CN1914523A - Antidazzle coating composition, antidazzle film and process for producing the same - Google Patents
Antidazzle coating composition, antidazzle film and process for producing the same Download PDFInfo
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- CN1914523A CN1914523A CNA2005800037429A CN200580003742A CN1914523A CN 1914523 A CN1914523 A CN 1914523A CN A2005800037429 A CNA2005800037429 A CN A2005800037429A CN 200580003742 A CN200580003742 A CN 200580003742A CN 1914523 A CN1914523 A CN 1914523A
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- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0221—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133504—Diffusing, scattering, diffracting elements
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Abstract
An antidazzle coating composition capable of easily forming an antidazzle film improved with respect to extra reflection, white blur, etc. There is provided an antidazzle coating composition to be applied onto a transparent substrate to thereby form an antidazzle layer, which antidazzle coating composition comprises a first component and a second component that after application of this antidazzle coating composition onto a substrate, undergo a phase separation due to a difference in properties between the first component and the second component to thereby form a resin layer having a surface with random unevenness.
Description
Technical field
The present invention relates to give the antidazzle coating composition of transparent substrates antidazzles such as various transparent plastic films, transparent plastic sheet and glass and have the anti-anti-film of dazzling of dazzling layer that forms by this antidazzle coating composition.
Background technology
Advantages such as that liquid crystal indicator (LCD) has is slim, light weight, low power consumption are applied to various fields such as computing machine, word processor, televisor, mobile phone, portable information terminal.On the display surface of these liquid crystal indicators, be provided with anti-dazzling (AG:Anti Glare) film of surface roughening, low reflection (LR:LowReflection) film of adjusting refractive index, no reflection events film (AR:Anti Reflection) etc.Thus, can seek to remove because the contrast that external light reflection causes reduces and background reflectance is presented on problems such as display surface.
Improve the anti-manufacture method of dazzling film of liquid crystal indicator display performance as manufacturing, generally can enumerate when making film, by the method for processing such as cutting, mould extrusion modling, applying, the layer that contains resin particle perhaps is set with the method for film surface roughening etc. on film with its surface roughening.At present, the widespread use latter's setting on film contains the method for resin particle layer.
Put down in writing a kind of anti-film of dazzling in the TOHKEMY 2002-221610 communique (patent documentation 1), this film is the anti-layer anti-film of dazzling that forms of dazzling that lamination contains translucent resin and light transmission particulate, the difference of the refractive index of translucent resin and light transmission particulate be 0.3 or below, translucent resin is from anti-protrusion of surface 0.1～0.3 μ m that dazzles layer.This anti-dazzling in the manufacturing of film, for example can enumerate the problem of the inhomogeneous dispersion of used particulate.Control, adjust solution viscosity etc. for resin being evenly dispersed in the solution, for example must be noted that.As the inhomogeneous dispersion generation of particulate aggegation, then lip-deep concaveconvex shape has exceeded required scope, produces transmission image distinctiveness and reduces, and causes problems such as so-called white is fuzzy.
On the other hand, during thin film fabrication, when processing surface roughening by cutting, mould extrusion modling, applying etc., it is difficult randomly designing the concavo-convex of this uneven surface, concavo-convex certain rule of often following.Follow certain when rule when concavo-convex, often interfere mutually, become and cause the reason that strengthens reflected light or produce the demonstration problem of display such as moire fringe by the light of male and fomale(M﹠F) reflection.That is, it is former because with respect to the line of pixels column direction of display device that moire fringe produces, and the orientation of anti-micro concavo-convex structure of dazzling layer is overlapping.Arrange with respect to the pixel rule, the micro concavo-convex structure is positioned at the situation overlapping with this rule, has the tendency that takes place.In addition, when forming anti-dazzle layer by the mould extrusion modling, the anti-operations such as cleaning of dazzling the mould extrusion process of layer and being used for the mould of this mould extruding are necessary, thereby loaded down with trivial details.And, also must be noted that not make the molded surface of foreign matter attached to the mould that is used for the mould extruding.
