stirring~ 240 DEG C distillate methanol and carry out ester exchange reaction.Distillate after methanol, addition trimethyl phosphate 0.03 mass parts, germanium dioxide 0.04 Mass parts, reactant is transferred in reactor.Then slowly 0.3mmHg will be decompressed in reactor while stirring to heat up simultaneously To 292 DEG C, polycondensation reaction is carried out, M-phthalic acid copolymerization polyethylene terephthalate 1 is obtained.The fusing point of the polymer is 235℃。
< Production Examples 2:The synthesis > of M-phthalic acid copolymerization polyethylene terephthalate 2
Except being changed to the mass parts of dimethyl terephthalate (DMT) 129.0, the mass parts of DMIP 21.0(Relative to institute The 100 moles of % of all acid composition for obtaining polyester reach 14 moles of %)Outside, it is other same with above-mentioned Production Example 1, obtain isophthalic diformazan Sour copolymerization polyethylene terephthalate 2.The fusing point of the polymer is 215 DEG C.
< Production Examples 3:Particle master slice(マスターチップ)1 making >
Formed using a part for M-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and as hole The barium sulfate particles of 1.0 μm of the average grain diameter of agent(BaSO is designated as in table4), the NEX-T60 tandems manufactured with society of Kobe Steel Extruder, reaches that 60 mass % amount is mixed, in resin temperature with the content of barium sulfate particles relative to the quality of gained master slice 260 DEG C of extrusions of degree, make the particle master slice 1 containing barium sulfate particles.
< Production Examples 4:The making > of particle master slice 2
Formed using a part for M-phthalic acid copolymerization polyethylene terephthalate 2 obtained above and as hole The barium sulfate particles of 1.0 μm of the average grain diameter of agent, the NEX-T60 tandem extruders manufactured with society of Kobe Steel, with barium sulfate The content of particle reaches that 60 mass % amount is mixed relative to the quality of gained master slice, in 260 DEG C of extrusions of resin temperature, system Make the particle master slice 2 containing barium sulfate particles.
< Production Examples 5:The preparation > of particle 1 used in superficial layer B
By the mass parts of dimethyl terephthalate (DMT) 150, the mass parts of ethylene glycol 98, the mass parts of diethylene glycol (DEG) 1.0, the mass of manganese acetate 0.05 Part, the mass parts of lithium acetate 0.012 be encased in in rectifying column, the flask of distiller condenser, being heated to 150 while stirring~ 240 DEG C distillate methanol and carry out ester exchange reaction.Distillate after methanol, addition trimethyl phosphate 0.03 mass parts, germanium dioxide 0.04 Mass parts, reactant is transferred in reactor.Then slowly 0.3mmHg will be decompressed in reactor while stirring to heat up simultaneously To 292 DEG C, polycondensation reaction is carried out, polyethylene terephthalate 3 is obtained.By the polyethylene terephthalate 3 of gained From wire drawing die head(ストランドダイ)Thus extrusion, severing after cooling is made graininess.Then, the particle of gained is passed through Make in baking oven in 170 DEG C of heating after its drying crystalline within 3 hours, the ア ト マ イ ザ ー ミ Le manufactured with Co., Ltd. マ ツ ボ ー Crushed while TAP-1 is cooled down with liquid nitrogen, thus obtain the polyester granules that average grain diameter is 60 μm.Further, pass through The polyester granules are subjected to air classification and obtain the particle 1 that average grain diameter is 40 μm(Non-spherical particle).
Particle 2:In addition to the nylon 66 resin CM3006 produced using Dongli Ltd. particle, with above-mentioned manufacture Example 5 is similarly crushed, is classified the non-spherical particle that obtained average grain diameter is 40 μm.
Particle 3:In addition to the nylon 66 resin CM3006 produced using Dongli Ltd. particle, with above-mentioned manufacture Example 5 is similarly crushed, is classified the non-spherical particle that obtained average grain diameter is 10 μm.
