CN104769461A - White reflective film - Google Patents

White reflective film Download PDF

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Publication number
CN104769461A
CN104769461A CN201480002946.XA CN201480002946A CN104769461A CN 104769461 A CN104769461 A CN 104769461A CN 201480002946 A CN201480002946 A CN 201480002946A CN 104769461 A CN104769461 A CN 104769461A
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CN
China
Prior art keywords
particle
reflection film
film
layer
superficial layer
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CN201480002946.XA
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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
Priority to CN201710367396.7A priority Critical patent/CN107272091A/en
Priority to CN201710367240.9A priority patent/CN107315209B/en
Publication of CN104769461A publication Critical patent/CN104769461A/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

A white reflective film having a reflective layer (A), and a surface layer (B) comprising a resin composition containing particles, the white reflective film having projections formed by the particles on a surface of the surface layer (B) on the reverse side thereof from the reflective layer (A), the number of projections having a height of at least 5 [mu]m in the surface being 10<4> to 10<10>/m2, and the particles being non-spherical particles having an average particle diameter of 3-100 [mu]m and a 10% compressive strength of 0.1-15 MPa. In this film, adhesion to a light guide plate can be adequately suppressed, and at the same time, scratching of the light guide plate can be adequately suppressed.

Description

White reflection film
Technical field
The present invention relates to white reflection film.Particularly relate to the white reflection film for liquid crystal indicator.
Background technology
The back light unit of liquid crystal indicator (LCD) has and has light source at the back side of display panels and have the full run-down type of reflectance coating further at its back side and have the light guide plate of reflecting plate at the configuration back side, the back side of display panels, have the edge lighting-type (エ ッ ジ ラ イ ト type) of light source in the side of this light guide plate.Back light unit in the past used in large LCD mainly uses full run-down type (mainly full run-down type CCFL) from the viewpoint of the excellent in uniformity of brightness in the brightness and picture of picture, edge lighting-type is through being commonly used in the more small-sized LCD such as notebook type PC, but, in recent years, due to the development of light source or light guide plate, even the homogeneity in the brightness of edge lighting-type back light unit and picture also improves, be not only more small-sized LCD, in large LCD, also bring into use the back light unit of edge lighting-type.This is because there is the advantage that LCD can be made thinning.
In edge lighting-type back light unit, it is the structure that light guide plate directly contacts with reflectance coating.Therefore, in such an embodiment, paste if there is light guide plate and reflectance coating, then the brightness of the part of having pasted becomes exception, the problem of deviation in the face occurring brightness.Therefore, must make, between light guide plate and reflectance coating, there is gap, and keep this clearance constant.Such as, the gap remained constant that by making the surface of reflectance coating, there is pearl and can make between light guide plate and reflectance coating, thus can prevent them from pasting.But if the light guide plate now formed by softer material contacts with reflectance coating, then the pearl that there is reflectance coating or surface can damage the problem of light guide plate.As its countermeasure, have such as patent documentation 1 ~ 3, on the surface of reflectance coating by being coated with the report of the antisitic defect layer formed containing elastic system pearl.
But, although the such antisitic defect layer of patent documentation 1 ~ 3 has light guide plate injury inhibitory effect to a certain degree, its object originally, namely guarantee that there is the tendency of variation gap (suppressing to paste) aspect.The present inventor is learnt by research, is only conceived to the number of projection as in the past, sometimes fully can not meet the stickup of in recent years required suppression and light guide plate and suppress damage two aspects of light guide plate.
(patent documentation 1) Japanese Unexamined Patent Publication 2003-92018 publication
(patent documentation 2) Japanese Unexamined Patent Application Publication 2008-512719 publication
(patent documentation 3) Japanese Unexamined Patent Publication 2009-244509 publication.
Summary of the invention
The object of this invention is to provide and can fully suppress and the stickup of light guide plate, the white reflection film that simultaneously fully can suppress the damage of light guide plate.
The present invention adopts following formation to solve above-mentioned problem.
1. white reflection film, its superficial layer B that there is reflection horizon A and manufactured by the resin combination containing particle,
Having with the surface of reflection horizon A opposite side the projection formed by above-mentioned particle at superficial layer B, is highly that the projection number of more than 5 μm is 10 in this surface 4~ 10 10individual/m 2,
The non-spherical particle that above-mentioned particle is mean grain size is 3 ~ 100 μm, 10% compression strenght is 0.1 ~ 15MPa.
2. the white reflection film described in above-mentioned 1, wherein above-mentioned particle is by polymkeric substance being pulverized the pulverizing polymer particle obtained.
3. the white reflection film described in above-mentioned 2, wherein above-mentioned polymkeric substance is polyester.
4. the white reflection film in above-mentioned 1 ~ 3 described in any one, wherein above-mentioned particle is the average out to more than 1.31, less than 1.80 of length breadth ratio (major diameter/minor axis), and the standard deviation of length breadth ratio is the non-spherical particle of 0.15 ~ 0.50.
5. the white reflection film in above-mentioned 1 ~ 3 described in any one, wherein in superficial layer B the content of above-mentioned particle with the quality of superficial layer B for benchmark is 1 ~ 70 quality %.
6. the white reflection film in above-mentioned 1 ~ 3 described in any one, wherein volatile organic solvent amount is below 10ppm.
7. the white reflection film in above-mentioned 1 ~ 3 described in any one, wherein reflection horizon A contains hole, and its volume of voids rate is 15 more than volume %, 70 below volume %.
8. the white reflection film described in above-mentioned 7, it also has volume of voids rate and is 0 more than volume % and the supporting layer C being less than 15 volume %.
9. the white reflection film described in above-mentioned 7, wherein superficial layer B is the layer formed by the coating of masking liquid.
10. the white reflection film in above-mentioned 1 ~ 3 described in any one, it is as the area source reflecting plate with light guide plate.
Accompanying drawing explanation
Fig. 1,2 is examples of the electron micrograph of the projection formed by non-spherical particle in the present invention.
Fig. 3 is the schematic diagram representing the Damage Evaluation of light guide plate in the present invention and the evaluation method that comes off of particle.
Fig. 4 is the schematic diagram of structure used during closely sealed inequality of the present invention is evaluated.
The preferred forms of invention
White reflection film of the present invention has reflection horizon A and superficial layer B.
Below describe in detail and form each constituent of the present invention.
[ reflection horizon A ]
Reflection horizon A of the present invention contains thermoplastic resin and pore former, contains pore former and in layer, comprise hole by making it, makes it be white.Described pore former will describe in detail below, can use such as inorganic particulate, the resin (hereinafter sometimes referred to immiscible resin) immiscible with the thermoplastic resin forming this reflection horizon A.In addition, the reflectivity of reflection horizon A under wavelength 550nm is preferably more than 95%, is more preferably more than 96%, is particularly preferably more than 97%.The reflectivity of white reflection film more easily reaches preferable range thus.
Reflection horizon A has hole as mentioned above in layer, the volume of this hole relative to reflection horizon A volume shared by ratio (volume of voids rate) be preferably 15 more than volume %, 70 below volume %.Improve effect by can make reflectivity in such scope to improve, easily obtain above-mentioned reflectivity.In addition, masking stretchability can also be made to improve effect improve.When volume of voids rate is too low, there is the tendency being difficult to obtain preferred reflectivity.Consider from above-mentioned viewpoint, the volume of voids rate in the A of reflection horizon is more preferably 30 more than volume %, is particularly preferably 40 more than volume %.On the other hand, when volume of voids rate is too high, there is the tendency that the raising effect of masking stretchability reduces.Consider from above-mentioned viewpoint, the volume of voids rate in the A of reflection horizon is more preferably 65 below volume %, is particularly preferably 60 below volume %.
Volume of voids rate can be reached by the kind of pore former in adjustment reflection horizon A or size, amount.
(thermoplastic resin)
The thermoplastic resin of formation reflection horizon A can enumerate the thermoplastic resin such as manufactured by polyester, polyolefin, polystyrene, acrylic compounds (ア Network リ Le).Wherein, from the viewpoint of the white reflection film obtaining mechanical property and excellent heat stability, preferred polyester.