Put down in writing a kind of in the TOHKEMY 2003-004917 communique (patent documentation 2) with anti-polarized light piece of dazzling layer, this polarized light piece is to have the anti-anti-polarized light piece of dazzling layer of band of dazzling film and polarizer, it is characterized in that the orientation of described anti-micro concavo-convex structure of dazzling layer is 22.5 ° ± 12.5 ° with respect to the absorption axes direction or the axis of homology direction of described polarizer.Such as described, when the micro concavo-convex structure being set by processing, the angle of necessary careful adjusting orientation etc., manufacturing process is loaded down with trivial details.And as because the height of display frame becomes more meticulous, colorize, and the pixel of display element becomes littler, then the occurrence probability of moire fringe is higher.Therefore, the technology that need address this problem.
Put down in writing the manufacture method of reflection-type liquid-crystal display device with electrode substrate in the TOHKEMY 2000-267086 communique (patent documentation 3), this method comprises the operation that coating is mixed with the mixed resin liquid of the multiple resin that easily is separated each other.In addition, put down in writing a kind of reflecting plate in TOHKEMY 2001-305316 communique (patent documentation 4), the formation that this reflecting plate has by 2 kinds of resin portion of mutual dispersion maintenance at least forms concavo-convex resin bed.But, because can giving no thought to background reflectance, these substrates or reflecting plate be presented on display surface, transmission image distinctiveness, white blur performances such as (white Pot け), therefore different with the anti-film problem to be solved of dazzling of paying attention to these performances.
Patent documentation 1: TOHKEMY 2002-221610 communique
Patent documentation 2: TOHKEMY 2003-004917 communique
Patent documentation 3: TOHKEMY 2000-267086 communique
Patent documentation 4: TOHKEMY 2001-305316 communique
Summary of the invention
Problem of the present invention is to solve above-mentioned prior art problems point.Particularly, problem of the present invention is to provide and can forms extra reflection (Ying り Write body easily), improved anti-antidazzle coating composition of dazzling film such as white blur.
The invention provides a kind of antidazzle coating composition, said composition is to coat to form anti-antidazzle coating composition of dazzling layer on the transparent substrates,
This antidazzle coating composition contains the 1st composition and the 2nd composition,
After being coated on this antidazzle coating composition on the substrate, because the rerum natura of the 1st composition and the 2nd composition is poor, the 1st composition and the 2nd composition are separated, and form on the surface to have random concavo-convex resin bed, achieve the above object thus.
Above-mentioned the 1st composition and the 2nd composition are independent separately, are preferably a kind or 2 kinds or above combination being selected from monomer, oligomer and the resin.
The difference of the SP value of the 1st composition and the SP value of the 2nd composition be preferably 0.5 or more than.
Antidazzle coating composition of the present invention can also contain organic solvent.And, the SP value (SP of preferred the 1st composition
1), the SP value (SP of the 2nd composition
2) and the SP value (SP of organic solvent
Sol) satisfy following condition:
SP
1＜SP
2, and
SP
1And SP
SolDifference be 2 or below.
Preferred above-mentioned the 1st composition is oligomer or resin, and above-mentioned the 2nd composition is a monomer.
Preferred in addition above-mentioned the 1st composition is the acrylic copolymer with unsaturated double-bond, and above-mentioned the 2nd composition is the multi-functional monomer that contains unsaturated double-bond.
Preferred above-mentioned the 1st composition is the siloxane acrylic block copolymers, and above-mentioned the 2nd composition is an acrylic copolymer.
In the preferred antidazzle coating composition of the present invention, above-mentioned the 1st composition and the 2nd composition are resin, in the 1st composition and the 2nd composition any one has the Tg of the environment temperature when being lower than the composition coating, and another has the Tg of the environment temperature when being higher than the composition coating.
In addition, in the preferred antidazzle coating composition of the present invention, any one of above-mentioned the 1st composition or the 2nd composition is monomer,
The difference of the Tg of the 1st composition and the 2nd composition be 20 ℃ or more than, and
The Tg that has the composition of higher Tg in the 1st composition and the 2nd composition be 20 ℃ or more than.
Antidazzle coating composition of the present invention can also contain hardening agent.
Antidazzle coating composition of the present invention is characterised in that, preferably not resinous particle.
The present invention also provides the anti-film of dazzling.Should anti-dazzle film and have transparent substrates and the anti-layer of dazzling, this anti-layer of dazzling is formed by above-mentioned antidazzle coating composition.