Particle 4:In addition to the nylon 6 resin CM1017 produced using Dongli Ltd. particle, with above-mentioned manufacture Example 5 is similarly crushed, is classified the non-spherical particle that obtained average grain diameter is 10 μm.
Particle 5:The MBX-40 of ponding finished industrial society production(Spherical shape acrylic particles(ア Network リ Le particles), it is flat Equal particle diameter is 40 μm).
Particle 6:Except gathering for being produced using Sumitomo Chemical Co(Methyl methacrylate)(PMMA)Resin ス ミ ペ Beyond ッ Network ス MGSS particle, crushed in the same manner as above-mentioned Production Example 5, to be classified obtained average grain diameter non-for 10 μm Spherical particle.
Particle 7:The SP-10 of Dongli Ltd.'s production(Spherical shape nylon particle, average grain diameter are 10 μm).
< Production Examples 6:The preparation > of particle 8 used in superficial layer B
In the same manner as above-mentioned Production Example 5, polyethylene terephthalate 3 is extruded from wire drawing die head, severing after cooling, thus Graininess is made.The result of adjustment wire shape is that the shape of the particle is substantially cubical shape, the average out to 4mm of shape ×3mm×2mm.Then, the polyester granules that average grain diameter is 60 μm are obtained in the same manner as above-mentioned Production Example 5.By further will The polyester granules carry out air classification and obtain the particle 8 that average grain diameter is 43 μm(Non-spherical particle).
< Production Examples 7:The preparation > of particle 9 used in superficial layer B
Using the particle obtained in above-mentioned Production Example 6, generally used in the biaxially-stretched film of polyethylene terephthalate Condition(3.0 times of longitudinal stretching multiplying power, 4.0 times of cross directional stretch multiplying power, heat-fixing temperature are set in 220 DEG C)Under obtain oriented crystalline Transparent biaxial stretch-formed polyethylene terephthalate film(Thickness is 50 μm).It is used in the same manner as above-mentioned Production Example 6 Liquid nitrogen is crushed while cooling, then carries out air classification, obtains the particle 9 that average grain diameter is 52 μm(Non-spherical particle).
< Production Examples 8:The preparation > of particle 10 used in superficial layer B
Using the particle obtained in above-mentioned Production Example 6, a diameter of 35 μm of polyester fiber is made up of conventional method, by its with it is upper State while Production Example 6 is similarly cooled down with liquid nitrogen and crush, obtain the particle 10 that average grain diameter is 40 μm(Non-spherical particle).
< Production Examples 9,10:The preparation > of particle 11,12 used in superficial layer B
By the particle drying obtained in Production Example 6 crystallization, similarly crushed, air classification, it is 35 μm to obtain average grain diameter Particle 11(Non-spherical particle).In addition, the film obtained in Production Example 7 is similarly crushed, air classification, be averaged Particle diameter is 50 μm of particle 12(Non-spherical particle).In above-mentioned, the condition of adjustment air classification makes the particle of gained reach in table 3 Shown form.
Particle 13:Except gathering for being produced using Sumitomo Chemical Co(Methyl methacrylate)(PMMA)Resin ス ミ It is 40 μm beyond ペ ッ Network ス MGSS particle, to be crushed in the same manner as above-mentioned Production Example 6, be classified obtained average grain diameter Non-spherical particle.
< Production Examples 11,12:The preparation > of particle 14,15 used in superficial layer B
Thickness in above-mentioned Production Example 7 is changed to 75 μm, crushed in the same manner as Production Example 7, air classification, particle is obtained 14(Non-spherical particle).In addition, making thickness similarly obtain particle 15 for 100 μm(Non-spherical particle).In above-mentioned, wind-force is adjusted The condition of classification makes the particle of gained reach the form shown in table 3.
< Production Examples 13~20:The preparation > of particle 16~23 used in superficial layer B
By the particle drying obtained in Production Example 6 crystallization, similarly crushed, air classification, obtained respectively with such as the institute of table 3 Show the particle 16~23 of composition(Non-spherical particle or spherical particle).In above-mentioned, the condition of adjustment air classification makes the grain of gained Son reaches the form shown in table 3.