Described polyester preferably uses the polyester manufactured by dicarboxylic acid component and diol component.This dicarboxylic acid component can enumerate derived from terephthalic acid (TPA), m-phthalic acid, NDA, 4, the composition of 4 '-biphenyl dicarboxylic acid, hexane diacid, decanedioic acid etc.Diol component can enumerate the composition derived from ethylene glycol, BDO, 1,4-CHDM, 1,6-hexanediol etc.Optimization aromatic polyester, particularly preferably polyethylene terephthalate in these polyester.Polyethylene terephthalate can be homopolymer, but from the viewpoint of by film single shaft or biaxial stretch-formed time suppress crystallization thus the raising effect of masking stretchability is improved, preferred copolymer.Copolymer composition can enumerate above-mentioned dicarboxylic acid component, diol component, but raising effect that is high from the viewpoint of thermotolerance, masking stretchability is high, preferred m-phthalic acid composition, NDA composition.The ratio of copolymer composition be with whole dicarboxylic acid component 100 % by mole of polyester for benchmark, be such as 1 ~ 20 % by mole, be preferably 2 ~ 18 % by mole, be more preferably 3 ~ 15 % by mole, be particularly preferably 7 ~ 11 % by mole.By making the ratio of copolymer composition in this scope, the raising excellent effect of masking stretchability.In addition, dimensional stability is also excellent.
(pore former)
In the A of reflection horizon, when using inorganic particulate as pore former, inorganic particulate preferred white inorganic particulate.This white inorganic particle can enumerate the particle of barium sulphate, titania, silicon dioxide, calcium carbonate.As long as there is suitable reflectivity for these inorganic particulates selection mean grain size, content to make white reflection film, be not particularly limited.Preferably make reflection horizon A, the reflectivity of white reflection film reaches preferable range of the present invention.In addition, the volume of voids rate of reflection horizon A is made to reach preferable range of the present invention.Consider these, the mean grain size of inorganic particulate is such as 0.2 ~ 3.0 μm, is preferably 0.3 ~ 2.5 μm, is more preferably 0.4 ~ 2.0 μm.Its content is preferably 20 ~ 60 quality % with the quality of reflection horizon A for benchmark, is more preferably 25 ~ 55 quality %, most preferably is 31 ~ 53 quality %.By adopting such particle shape, particle appropriateness dispersion in the polyester can be made, be difficult to the aggegation that particle occurs, thus the film not having thick projection can be obtained.In addition, be that the disrumpent feelings of starting point is also inhibited with oversize grain during stretching.Inorganic particulate can be any shape of particle, such as, can be tabular, spherical.Inorganic particulate can carry out for improving dispersed surface treatment.
When using immiscible resin as pore former, as long as immiscible resin is immiscible with the thermoplastic resin of constituting layer, be not particularly limited.Such as, when described thermoplastic resin is polyester, preferred polyolefm, polystyrene etc.These resins can be particle shapes.Its content, in the same manner as the situation of inorganic particulate, as long as selection mean grain size, content have suitable reflectivity to make white reflection film, is not particularly limited.Preferably make reflection horizon A, the reflectivity of white reflection film reaches preferable range of the present invention.In addition, the volume of voids rate of reflection horizon A is made to reach preferable range of the present invention.Consider these, content is preferably 10 ~ 50 quality % with the quality of reflection horizon A for benchmark, is more preferably 12 ~ 40 quality %, most preferably is 13 ~ 35 quality %.
(other composition)
In the A of reflection horizon, only otherwise damage object of the present invention, other composition can also be contained, such as ultraviolet light absorber, antioxidant, antistatic agent, fluorescer, wax, the particle different from pore former, resin etc.
[ superficial layer B ]
Superficial layer B of the present invention, by the resin combination manufacture containing particle in resin, is form bossed layer by this particle on surface.Described resin preferred thermoplastic resin.In addition, cross-linked structure can be had by crosslinking chemical.In this case, can use and have and can form with the thermoplastic resin of the functional group of the reaction-ity group reaction of crosslinking chemical the cross-linked structure formed by crosslinking chemical and thermoplastic resin, also can be use do not have can with the thermoplastic resin of the functional group of the reaction-ity group reaction of crosslinking chemical, the form with the matrix of the matrix of thermoplastic resin and the cross-linked structure of cross-linking agents.When there is cross-linked structure, there is the tendency that the intensity of superficial layer B improves.On the other hand, when having cross-linked structure too much, during by film reclaiming, have non-fused mass to become the tendency that the recyclability of film is deteriorated such as many, consider from above-mentioned viewpoint, preferred cross-linked structure is exceeded.
Superficial layer B can be formed by coating masking liquid in the manufacture process of film or after manufacturing, and such as coetrusion etc. also can be adopted to be formed with reflection horizon A simultaneously.In order to superficial layer B described above has cross-linked structure, the coating preferably by masking liquid is formed.Consider from above-mentioned viewpoint, the content of crosslinking chemical, to form the solid constituent of masking liquid for benchmark, is preferably below 35 quality %, is more preferably below 30 quality %, more preferably below 25 quality %, is particularly preferably below 20 quality %.In addition, be preferably more than 1 quality %, be more preferably more than 2 quality %, more preferably more than 3 quality %, be particularly preferably more than 5 quality %.
(thermoplastic resin)
The thermoplastic resin forming superficial layer B can use the thermoplastic resin same with the thermoplastic resin of above-mentioned formation reflection horizon A.Wherein, preferred acrylic compounds, polyester, particularly from the viewpoint of the white reflection film obtaining mechanical property and excellent heat stability, preferred polyester.
Described polyester can use the polyester same with the polyester in above-mentioned reflection horizon A.In these polyester, from the viewpoint of the white reflection film obtaining mechanical property and excellent heat stability, optimization aromatic polyester, particularly preferably polyethylene terephthalate.Polyethylene terephthalate can be homopolymer, but from the viewpoint of the effect obtaining the softening superficial layer B of appropriateness, suppress particle to come off, preferred copolymer, particularly preferably copolymerization polyethylene terephthalate.Apply with external force such as light guide plate frictions even if having thus, particle is also difficult to come off.Described copolymer composition can enumerate above-mentioned dicarboxylic acid component, diol component, and raising effect that is high from the viewpoint of thermotolerance, masking stretchability is high, preferred m-phthalic acid composition, NDA composition.The ratio of copolymer composition for benchmark with whole dicarboxylic acid component 100 % by mole of polyester, such as, is 1 ~ 20 % by mole, is preferably 2 ~ 18 % by mole, is more preferably 3 ~ 17 % by mole, is particularly preferably 12 ~ 16 % by mole.By making the ratio of copolymer composition in above-mentioned scope, the raising excellent effect of masking stretchability.In addition, dimensional stability is also excellent.
By when in the manufacture process of film or after manufacturing, coating masking liquid forms superficial layer B, in order to obtain above-mentioned effect, in addition in order to improve the stability of masking liquid, preferably the side chain of these polyester or main chain are with the group with the function improving said solvophilic.The group here with the function improving said solvophilic preferably enumerates the group of metal organic sulfonate (being preferably sulfonate sodium), the group of hydroxyl, alkyl ether, the group etc. of carboxylate.The m-phthalic acid composition preferably 3 ~ 30 % by mole, more preferably 5 ~ 20 % by mole, the further preferred embodiment of 5 ~ 15 % by mole that comprise the group with metal organic sulfonate relative to all acid composition 100 % by mole of polyester particularly preferably are in the present invention.In addition, also preferably comprise diglycol composition from the same viewpoint, relative to all acid composition 100 % by mole of polyester, preferably containing this composition 3 ~ 30 % by mole, more preferably 5 ~ 20 % by mole, the further preferred embodiment of 5 ~ 15 % by mole.
(non-spherical particle)
In the present invention, must to be mean grain size the be non-spherical particle of 3 ~ 100 μm of the particle in superficial layer B.By making mean grain size in above-mentioned scope, easily forming the mode of aftermentioned projection number, more easily guaranteeing gap.If mean grain size is excessive, then easily there is particle and come off, cause the defect on picture.On the other hand, if mean grain size is too small, as original object guarantee become with the gap of light guide plate difficulty.Consider from above-mentioned viewpoint, be more preferably more than 5 μm, more preferably more than 7 μm, be particularly preferably more than 8 μm, and, be more preferably less than 80 μm, more preferably less than 70 μm, be particularly preferably less than 50 μm.
In addition, being that non-spherical particle can guarantee the gap with light guide plate by making the particle forming projection in outermost surface, the effect suppressing light guide plate damage can be improved simultaneously.In the present invention, non-spherical particle refers to that the maximum dimension D x(of particle is designated as x direction) and the direction vertical with x direction (be designated as y direction and z direction.Z direction is also vertical with y direction direction) in maximum dimension D y and Dz(Dy≤Dz) maximum gauge in these all directions difference (Dx-Dy, Dx-Dz, Dy-Dz) at least any 1 more than Dx 20% particle.