[ embodiment 1-1 ]
(The manufacture of white reflection film)
Respectively reflecting layer is used as with M-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and particle master slice 1 (A layers)Raw material, M-phthalic acid copolymerization polyethylene terephthalate 2 and particle master slice 2 be used as supporting layer(C layers)Original Material, carrying out mixing makes quality of the content of reflecting layer A mesopores forming agent relative to reflecting layer A in 49 mass %, supporting layer C Quality of the content of pore former relative to supporting layer C is 3 mass %, is put into extruder, A layers of melting extrusion temperature 255 DEG C, C layers of 230 DEG C of melting extrusion temperature, make the Rotating fields that its interflow forms C layer/A layers/C layers, holding using 3 layers of supply head device The layer-by-layer state die head(ダイス)It is shaped to sheet.Now adjusting the discharge-amount of each extruder makes C layers/A layers/C layers of thickness Degree after biaxial stretch-formed than reaching 10/80/10.Cooling further is made for 25 DEG C of chilling roll in the piece timber-used surface temperature The unstretching film of solidification.Make the unstretching film by 73 DEG C of preheated zone, then by 75 DEG C of preheated zone, imported into guarantor Hold 92 DEG C of regions of longitudinal stretch, 2.9 times of longitudinal stretching, cooled down with 25 DEG C of roller groups, obtain monadic stretching membrane.Then, exist In the one side of the monadic stretching membrane of gained using reverse roll coating method be coated with it is following shown in be used for form superficial layer(B layers)Masking liquid 1。
The > of < masking liquids 1
The Z-465 of the mutual induction KCC production of resin will be used as(Relative to whole in polyethylene terephthalate Sour 100 moles of % of composition contain 10 moles of % of sulfoisophthalic acid sodium composition, 10 moles of % of diethylene glycol (DEG) composition copolymer polyester resin (The copolyester is designated as resin 1), solid component concentration is the 15 mass % aqueous solution)And it is used as the above-mentioned Production Example of particle The particle 1 that is obtained in 5 and as retarder thinner ion exchange water with resin and particle reach content ratio shown in table 1, And the solid component concentration of masking liquid reaches that 20 mass % mode carries out being mixed and made into masking liquid 1.
After coating, 115 DEG C of preheated zone is passed to while the two ends of film are kept with clip it imported into be maintained at 130 DEG C of regions of lateral stretch, 3.6 times of cross directional stretch.Then heat fixation is carried out in 185 DEG C in stenter, in contracting rate(Width Enter れ rates)It is that horizontal contracting is carried out under conditions of 130 DEG C for 2%, contracting temperature, film two ends is then cut away, with longitudinal relaxation rate 2% Hot wire-CVD is carried out, room temperature is cooled to, obtains biaxially-stretched film.The evaluation result of gained film is as shown in table 2.
[ embodiment 1-2,1-3,1-5, comparative example 1-1~1-3 ]
Except making superficial layer(B layers)Beyond the form difference of particle used is as shown in table 1, obtained in the same manner as embodiment 1-1 Biaxially-stretched film.The evaluation result of gained film is as shown in table 2.
[ embodiment 1-4 ]
Except reflecting layer A pore former to be changed to the resin immiscible with polyester(Cycloolefin, Port リ プ ラ ス チ ッ Network ス " the TOPAS 6017S-04 " of company's production), make quality of the content of pore former relative to reflecting layer A for 20 mass % with Outside, other that biaxially-stretched film is made in the same manner as embodiment 1-1 and is evaluated, evaluation result is as shown in table 2.
[ embodiment 1-6 ]
Except after uniaxial tension, it is biaxial stretch-formed before be not coated with masking liquid in addition to, it is other obtained in the same manner as embodiment 1-1 twin shafts drawing Film is stretched, with direct gravure device using wet thickness as 15g/m on the biaxially-stretched film2Coating weight coating comprising following For forming superficial layer(Layer B)Masking liquid 2 shown in composition masking liquid, be then dried to obtain film in 80 DEG C in baking oven.