Think that obtaining above-mentioned effect by such non-spherical particle is due to following mechanism.That is, thinking by making the shape of particle be non-spherical, becoming greatly with the contact area of light guide plate, causing pressure dissipation, being not easy thus to cause damage.When the shape of particle is the non-spherical as afore mentioned rules, particle has maximum gauge in one direction, when being included in superficial layer B, easily becomes the direction almost parallel with the direction, face of superficial layer B from this maximum gauge direction of probability.Therefore, the projection formed by described particle and the contact area of light guide plate become greatly, and pressure is disperseed.On the contrary, when particle is spherical, the area of the part contacted with light guide plate narrows, and therefore pressure is concentrated thus easily caused damage.Even use soft particle like this, also owing to being spherical and become and easily damage light guide plate.
The present invention in superficial layer B by having particle shape as above specific, the narrow range concentrating on projection summit with it contacts light guide plate, not as be taken at keep projection quantity while increase the contact area of projection and light guide plate, make the embodiment of pressure dissipation thus, because the quantity of the contact point with light guide plate is suitable, while gap is guaranteed in realization, each projection is reduced the pressure of light guide plate, suppresses the damage of light guide plate thus.If not in above-mentioned scope, then become the form of the narrow range contact light guide plate only concentrating on such as projection summit, this part applied pressure is raised, becomes and easily cut.
In the present invention, suppress the effect of light guide plate damage and the effect suppressing to paste with light guide plate, the average out to more than 1.31, less than 1.80 of the length breadth ratio (major diameter/minor axis) of preferred particle to improve further.This length breadth ratio is more preferably more than 1.35, is more preferably less than 1.75 in addition.In order to obtain above-mentioned effect, preferred length breadth ratio is large, if but excessive, have that to be difficult to maintain in outermost surface be highly the tendency of the projection number of more than 5 μm.Here length breadth ratio is undertaken observing trying to achieve by using electron microscope described later.In described observation, using the maximum gauge of particle as major diameter, the maximum gauge on the direction vertical with this maximum gauge is as minor axis.
Meanwhile, when inferring that the shape of particle has the deviation of appropriateness, namely the shape of particle becomes moderately inconsistent, is difficult to thus apply pressure to specific particle, thus is difficult to damage light guide plate.
Therefore, the standard deviation of the preferred length breadth ratio of described particle is 0.15 ~ 0.50.That is, this represents that the shape of each particle has the deviation of appropriateness.By the shape of the particle forming projection, there is appropriate deviation, while the gap with light guide plate can be guaranteed, improve the effect suppressing light guide plate damage further.Deviation hour, guarantees that the raising effect that gap and damage suppress reduces.On the other hand, when deviation is excessive, easily occur bad problem when adding superficial layer B to, have the tendency being difficult to the projection frequency obtaining imagination, result is difficult to play the raising effect guaranteeing gap, damage suppression.Consider from above-mentioned viewpoint, the standard deviation of the length breadth ratio of particle is more preferably more than 0.16, more preferably more than 0.17, is more preferably less than 0.45, more preferably less than 0.43 in addition.
In the present invention, 10% compression strenght of above-mentioned particle is necessary for 0.1 ~ 15MPa.Can gap be guaranteed thus, the damage to light guide plate can also be suppressed.When compression strenght is too low, can stress and excessive deformation, therefore as original object guarantee become difficulty with the gap of light guide plate.On the other hand, when compression strenght is too high, even non-spherical particle also easily damages light guide plate.Consider from above-mentioned viewpoint, 10% compression strenght is preferably more than 0.2MPa, is more preferably more than 0.3MPa, more preferably more than 3MPa, be particularly preferably more than 8MPa, be preferably below 14MPa, more preferably below 13MPa in addition, be more preferably below 12MPa.
The content of the non-spherical particle in the present invention in superficial layer B can use the particle of mean grain size as above, carries out suitably adjustment in the mode meeting aftermentioned projection number.Such as, when having the tendency thin relative to the mean grain size superficial layer B thickness of particle, have the tendency easily forming projection, therefore content can be more less; Time contrary, preferred content is more, can consider that such tendency suitably adjusts.Particularly, with the quality of superficial layer B for benchmark, be preferably 1 ~ 70 quality %, be more preferably more than 5 quality %, more preferably more than 10 quality %, be particularly preferably more than 20 quality %, be more preferably below 60 quality %, more preferably below 50 quality % in addition, be particularly preferably below 30 quality %.
Particle in the present invention contained by superficial layer B no matter its kind how, can be organic filler, also can be inorganic particulate, can also be organo-mineral complexing particle.From the viewpoint of the mode easily meeting above-mentioned particle, preferably by the polymer particle of the polymers manufacturings such as acrylic compounds, polyester, polyurethane, nylon, polyolefin, polyethers.Be more preferably polyester, nylon, so easy acquisition more suitably 10% compression strenght.Be particularly preferably polyester (wherein more preferably polyethylene terephthalate), it has the advantage reclaiming masking excellence.
In the present invention, the method realizing above-mentioned shape of particle is not particularly limited, but from easily obtaining the viewpoint of the particle with particularly preferably shape and considering from manufacturing cost, productive viewpoint, preferably solid polymer is pulverized the method obtaining particle.The particle obtained by this operation is called pulverizing polymer particle.The polymer sheet of this operation more specifically by such as granulating after preferred polymeric makes its crystallization preferably by thermal treatment, normal temperature or lower than the low temperature of normal temperature under carry out the method pulverized.From the viewpoint of more easily pulverizing, preferably pulverizing under lower than the low temperature of normal temperature, as obtaining the method for described low temperature, preferably can enumerate and carrying out by liquid nitrogen the method that cools.
Except polymer sheet except above-mentioned granulating, the polymer fiber etc. of the polymer film of shaping polymer composition, masking, throwing is pulverized and also can prepare object and pulverize polymer particle.By select like this form of polymkeric substance to be comminuted (comprise be such as particle time change size, be film time change thickness, be fiber time change diameter), the particle with various non-spherical form (length breadth ratio) can be obtained, in addition, the deviation (standard deviation) of shape of particle can also be adjusted.
The polymkeric substance pulverizing polymer particle can be the blend of copolymerization or 2 kinds of polymkeric substance, can also comprise diameter inorganic particulate, the organic filler less than it in pulverizing polymer particle inside, or containing ultraviolet light absorber, lubricant etc.
(form of superficial layer B)
In the present invention, the superficial layer B manufactured by the resin combination containing particle as above forms the outermost layer of at least one party of white reflection film.Further, with the surface (hereinafter sometimes referred to outermost surface) of reflection horizon A opposite side, there is the projection formed by above-mentioned particle at this formation outermost superficial layer B.This projection, from the viewpoint of the gap of guaranteeing light guide plate and film, must have the projection of proper height at outermost surface with suitable frequency.
Therefore, in the present invention, in outermost surface, must be highly the projection number (projection frequency) of more than 5 μm be 10 usually 4~ 10 10individual/m 2.Fully can guarantee the gap of light guide plate and film thus, guarantee to paste inhibition.Inhibition is pasted poor during projection underfrequency.On the other hand, when projection frequency is too high, the probability rising having particle to come off or the tendency of reflectance reduction.
(other composition)
Can also containing the composition beyond above-mentioned constituent at the boundary surface layer B not damaging the object of the invention.Described composition can enumerate such as ultraviolet light absorber, antioxidant, antistatic agent, fluorescer, wax, surfactant, the particle different from above-mentioned particle, resin etc.
[ Rotating fields ]
In the present invention, the thickness of reflection horizon A is preferably 80 ~ 350 μm.The effect of raising reflectivity can be made thus to improve.If the thickness of reflection horizon A is crossed thin, the effect improving reflectivity is low, and blocked up then right and wrong are efficient.From the viewpoint, the thickness of reflection horizon A is more preferably 80 ~ 300 μm, more preferably 100 ~ 320 μm, is particularly preferably 150 ~ 250 μm.
In the present invention, the thickness of superficial layer B is preferably 5 ~ 100 μm.Be more preferably 5 ~ 80 μm.Now the thickness of superficial layer B refers to the thickness sum of the particle diameter of particle and the resin portion on its surface coating.
In addition, the thickness maintaining the resin portion of the particle of superficial layer B is preferably 0.2 ~ 50 μm.Projection frequency easily becomes preferred embodiment thus, easily guarantees the gap with light guide plate.If the thickness of the above-mentioned resin portion of superficial layer B is excessively thin, then the tendency that the particle in the projection having the surface of superficial layer B to be formed easily comes off.And blocked up, there is the tendency being difficult to obtain preferred projection frequency.Consider from above-mentioned viewpoint, be more preferably more than 0.3 μm, more preferably more than 0.5 μm, be particularly preferably more than 1 μm, most preferably be more than 2 μm, and be more preferably less than 40 μm.Further, if consider deciduous, be preferably more than 1 μm, be preferably more than 2 μm.
Reflection horizon A is expressed as A, superficial layer B is when being expressed as B, the rhythmo structure of white reflection film can enumerate 2 Rotating fields of B/A, B/A/B 3-tier architecture or B is configured in the sandwich construction of outermost more than 4 layers of at least any one party.Be particularly preferably the supporting layer C(had further for making masking stable and be expressed as C), the 3-tier architecture of B/C/A or B/A/C, 4 Rotating fields of B/C/A/C.Most preferably be 4 Rotating fields of B/C/A/C, masking stretchability is more excellent.And be difficult to the problems such as curling occur.In the present invention, preferably there is the embodiment of such supporting layer C.Described supporting layer C is preferably by the embodiment of the polyester manufacture same with reflection horizon A, volume of voids rate lower (be preferably 0 more than volume % and be less than 15 volume %, be more preferably 5 below volume %, be particularly preferably 3 below volume %).In addition, the thickness (referring to gross thickness when having multiple supporting layer C) of described supporting layer C is preferably 5 ~ 140 μm, is more preferably 20 ~ 140 μm.
In the present invention, except reflection horizon A, superficial layer B and supporting layer C, only otherwise damage the layer that object of the present invention can also have other.Such as can also have the layer of the function such as imparting easy-adhesion, windability (slickness), antistatic behaviour, electric conductivity, UV-durability, for adjusting the layer of optical characteristics.
[ manufacture method of film ]
One of the method manufacturing white reflection film of the present invention example is below described.
When manufacturing white reflection film of the present invention, can by molten resin rubbing method (comprise and melt extrude resin-coated method), coetrusion and lay-up method and use the masking liquid for the formation of superficial layer B to form superficial layer B by masking liquid rubbing method on the reflection horizon A obtained by extrusion by melting etc.Wherein, particularly preferably in by reflection horizon A and supporting layer C by the stacked manufactured laminated body of coetrusion being carried out the method for laminate surface layer B by masking liquid rubbing method.By the distribution utilizing masking liquid rubbing method laminate surface layer B easily can control particle by changing drying condition etc., thus can the cheap and projection number that easily volume production is predetermined.In addition, even the particle that 10% compression strenght is less, process also becomes easy.Further, keep the specified particle shape in the present invention to become easy, easily make the form of projection be preferred form.
Below to adopt polyester as form reflection horizon A thermoplastic resin and form supporting layer C thermoplastic resin, adopt coetrusion as reflection horizon A and supporting layer C laminating method, adopt masking liquid rubbing method as superficial layer B laminating method time manufacture method be described, but the invention is not restricted to this manufacture method, also can similarly be manufactured by alternate manner with reference to following.Now, do not comprise when extruding operation, following " melt extruding temperature " can separately read as such as " melt temperature ".The fusing point of polyester used is here designated as Tm(unit: DEG C), glass transition temperature is designated as Tg(unit: DEG C).
First, as the polymer blend for the formation of reflection horizon A, prepare potpourri polyester, pore former and other optional member mixed.In addition, as the polymer blend for the formation of supporting layer C, prepare potpourri polyester and optional pore former and other optional member mixed.These polymer blends are dry, fully removing moisture use.
Then, the polymer blend by drying to be put into respectively in different extruders and is melt extruded.Melt extruding temperature must be more than Tm, is set in about Tm+40 DEG C.
Now, the non-weaving cloth type filter being 10 ~ 100 μm for the polymer blend making film, the average pore size that forms especially for the polymer blend of the reflection horizon A stainless steel fine rule that preferably to use by wire diameter be less than 15 μm filters.By carrying out this filtration, usually easily aggegation can be suppressed and become the aggegation of the particle of thick agglutination particle, thus obtaining the film of thick few foreign.The average pore size of non-weaving cloth is preferably 20 ~ 50 μm, is more preferably 15 ~ 40 μm.Polymer blend after filtration is extruded from die head with multilayered state for multilayer extrusion method (coetrusion) while stub bar by using in the molten state, thus manufactures non-stretch laminate sheet.The non-stretch laminate sheet curtain coating drum cooling curing extruded from die head is made non-stretch laminate film.
Then, by this non-stretch laminate film by heating such as roller heating, infrared heatings, carry out stretching along masking machinery direction of principal axis (hereinafter sometimes referred to longitudinal direction or length direction or MD) and obtain longitudinal stretching film.This stretching preferably utilizes the difference of the roller of more than 2 to carry out.Film after longitudinal stretching is then imported in stenter, and at the direction vertical with thickness direction with longitudinal direction (hereinafter sometimes referred to transverse direction or Width or TD), stretching obtains biaxially-stretched film.
As draft temperature, preferably carry out at the temperature of less than more than Tg, Tg+30 DEG C of polyester (being preferably the polyester forming reflection horizon A), such masking stretchability is more excellent, and easily forms hole satisfactorily.As stretching ratio, longitudinally, be laterally all preferably 2.5 ~ 4.3 times, be more preferably 2.7 ~ 4.2 times.When stretching ratio is too low, the uneven thickness of film has the tendency of variation, and has the tendency being difficult to form hole, and when stretching ratio is too high, has and easily disrumpent feelings tendency occurs in masking.When implementing to carry out after longitudinal stretching cross directional stretch progressively biaxial stretch-formed, the 2nd stage (being now cross directional stretch) is preferably high than the draft temperature in the 1st stage about 10 ~ 50 DEG C.This is the cause because the stretch orientation in the 1st stage makes the Tg of uniaxial film raise.
In addition, preferred by film preheating before each stretching.The thermal pretreatment of such as cross directional stretch can slow intensification from the temperature of Tg+5 DEG C high than polyester (being preferably the polyester forming reflection horizon A).Intensification in cross directional stretch process can be continuous print, also can be interim (progressively), but normally progressively heat up.Such as the regions of lateral stretch of stenter is divided into several region along film moving direction, the heating medium that predetermined temperature is flow through in each region heats up.
Film after biaxial stretch-formed then carries out heat fixation successively, Biaxially oriented film is made in hot wire-CVD (Hot relaxation Slow) process, but then can stretch by melt extruding, and these process also can be carried out while making film movement.
Film after biaxial stretch-formed can under the state holding two ends with clip, when the fusing point of the polyester polyester of reflection horizon A (be preferably form) is designated as Tm, under (Tm-20 DEG C) ~ (Tm-100 DEG C), constant-breadth or less than 10% Kuan Du Minus few under heat-treat, heat fixation, percent thermal shrinkage reduced.When described heat treatment temperature is too high, the planarity of film has the tendency of variation, uneven thickness to have the tendency that change is large; Too low, there is the tendency that percent thermal shrinkage becomes large.
In addition, in order to adjust thermal shrinking quantity, the two ends of the film of holding can be cut away, the haulage speed of adjustment film longitudinal direction, relaxes in the vertical.Lax method is the speed of the roller group of adjustment tenter outlet side.As lax ratio, relative to the film linear velocity of stenter, the speed of roller group is reduced, implement preferably 0.1 ~ 2.5%, further that preferably the reduction of speed of 0.2 ~ 2.3%, particularly preferably 0.3 ~ 2.0%, by film lax (this value is called " relaxation rate "), adjusts longitudinal percent thermal shrinkage by controlling relaxation rate.In addition, for film laterally, can in the process before being cut away at two ends, width be reduced, thus obtain the percent thermal shrinkage of expectation.
When carrying out biaxial stretch-formed, except progressively biaxial stretching process longitudinally as above-horizontal, also can be laterally-longitudinal progressively biaxial stretching process.In addition, biaxial stretching process simultaneously can also be adopted to carry out masking.The while of employing during biaxial stretching process, stretching ratio is is longitudinally, laterally all such as 2.7 ~ 4.3 times, be preferably 2.8 ~ 4.2 times.
Superficial layer B can be formed preferably by so-called online rubbing method, namely, after the longitudinal stretching of above-mentioned operation, the masking liquid of coating for forming superficial layer B on longitudinal stretching film, the heat described in utilizing in preheating procedure, cross directional stretch operation, heat fixation operation etc. carries out drying, solidification.Masking liquid can by the composition of mixing formation superficial layer B, in order to make its easy coating optionally obtain with solvent dilution.Now, solvent is preferably water, can reduce aftermentioned volatile organic solvent amount like this.Be not particularly limited the coating process of masking liquid, preferred method can enumerate inverse roller rubbing method, gravure method, die head rubbing method, spraying process etc.In addition, the Biaxially oriented film that obtains at biaxial stretch-formed, heat fixation is formed by so-called off-line rubbing method superficial layer B.In off-line rubbing method, because the reasons such as film distortion cause being difficult to during drying apply high heat, therefore usually use easily dry organic solvent as solvent.But the tendency like this having aftermentioned volatile organic solvent amount to increase, therefore particularly preferably online rubbing method in the present invention.