< masking liquids 2, solid component concentration are 30 mass % >
Particle:The particle 1 obtained in above-mentioned Production Example 5(Non-spherical particle)7.5 mass %
Acrylic resin(Thermoplastic resin):The ア Network リ デ ィ ッ Network A-817BA of DIC companies production(Solid component concentration is Resin 2 is designated as in 50 mass %, table)30 mass %
Crosslinking agent:The U ロ ネ ー ト HL of Japanese Port リ ウ レ タ Application industrial group production(Isocyanates system crosslinking agent, solid into Divide concentration for 75 mass %, crosslinking agent 1 is designated as in table)10 mass %
Retarder thinner:The mass % of butyl acetate 52.5.
The evaluation result of gained film is as shown in table 2.Wherein, the solid constituent ratio of each composition is as follows in masking liquid 2.
Particle:25 mass %
Acrylic resin(Thermoplastic resin):50 mass %
Crosslinking agent:25 mass %.
[ embodiment 2-1 ]
(The manufacture of white reflection film)
M-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and particle master slice 1 are used respectively as reflection Layer(A layers)Raw material, M-phthalic acid copolymerization polyethylene terephthalate 2 and particle master slice 2 be used as supporting layer(C layers)'s Raw material, carrying out mixing makes quality of the content of reflecting layer A mesopores forming agent relative to reflecting layer A be 49 mass %, supporting layer C Quality of the content of mesopore forming agent relative to supporting layer C is 3 mass %, is put into extruder, A layers of melting extrusion temperature 265 DEG C, C layers of 240 DEG C of melting extrusion temperature, its interflow is formed C layer/A layers/C layers of Rotating fields using 3 layers of supply head device, holding The layer-by-layer state is shaped to sheet with die head.Now adjusting the discharge-amount of each extruder makes C layers/A layers/C layers of thickness ratio double 10/80/10 is reached after axle stretching.Cooling and solidifying further is made not for 25 DEG C of chilling roll in the piece timber-used surface temperature Stretched film.Make the unstretching film by 73 DEG C of preheated zone, then by 75 DEG C of preheated zone, and imported into and be maintained at 92 DEG C regions of longitudinal stretch, 2.9 times of longitudinal stretching cools down with 25 DEG C of roller groups, obtains monadic stretching membrane.Then, in gained In the one side of monadic stretching membrane using reverse roll coating method be coated with it is following shown in be used for form superficial layer(B layers)Masking liquid 3.
The > of < masking liquids 3
The Z-465 of the mutual induction KCC production of resin will be used as(Resin 1)Obtained with the above-mentioned Production Example 6 as particle To particle 8 and as the ion exchange water of retarder thinner resin reached with the solid component content ratio of resin and particle: Particle=75:25(Quality %)And the solid component concentration of masking liquid reaches that 20 mass % mode is mixed, and masking liquid 3 is made.
After coating, 115 DEG C of preheated zone is passed to while the two ends of film are kept with clip it imported into be maintained at 130 DEG C of regions of lateral stretch, 3.6 times of cross directional stretch.Then heat fixation is carried out in 185 DEG C in stenter, is in contracting rate 2%th, contracting temperature is the horizontal contracting of progress under conditions of 130 DEG C, then cuts away film two ends, hot pine is carried out with longitudinal relaxation rate 2% Relax, be cooled to room temperature, obtain biaxially-stretched film.The evaluation result of gained film is as shown in table 4.
[ embodiment 2-2~2-5,2-8~2-15, comparative example 2-1~2-5 ]
Except making superficial layer(B layers)The form and Rotating fields of particle used respectively as shown in Table 3 and Table 4 beyond, it is other with it is real Apply a 2-1 and similarly obtain biaxially-stretched film.The evaluation result of gained film is as shown in table 4.
[ embodiment 2-6 ]
Except reflecting layer A pore former to be changed to the resin immiscible with polyester(Cycloolefin, Port リ プ ラ ス チ ッ Network ス " the TOPAS 6017S-04 " of company's production), make quality of the content of pore former relative to reflecting layer A for 20 mass % with Outside, other that biaxially-stretched film is made in the same manner as embodiment 2-1 and is evaluated, evaluation result is as shown in table 4.