White reflection film of the present invention can be obtained like this.
[ characteristic of white reflection film ]
(reflectivity, brightness)
The reflectivity (reflectivity wavelength 550nm) that white reflection film of the present invention measures from superficial layer B side is preferably more than 95%, is more preferably more than 96%, more preferably more than 97%, be further preferably more than 97.5%, be particularly preferably more than 98%.Be more than 95% or more than 96% by reflectivity, during for liquid crystal indicator or illumination etc., can high brightness be obtained.This reflectivity can pass through as being issued to: get the preferred configuration such as the volume of voids rate improving reflection horizon A, the thickness of increasing reflection horizon A or the thickness etc. of reduction superficial layer B and make the form of each layer be preferred form etc.
In addition, the brightness measured from superficial layer B side is tried to achieve by assay method described later, is preferably 5400cd/m 2above, 5450cd/m is more preferably 2above, 5500cd/m is particularly preferably 2above.
Above-mentioned reflectivity and brightness, in white reflection film, when using together with light guide plate, are the values in the face of light guide plate side.
(volatile organic solvent amount)
The volatile organic solvent amount that white reflection film of the present invention is measured by aftermentioned method is preferably below 10ppm.This can be formed by rubbing method with an organic solvent by presentation surface layer B.In addition, obtaining in time reclaiming raw material and use it to carry out masking, be difficult to produce air marks (ガ ス マ ー Network), masking stretchability (reclaiming masking) improves.Consider from above-mentioned viewpoint, be more preferably below 5ppm, more preferably below 3ppm, it is desirable to 0ppm.In the present invention, in order to make volatile organic solvent amount few, when forming superficial layer B, preferably not adopting solution rubbing method with an organic solvent and adopting above-mentioned method.
Embodiment
Describe the present invention in detail by the following examples.Wherein, each characteristic value is measured by following method.
(1) light reflectance
Integrating sphere installed by spectrophotometer (UV-3101PC that Shimadzu Seisakusho Ltd. manufactures), measures with BaSO under wavelength 550nm 4reflectivity when blank is 100%, using this value as reflectivity.The surface being determined at superficial layer B side is carried out.When there is in table different superficial layer B, measure on the superficial layer B surface of light guide plate side.
(2) mean grain size of particle
The size-grade distribution (standard deviation of particle diameter) of particle is tried to achieve, using the particle diameter (benchmark that by volume distributes reaches the particle diameter of the distribution of 50% from little side) of d50 as mean grain size with laser light scattering type particle size distribution machine (SALD-7000 that Shimadzu Seisakusho Ltd. manufactures).
(3) shape of particle
(3-1) shape of particle 1
Be fixed on by particle powder electric conductivity adhesive tape and measure on platform, the S-4700 type electric field transmitted scanning electron microscope using Hitachi to produce is observed under the multiplying power of 1000 times, observes the shape of particle.To 30 particles selected at random, the maximum dimension D x(obtaining particle is designated as x direction) (be designated as y direction and z direction with, the direction vertical with x direction.Z direction is the direction also vertical with y direction) on maximum dimension D y and Dz(Dy≤Dz), calculate mean value respectively, be designated as Dxave, Dyave, Dzave, obtain Dxave-Dyave, Dxave-Dzave, Dyave-Dzave, by at least 1 in them more than Dx 20% particle be judged to be non-spherical, the judgement do not exceeded is spherical.
(3-2) standard deviation of shape of particle 2(length breadth ratio and length breadth ratio)
Glass bar is used to make particle be attached on electric conductivity adhesive tape gently, be fixed to and measure on platform, the S-4700 type electric field transmitted scanning electron microscope using Hitachi to produce is observed under the multiplying power of 100 times from dead ahead (not with pitch angle), to 30 particles selected at random, using the maximum gauge of particle as major diameter, using the maximum gauge on the direction vertical with this maximum gauge as minor axis, major diameter/minor axis (length breadth ratio) is obtained respectively to each particle, averages as the mean value of length breadth ratio.In addition, the standard deviation of length breadth ratio is calculated by the value of each length breadth ratio.
The particle (anticipation be such as less than 3 μm) little to mean grain size, improves multiplying power (such as bringing up to 1000 times) and observes.
(4) the projection frequency (projection number) on film surface
Produce with three-dimensional roughness determinator SE-3CKT(Kosaka Laboratory Ltd.), the projection profile on film surface is measured, with height multiplying power 1000 times, direction of scanning multiplying power 200 times record projection profile under the condition of sample length (cut-off) 0.25mm, measured length 1mm, sweep span 2 μm, sweep trace 100.Being tried to achieve by the projection profile (transverse axis: rising height, the longitudinal axis: the projection profile of projection number) of gained is highly the projection number (individual/m of more than 5 μm 2) as projection frequency.Resolve and use three-dimensional roughness resolver SPA-11(Kosaka Laboratory Ltd. to produce).
(5) 10% compression strenghts
The micro-hardness tester ENT-1100a using エ リ オ ニ Network ス society to produce measures the compression strenght of each particle under load 3gf, adopts the compression strenght (MPa) during 10% distortion.Use the mean value measured for 5 times.
(6) volatile organic solvent amount
The membrane sample of 1g is loaded in the bag of the fluororesin of 10L under room temperature (23 DEG C), sealing after wherein purging with purity nitrogen.Then from the nitrogen described bag, in 2 analysis TENAX-TA trap tubes, gather the nitrogen of 0.2L, 1.0L immediately with the flow of 0.2L/ minute respectively, use these pipes to be carried out quantitatively the quality of Elements in Organic Solvents contained in gathered nitrogen by HPLC and GCMS.The value of gained is scaled the amount in 10L nitrogen, tries to achieve the quality being evaporate into the organic solvent in 10L nitrogen by the membrane sample of 1g, it can be used as volatile organic solvent amount (unit: ppm, with the quality of membrane sample for benchmark).Wherein, aldehydes be with acetonitrile by aldehyde derivatives stripping from trap tube, undertaken quantitatively by HPLC.When the value of HPLC with GCMS is different, adopt the value that detected level is many.
(7) film thickness and Rotating fields
With microtome, white reflection film section is exposed cross section, the S-4700 type electric field transmitted scanning electron microscope using Hitachi to produce observes this cross section under the multiplying power of 500 times, obtains the thickness of film entirety, reflection horizon A, superficial layer B, supporting layer C respectively.For superficial layer B, get arbitrarily thickness 10 point of particle existence part, using their mean value as thickness.
(8) the calculating of volume of voids rate
Bulk density is obtained by asking the polymkeric substance of the layer of volume of voids rate, the density of adding particle and other each composition and compounding ratio.Be separated by stripping etc. by this layer, quality measurement and volume, calculate actual density by these, tries to achieve volume of voids rate by bulk density and actual density by following formula simultaneously.
Volume of voids rate=100 × (1-(actual density/bulk density))
The density of m-phthalic acid copolymerization polyethylene terephthalate (after biaxial stretch-formed) is 1.39g/cm 3, barium sulphate density be 4.5g/cm 3.
In addition, only the layer measuring volume of voids rate is separated, tries to achieve the quality of unit volume, thus try to achieve actual density.Volume calculates as follows: sample is cut out 3cm 2area, measure the thickness of this size with electric micrometer (ア Application リ Star produce K-402B), measure at 10 and average as thickness, calculate volume with the form of area × thickness.Quality electronic balance weighs.
The proportion of particle (comprising agglutination particle) uses the Bulk Specific Gravity value of being tried to achieve by following graduated cylinder method.Be the particle of filling absolute dry condition in the graduated cylinder of 1000ml toward volume, measure overall weight, the weight deducting graduated cylinder from the weight of this entirety tries to achieve the weight of this particle, measures the appearance Plot of this graduated cylinder, by the weight (g) of this particle divided by this volume (cm 3) try to achieve.
(9) fusing point, glass transition temperature
Use means of differential scanning calorimetry determinator (TA Instruments 2100 DSC), try to achieve with the determination of heating rate of 20 DEG C/min.
(10) brightness
Reflectance coating is taken out from the LED liquid crystal television (LG42LE5310AKR) that LG company produces, the superficial layer B side of the various reflectance coatings recorded in embodiment is arranged on picture side (side contacted with light guide plate), with the Model MC-940 that nitometer (great mound electronics is produced under the state of back light unit) from dead ahead with the brightness at the mensuration range determination backlight center of 500mm.
(11) Damage Evaluation (ploughing evaluation) of light guide plate
(11-1) Damage Evaluation 1
As shown in Figure 3, the iron plate (2 of wide 200mm × long 200mm × thick 3mm is sticked securely in the end of handle portion (1), weight is about 200g), paste the reflectance coating (3) evaluating supine wide 250mm × long 200mm thereon, the part making reflectance coating (3) Width two ends play each 25mm is exposed (part of central 200mm × 200mm is overlapping with iron plate) from iron plate.The evaluation face of reflectance coating (surperficial aspect) is now made to be outside.In addition, the part of the 25mm had more than needed in reflectance coating Width two ends goes back to the inboard of iron plate, and the impact of light guide plate is cut in the end (part that during sampling, the sword of cutter etc. enters) eliminating reflectance coating.
Then, the supine light guide plate (4 of point of point (401) will be had, size is at least 400mm × 200mm) be fixed on the table of level, the above-mentioned reflectance coating be fixed on iron plate be made is made facing down of reflectance coating side in the mode that evaluation face contacts with light guide plate and is placed on light guide plate, load the weight (5) of 500g further thereon, with the distance of 200mm (being moved by the reflectance coating be fixed on iron plate in the region of 400mm × 200mm) by 1 speed back and forth movement 15 times of about 5 ~ 10 seconds back and forth.Then, observe its scraping situation with the magnifieres of 20 times in light guide plate surface and whether have the particle come off from reflectance coating, evaluating according to following benchmark.
400mm × 200mm the gamut nuzzled up in light guide plate, do not have after back and forth movement 20 times during the damage can observed with magnifier, to be designated as " not having scraping " (scraping evaluates zero), there is no the damage that observe after back and forth movement 10 times but have during the damage that can observe after back and forth movement 20 times to be designated as " not easily scraping " (△ is evaluated in scraping), have during the damage that can observe after back and forth movement 10 times and be designated as " scraping " (scraping evaluation ×).
When carrying out above-mentioned evaluation, in order to the impact of inhibition point size as much as possible, the region that selected element size is large as far as possible in light guide plate, each assess sample is unanimously evaluated.
(11-2) Damage Evaluation 2
Be that 400mm × 200mm(correspondingly makes that the size of reflectance coating is 400mm × 250mm, the size of light guide plate is at least 400mm × 400mm except making the size of iron plate (2) in above-mentioned (11-1).Make to be fixed on the reflectance coating motion on iron plate in the region of 400mm × 400mm, range of observation also becomes this scope), the weight of weight (5) is that 1000g(pressure is identical with above-mentioned (11-1)) beyond, other is similarly evaluated.
(12) white point evaluation
(12-1) white point evaluates 1
Use the reflectance coating and light guide plate that use in the evaluation of above-mentioned (11-1), being placed in by reflectance coating on table makes its superficial layer face up, light guide plate is placed thereon to put ventricumbent mode, place the weight of each 300g on four limits of light guide plate respectively and fix, the back light of the LED liquid crystal television (LG42LE5310AKR) using LG company to produce, make light from the incident sideways of light guide plate, if the bright spot beyond the light guide plate point having range estimation to observe, be evaluated as white point and produced (evaluating △), if do not estimate the abnormal bright spot that can observe, be evaluated as and do not have white point to produce (evaluating zero).
(12-2) white point evaluates 2
Except using the reflectance coating and light guide plate that use in the evaluation of above-mentioned (11-2), metewand changes into as follows, and other evaluates in the same manner as above-mentioned (12-1).Metewand: if there is the bright spot estimated beyond the light guide plate point that can observe, be evaluated as white point produce (evaluation ×) if do not have can visual observations to abnormal bright spot; be evaluated as and do not have white point to produce (evaluating zero) although there is the bright spot beyond the light guide plate point of estimating and can observe very light, be evaluated as some white points and produced (evaluating △).
(13) closely sealed inequality is evaluated (paste and evaluate)
(13-1) evaluation 1 is pasted
As shown in Figure 4, the LED liquid crystal television (47 inches of sizes) of producing from LG company takes out underframe (6), be placed on level table in television internal side mode upward, place the size reflectance coating roughly the same with underframe thereon, its superficial layer is faced up, place thereon further TV originally with light guide plate and optical sheet 3 (7, diffusion barrier 2,1, prism).Then, in its face, comprising the region of the concavo-convex the best part of underframe, place as shown in Figure 4 and there is the estrade (801) that three diameters are the equilateral triangle of the cylindric leg of 5mm, load the weight (802) of 10kg thereon further, the region that this three legs of visual observations surround, if do not have abnormal bright part, is evaluated as " not having closely sealed uneven " (closely sealed inequality evaluates zero).When having abnormal bright part, 3 optical sheets are placed further TV originally with DBEF sheet, similarly visual observations, abnormal bright part is not corrected the words of coming and is evaluated as " having closely sealed inequality " (evaluation ×), and the words of abnormal bright partial disappearance are evaluated as " almost not having closely sealed inequality " (evaluating △).Wherein, the length on Shi Ge limit, region that three legs surround is the roughly equilateral triangle of 10cm.
(13-2) evaluation 2 is pasted
Be that except 15kg, other is similarly evaluated except making the weight of weight (802) in above-mentioned (13-1).
(14) masking evaluation is reclaimed
The biaxially-stretched film of gained in embodiment being pulverized, melt extruded and make fragment, making thus from reclaiming raw material.This is added in the A of reflection horizon from reclaiming raw material, addition with the quality of reflection horizon A for benchmark is 35 quality %, make other polyester identical with original film with the quality ratio of pore former, make in the same manner as original film containing from the biaxially-stretched film reclaiming raw material, evaluate according to following benchmark.
◎: can the length of stably more than masking 2000m.
Zero: can stably more than masking 1000m but be less than the length of 2000m.
△: there occurs 1 cut-out in the length being less than 1000m.
×: there occurs more than 2 times in the length being less than 1000m and cut off.
< Production Example 1: the synthesis > of m-phthalic acid copolymerization polyethylene terephthalate 1
Dimethyl terephthalate (DMT) 136.5 mass parts, dimethyl isophthalate 13.5 mass parts (reaching 9 % by mole relative to all acid composition 100 % by mole of gained polyester), ethylene glycol 98 mass parts, diglycol 1.0 mass parts, manganese acetate 0.05 mass parts, lithium acetate 0.012 mass parts are encased in the flask with rectification column, distiller condenser, are heated to 150 ~ 240 DEG C while stirring and distillate methyl alcohol and carry out ester exchange reaction.After distillating methyl alcohol, add trimethyl phosphate 0.03 mass parts, germanium dioxide 0.04 mass parts, by reactant transfer in reactor.Then being warming up to 292 DEG C by being slowly decompressed to 0.3mmHg in reactor while stirring simultaneously, carrying out polycondensation reaction, obtain m-phthalic acid copolymerization polyethylene terephthalate 1.The fusing point of this polymkeric substance is 235 DEG C.
< Production Example 2: the synthesis > of m-phthalic acid copolymerization polyethylene terephthalate 2
Except changing to dimethyl terephthalate (DMT) 129.0 mass parts, dimethyl isophthalate 21.0 mass parts (reaching 14 % by mole relative to all acid composition 100 % by mole of gained polyester), other is same with above-mentioned Production Example 1, obtains m-phthalic acid copolymerization polyethylene terephthalate 2.The fusing point of this polymkeric substance is 215 DEG C.
< Production Example 3: the making > of particle master slice (マ ス タ ー チ ッ プ) 1
Use a part for m-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and (in table, be designated as BaSO as the barium sulfate particles of the mean grain size 1.0 μm of pore former 4), the NEX-T60 tandem extruder manufactured with society of Kobe Steel, mixes with the amount that the content of barium sulfate particles reaches 60 quality % relative to the quality of gained master slice, extrudes resin temperature 260 DEG C, makes the particle master slice 1 containing barium sulfate particles.
< Production Example 4: the making > of particle master slice 2
Use the barium sulfate particles of a part for m-phthalic acid copolymerization polyethylene terephthalate 2 obtained above and the mean grain size 1.0 μm as pore former, with the NEX-T60 tandem extruder that society of Kobe Steel manufactures, mix with the amount that the content of barium sulfate particles reaches 60 quality % relative to the quality of gained master slice, extrude resin temperature 260 DEG C, make the particle master slice 2 containing barium sulfate particles.