[ embodiment 2-7 ]
Except after uniaxial tension, it is biaxial stretch-formed before be not coated with masking liquid in addition to, it is other obtained in the same manner as embodiment 2-1 twin shafts drawing Film is stretched, with direct gravure device using wet thickness as 15g/m on the biaxially-stretched film2Coating weight coating comprising following For forming superficial layer(Layer B)Masking liquid 4 shown in composition masking liquid, be then dried to obtain film in 80 DEG C in baking oven.
< masking liquids 4, solid component concentration are 30 mass % >
Particle:The particle 8 obtained in above-mentioned Production Example 6(Non-spherical particle)7.5 mass %
Acrylic resin(Thermoplastic resin):The ア Network リ デ ィ ッ Network A-817BA of DIC companies production(Resin 2)30 matter Measure %
Crosslinking agent:The U ロ ネ ー ト HL of Japanese Port リ ウ レ タ Application industrial group production(Crosslinking agent 1)10 mass %
Retarder thinner:The mass % of butyl acetate 52.5.
The evaluation result of gained film is as shown in table 4.Wherein, the solid constituent ratio of each composition is as follows in masking liquid 4.
Particle:25 mass %
Acrylic resin(Thermoplastic resin):50 mass %
Crosslinking agent:25 mass %.
Invention effect
The present invention, which can be provided, can fully suppress stickup with light guide plate, while can fully suppress the white of the damage of light guide plate Reflectance coating.
Industrial applicability
The white reflection film of the present invention is due to can fully suppress stickup with light guide plate, can fully suppress the damage of light guide plate in addition Wound, therefore the area source reflecting plate with light guide plate is especially suitable for use as, particularly used in such as liquid crystal display device Edge lighting-type back light unit used in reflectance coating.

Claims (9)

1. white reflection film, it has the reflecting layer A and superficial layer B by the resin combination manufacture containing particle,
Highly it is during there is the projection formed by above-mentioned particle, the surface on superficial layer B and reflecting layer A opposite side surface More than 5 μm of projection number is 104~1010Individual/m2,
Above-mentioned particle is the crushing polymer particle that average grain diameter is 3~100 μm, manufactured by polyethylene terephthalate.
2. white reflection film according to claim 1, wherein the length-width ratio of above-mentioned particle(Major diameter/minor axis)Average out to More than 1.31, less than 1.80, and the standard deviation of length-width ratio is 0.15~0.50.
3. the content of above-mentioned particle is with superficial layer B's in white reflection film according to claim 1 or 2, wherein superficial layer B It is 1~70 mass % on the basis of quality.
4. white reflection film according to claim 1 or 2, wherein volatile organic solvent amount are below 10ppm.
5. white reflection film according to claim 1 or 2, wherein reflecting layer A contains hole, its pore volume rate is 15 bodies Product more than %, below 70 volume %.
6. white reflection film according to claim 1 or 2, it is 0 volume % less than 15 that it, which also has pore volume rate, Volume % supporting layer C.
7. white reflection film according to claim 1 or 2, wherein superficial layer B are the layers formed by the coating of masking liquid.
8. white reflection film according to claim 1 or 2, it is used as the area source reflecting plate with light guide plate.
9. the manufacture method of white reflection film, it is with reflecting layer A and by the surface of the resin combination manufacture containing particle The manufacture method of layer B white reflection film,
White reflection film has the projection formed by above-mentioned particle, the table in superficial layer B and the surface of reflecting layer A opposite side Projection number in face highly for more than 5 μm is 104~1010Individual/m2,
Above-mentioned particle is that average grain diameter is 3~100 μm, by the way that polymer is crushed into obtained crushing polymer particle, described poly- Compound is polyethylene terephthalate.
CN201710367396.7A 2013-08-07 2014-08-04 White reflection film Pending CN107272091A (en)

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