< Production Example 5: the preparation > of the particle 1 that superficial layer B is used
Dimethyl terephthalate (DMT) 150 mass parts, ethylene glycol 98 mass parts, diglycol 1.0 mass parts, manganese acetate 0.05 mass parts, lithium acetate 0.012 mass parts are encased in the flask with rectification column, distiller condenser, are heated to 150 ~ 240 DEG C while stirring and distillate methyl alcohol and carry out ester exchange reaction.After distillating methyl alcohol, add trimethyl phosphate 0.03 mass parts, germanium dioxide 0.04 mass parts, by reactant transfer in reactor.Then being warming up to 292 DEG C by being slowly decompressed to 0.3mmHg in reactor while stirring simultaneously, carrying out polycondensation reaction, obtaining polyethylene terephthalate 3.Extruded from wire drawing die head (ス ト ラ Application De ダ イ) by the polyethylene terephthalate 3 of gained, severing after cooling, makes graininess thus.Then, by the particle of gained by baking oven in 170 DEG C heating within 3 hours, make its drying crystalline after, pulverize while the ア ト マ イ ザ ー ミ Le TAP-1 cooled with liquid nitrogen manufactured with Co., Ltd. マ ツ ボ ー, obtain the polyester granules that mean grain size is 60 μm thus.Further, obtain by this polyester granules being carried out air classification the particle 1(non-spherical particle that mean grain size is 40 μm).
Particle 2: except the particle of the nylon 66 resin CM3006 produced except using Dongli Ltd., the mean grain size of carrying out pulverizing, classification obtains in the same manner as above-mentioned Production Example 5 is the non-spherical particle of 40 μm.
Particle 3: except the particle of the nylon 66 resin CM3006 produced except using Dongli Ltd., the mean grain size of carrying out pulverizing, classification obtains in the same manner as above-mentioned Production Example 5 is the non-spherical particle of 10 μm.
Particle 4: except the particle of the nylon 6 resin CM1017 produced except using Dongli Ltd., the mean grain size of carrying out pulverizing, classification obtains in the same manner as above-mentioned Production Example 5 is the non-spherical particle of 10 μm.
Particle 5: the MBX-40(spherical shape acrylic particles (ア Network リ Le particle) that ponding finished industrial society produces, mean grain size are 40 μm).
Particle 6: except the particle of poly-(methyl methacrylate) (PMMA) resin ス ミ ペ ッ Network ス MGSS produced except using Sumitomo Chemical Co, the mean grain size of carrying out pulverizing, classification obtains in the same manner as above-mentioned Production Example 5 is the non-spherical particle of 10 μm.
Particle 7: the SP-10(spherical shape nylon particle that Dongli Ltd. produces, mean grain size are 10 μm).
< Production Example 6: the preparation > of the particle 8 that superficial layer B is used
In the same manner as above-mentioned Production Example 5, extruded by polyethylene terephthalate 3 from wire drawing die head, severing after cooling, makes graininess thus.Average out to 4mm × 3mm × the 2mm of the result of adjustment wire shape to be the shape of this particle be roughly cubical shape, shape.Then, the polyester granules that mean grain size is 60 μm is obtained in the same manner as above-mentioned Production Example 5.The particle 8(non-spherical particle that mean grain size is 43 μm is obtained) by further this polyester granules being carried out air classification.
< Production Example 7: the preparation > of the particle 9 that superficial layer B is used
Use the particle obtained in above-mentioned Production Example 6, under the condition (longitudinal stretching multiplying power 3.0 times, cross directional stretch multiplying power 4.0 times, heat fixation temperature are set in 220 DEG C) that the biaxially-stretched film of polyethylene terephthalate adopts usually, obtain the transparent biaxial stretch-formed polyethylene terephthalate film (thickness is 50 μm) of oriented crystalline.It is pulverized with while cooled with liquid nitrogen in the same manner as above-mentioned Production Example 6, then carries out air classification, obtain the particle 9(non-spherical particle that mean grain size is 52 μm).
< Production Example 8: the preparation > of superficial layer B particle 10 used
Use the particle obtained in above-mentioned Production Example 6, make by conventional method the dacron that diameter is 35 μm, it is pulverized with while cooled with liquid nitrogen in the same manner as above-mentioned Production Example 6, obtains the particle 10(non-spherical particle that mean grain size is 40 μm).
< Production Example 9,10: the preparation > of superficial layer B particle 11,12 used
By the particle drying crystallization obtained in Production Example 6, similarly carry out pulverizing, air classification, obtain the particle 11(non-spherical particle that mean grain size is 35 μm).In addition, the film obtained similarly is carried out pulverize, air classification in Production Example 7, obtain the particle 12(non-spherical particle that mean grain size is 50 μm).In above-mentioned, the condition of adjustment air classification makes the particle of gained reach the form shown in table 3.
Particle 13: except the particle of poly-(methyl methacrylate) (PMMA) resin ス ミ ペ ッ Network ス MGSS produced except using Sumitomo Chemical Co, the mean grain size of carrying out pulverizing, classification obtains in the same manner as above-mentioned Production Example 6 is the non-spherical particle of 40 μm.
< Production Example 11,12: the preparation > of superficial layer B particle 14,15 used
Thickness in above-mentioned Production Example 7 is changed to 75 μm, carries out pulverizing in the same manner as Production Example 7, air classification, obtain particle 14(non-spherical particle).In addition, make thickness be 100 μm and similarly obtain particle 15(non-spherical particle).In above-mentioned, the condition of adjustment air classification makes the particle of gained reach the form shown in table 3.
< Production Example 13 ~ 20: the preparation > of superficial layer B particle 16 ~ 23 used
By the particle drying crystallization obtained in Production Example 6, similarly carry out pulverizing, air classification, be there is particle 16 ~ 23(non-spherical particle or the spherical particle of formation as shown in table 3 respectively).In above-mentioned, the condition of adjustment air classification makes the particle of gained reach the form shown in table 3.
[ embodiment 1-1 ]
(manufacture of white reflection film)
Respectively with m-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and particle master slice 1 raw material as reflection horizon (A layer), m-phthalic acid copolymerization polyethylene terephthalate 2 and particle master slice 2 are as the raw material of supporting layer (C layer), carry out mixing and make the content of A mesoporosity, reflection horizon forming agent be 49 quality % relative to the quality of reflection horizon A, the content of supporting layer C mesoporosity forming agent is 3 quality % relative to the quality of supporting layer C, drop in extruder, A layer melt extrudes temperature 255 DEG C, C layer melt extrudes temperature 230 DEG C, 3 layers of feed head unit are used to make it collaborate to be formed the Rotating fields of C layer/A layer/C layer, this layer-by-layer state die head (ダ イ ス) is kept to be shaped to sheet.The discharge-amount now adjusting each extruder makes the Thickness Ratio of C layer/A layer/C layer reach 10/80/10 after biaxial stretch-formed.The chilling roll being 25 DEG C by this sheet material surface temperature further makes the unstretching film of cooling curing.Make this unstretching film by the preheated zone of 73 DEG C, then by the preheated zone of 75 DEG C, import to the regions of longitudinal stretch remaining on 92 DEG C, longitudinal stretching 2.9 times, with the roller groups cooling of 25 DEG C, obtain monadic stretching membrane.Then, the one side of the monadic stretching membrane of gained adopts the following shown masking liquid 1 for the formation of superficial layer (B layer) of inverse roller rubbing method coating.
< masking liquid 1 >
Using in the Z-465(polyethylene terephthalate that the mutual induction KCC of resin produces relative to all acid composition 100 % by mole containing sulfoisophthalic acid sodium composition 10 % by mole, the copolymer polyester resin (this copolyester is designated as resin 1) that diglycol composition is 10 % by mole, solid component concentration is the aqueous solution of 15 quality %), with as the particle 1 obtained in the above-mentioned Production Example 5 of particle, and reach the content ratio shown in table 1 as the ion exchange water of diluting solvent with resin and particle, and the mode that the solid component concentration of masking liquid reaches 20 quality % carries out being mixed and made into masking liquid 1.
After coating, the preheated zone making it by 115 DEG C while the two ends clip maintenance of film is imported to the regions of lateral stretch remaining on 130 DEG C, cross directional stretch 3.6 times.Then in stenter, heat fixation is carried out in 185 DEG C, contracting amplitude-frequency (width enters れ and leads) be 2%, contracting width temperature carries out transverse direction contracting width under being the condition of 130 DEG C, then cut away film two ends, carry out hot wire-CVD with longitudinal relaxation rate 2%, be cooled to room temperature, obtain 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 the form of the particle that makes superficial layer (B layer) used is as shown in table 1 respectively, obtain biaxially-stretched film in the same manner as embodiment 1-1.The evaluation result of gained film is as shown in table 2.
[ embodiment 1-4 ]
Except the pore former of reflection horizon A is changed to the resin (cycloolefin immiscible with polyester, Port リ プ ラ ス チ ッ Network ス company produce " TOPAS 6017S-04 "), make the content of pore former be beyond 20 quality % relative to the quality of reflection horizon A, other makes biaxially-stretched film and evaluates in the same manner as embodiment 1-1, and evaluation result is as shown in table 2.
[ embodiment 1-6 ]
Except after uniaxial tension, biaxial stretch-formed before be not coated with except masking liquid, other obtains biaxially-stretched film in the same manner as embodiment 1-1, and this biaxially-stretched film is 15g/m with direct gravure device with wet thickness 2coating weight coating comprise the masking liquid of the composition shown in the following masking liquid 2 for the formation of superficial layer (layer B), then in baking oven, obtain film in 80 DEG C of dryings.
< masking liquid 2, solid component concentration are 30 quality % >
Particle: the particle 1(non-spherical particle obtained in above-mentioned Production Example 5) 7.5 quality %
Acrylic resin (thermoplastic resin): the ア Network リ デ ィ ッ Network A-817BA(solid component concentration that DIC company produces is 50 quality %, is designated as resin 2 in table) 30 quality %
Crosslinking chemical: the コ ロ ネ ー ト HL(isocyanate-based crosslinking chemical that Japanese Port リ ウ レ タ Application industrial group produces, solid component concentration is 75 quality %, is designated as crosslinking chemical 1 in table) 10 quality %
Diluting solvent: butyl acetate 52.5 quality %.
The evaluation result of gained film is as shown in table 2.Wherein, in masking liquid 2, the solid constituent ratio of each composition is as follows.
Particle: 25 quality %
Acrylic resin (thermoplastic resin): 50 quality %
Crosslinking chemical: 25 quality %.
[ embodiment 2-1 ]
(manufacture of white reflection film)
Use m-phthalic acid copolymerization polyethylene terephthalate 1 obtained above and particle master slice 1 as the raw material of reflection horizon (A layer) respectively, m-phthalic acid copolymerization polyethylene terephthalate 2 and particle master slice 2 are as the raw material of supporting layer (C layer), carry out mixing and make the content of A mesoporosity, reflection horizon forming agent be 49 quality % relative to the quality of reflection horizon A, the content of supporting layer C mesoporosity forming agent is 3 quality % relative to the quality of supporting layer C, drop in extruder, A layer melt extrudes temperature 265 DEG C, C layer melt extrudes temperature 240 DEG C, 3 layers of feed head unit are used to make it collaborate to be formed the Rotating fields of C layer/A layer/C layer, this layer-by-layer state die head is kept to be shaped to sheet.The discharge-amount now adjusting each extruder makes the Thickness Ratio of C layer/A layer/C layer reach 10/80/10 after biaxial stretch-formed.The chilling roll being 25 DEG C by this sheet material surface temperature further makes the unstretching film of cooling curing.Make this unstretching film by the preheated zone of 73 DEG C, then by the preheated zone of 75 DEG C, and import to the regions of longitudinal stretch remaining on 92 DEG C, longitudinal stretching 2.9 times, with the roller groups cooling of 25 DEG C, obtain monadic stretching membrane.Then, the one side of the monadic stretching membrane of gained adopts the following shown masking liquid 3 for the formation of superficial layer (B layer) of inverse roller rubbing method coating.
< masking liquid 3 >
Z-465(resin 1 using producing as the mutual induction KCC of resin) and the particle 8 that obtains in the above-mentioned Production Example 6 of particle and reach resin with the solid component content ratio of resin and particle as the ion exchange water of diluting solvent: particle=75:25(quality %) and the mode that the solid component concentration of masking liquid reaches 20 quality % mix, make masking liquid 3.
After coating, the preheated zone making it by 115 DEG C while the two ends clip maintenance of film is imported to the regions of lateral stretch remaining on 130 DEG C, cross directional stretch 3.6 times.Then in stenter, carry out heat fixation in 185 DEG C, contracting amplitude-frequency be 2%, contracting width temperature carries out transverse direction contracting width under being the condition of 130 DEG C, then cut away film two ends, carry out hot wire-CVD with longitudinal relaxation rate 2%, 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 the form of the particle that makes superficial layer (B layer) used and Rotating fields respectively as shown in Table 3 and Table 4 except, other obtains biaxially-stretched film in the same manner as embodiment 2-1.The evaluation result of gained film is as shown in table 4.
[ embodiment 2-6 ]
Except the pore former of reflection horizon A is changed to the resin (cycloolefin immiscible with polyester, Port リ プ ラ ス チ ッ Network ス company produce " TOPAS 6017S-04 "), make the content of pore former be beyond 20 quality % relative to the quality of reflection horizon A, other makes biaxially-stretched film and evaluates in the same manner as embodiment 2-1, and evaluation result is as shown in table 4.
[ embodiment 2-7 ]
Except after uniaxial tension, biaxial stretch-formed before be not coated with except masking liquid, other obtains biaxially-stretched film in the same manner as embodiment 2-1, and this biaxially-stretched film is 15g/m with direct gravure device with wet thickness 2coating weight coating comprise the masking liquid of the composition shown in the following masking liquid 4 for the formation of superficial layer (layer B), then in baking oven, obtain film in 80 DEG C of dryings.
< masking liquid 4, solid component concentration are 30 quality % >
Particle: the particle 8(non-spherical particle obtained in above-mentioned Production Example 6) 7.5 quality %
Acrylic resin (thermoplastic resin): the ア Network リ デ ィ ッ Network A-817BA(resin 2 that DIC company produces) 30 quality %
Crosslinking chemical: the コ ロ ネ ー ト HL(crosslinking chemical 1 that Japanese Port リ ウ レ タ Application industrial group produces) 10 quality %
Diluting solvent: butyl acetate 52.5 quality %.
The evaluation result of gained film is as shown in table 4.Wherein, in masking liquid 4, the solid constituent ratio of each composition is as follows.
Particle: 25 quality %
Acrylic resin (thermoplastic resin): 50 quality %
Crosslinking chemical: 25 quality %.
Invention effect
The present invention can provide and can fully suppress and the stickup of light guide plate, the white reflection film that simultaneously fully can suppress the damage of light guide plate.
Industrial applicability
White reflection film of the present invention is owing to can fully suppress and the stickup of light guide plate, the damage that fully can suppress light guide plate in addition, therefore the area source reflecting plate with light guide plate is especially suitable for use as, particularly at the reflectance coating that the back light unit of the middle edge lighting-type used such as such as liquid crystal indicator is used.

Claims (10)

1. white reflection film, its superficial layer B that there is reflection horizon A and manufactured by the resin combination containing particle,
Having with the surface of reflection horizon A opposite side the projection formed by above-mentioned particle at superficial layer B, is highly that the projection number of more than 5 μm is 10 in this surface 4~ 10 10individual/m 2,
The non-spherical particle that above-mentioned particle is mean grain size is 3 ~ 100 μm, 10% compression strenght is 0.1 ~ 15MPa.
2. white reflection film according to claim 1, wherein above-mentioned particle is by polymkeric substance being pulverized the pulverizing polymer particle obtained.
3. white reflection film according to claim 2, wherein above-mentioned polymkeric substance is polyester.
4., according to the white reflection film in claims 1 to 3 described in any one, wherein above-mentioned particle is the average out to more than 1.31, less than 1.80 of length breadth ratio (major diameter/minor axis), and the standard deviation of length breadth ratio is the non-spherical particle of 0.15 ~ 0.50.
5. according to the white reflection film in claims 1 to 3 described in any one, wherein in superficial layer B the content of above-mentioned particle with the quality of superficial layer B for benchmark is 1 ~ 70 quality %.
6., according to the white reflection film in claims 1 to 3 described in any one, wherein volatile organic solvent amount is below 10ppm.
7. according to the white reflection film in claims 1 to 3 described in any one, wherein reflection horizon A contains hole, and its volume of voids rate is 15 more than volume %, 70 below volume %.
8. white reflection film according to claim 7, it also has volume of voids rate and is 0 more than volume % and the supporting layer C being less than 15 volume %.
9. white reflection film according to claim 7, wherein superficial layer B is the layer formed by the coating of masking liquid.
10., according to the white reflection film in claims 1 to 3 described in any one, it is as the area source reflecting plate with light guide plate.
CN201480002946.XA 2013-08-07 2014-08-04 White reflective film Pending CN104769461A (en)

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TWI589440B (en) 2017-07-01
CN107272091A (en) 2017-10-20

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