Preferably prevent dazzling the preformed casse degree of film less than 20%.
In addition, the preferred anti-R of film that dazzles
Z JIS94(10 mean roughness) is 1.0 μ m or following.
And preferred anti-average length (Sm) of dazzling the surfaceness curve element of film is 100 μ m or following.
Preferably there is not maximal value with respect to anti-scattered light intensity of dazzling the scattering angle of film.
The present invention also provides anti-manufacture method of dazzling film.Example as manufacture method can be enumerated the method that comprises following operation, and described operation has:
On transparent substrates the coating above-mentioned antidazzle coating composition painting process and
Make the curing process of gained curing of coating.
In addition, as other examples of manufacture method, can enumerate the method that comprises following operation, described operation has:
On transparent substrates the coating above-mentioned antidazzle coating composition painting process,
Make the gained dried coating film make its drying process that is separated and
Make the curing process of dry curing of coating.
In addition, as other examples of manufacture method, can also enumerate the method that comprises following operation, described operation has:
On transparent substrates the coating above-mentioned antidazzle coating composition painting process and
Film the rayed operation that it is separated and solidifies with the rayed gained.
The present invention also provides the anti-film of dazzling that utilizes above-mentioned anti-manufacture method of dazzling film to obtain.
The present invention also provides polarized light piece, and this polarized light piece is to have above-mentioned anti-polarized light piece of dazzling film and polarization element, prevents dazzling film surface and polarization element surface lamination in opposite directions, the described anti-anti-relative face of layer of dazzling that film surface is and is located at transparent substrates of dazzling.
The present invention also provides transmission display unit, and this device has plane light transmission display body, from the light supply apparatus of this light transmission display body of back side illuminaton be laminated to the above-mentioned anti-film of dazzling on this light transmission display body surface.
The present invention also is provided at the top layer of display and uses above-mentioned anti-liquid crystal indicator of dazzling film.
Antidazzle coating composition of the present invention is only by being coated with on substrate, and drying, curing as required just can be provided with the anti-layer of dazzling, and the described anti-layer of dazzling is the surperficial concavo-convex resin bed that has.Therefore, with form resin bed after form again as the thrust of concavo-convex substrate etc. and compare through the method for 2 operations, can form the surface with easier operation and have the concavo-convex anti-layer of dazzling.
In addition,, spontaneously determine concavo-convex configuration, thereby can dazzle laminar surface and form irregular concaveconvex shape anti-owing to utilize the present invention to form on anti-surface of dazzling layer when concavo-convex.Therefore, has the advantage that can not produce owing to the Moire fringe that systematicness caused of concavo-convex configuration.The antidazzle coating composition of the application of the invention can easily form the surface and have the concavo-convex anti-layer of dazzling, and uses it can easily make the anti-film of dazzling.Gained is anti-dazzles film and has no extra reflection, preformed casse degree (mist value) is low, all-optical transmittance is high excellent properties.The preformed casse degree here is meant the ratio of scattered light transmission amount and full transmittance amount.
Description of drawings
[Fig. 1] anti-schematic cross-section of dazzling film of the present invention.
[Fig. 2] parameters R
Z JIS94Key diagram.
The diagrammatic illustration figure of [Fig. 3] all-optical transmittance.
[Fig. 4] used the anti-cross section skeleton diagram of dazzling the polarized light piece of film of the present invention.
[Fig. 5] used the anti-cross section skeleton diagram of dazzling the transmission display unit of film of the present invention.
The anti-anti-3-D view of dazzling on the laminar surface of film of dazzling of the embodiment 1 that the super degree of depth measuring shape microscope of [Fig. 6] use obtains.
The anti-anti-3-D view of dazzling on the laminar surface of film of dazzling of the embodiment 2 that the super degree of depth measuring shape microscope of [Fig. 7] use obtains.
The anti-anti-3-D view of dazzling on the laminar surface of film of dazzling of the embodiment 3 that the super degree of depth measuring shape microscope of [Fig. 8] use obtains.
Symbol description
1... the anti-anti-layer, 5... transparent substrates, 10... polarized light piece, 12... polarization photosphere, 14... transparent substrates, 20... liquid crystal indicator, 22... polarized light piece, 24... liquid crystal panel, 26... polarized light piece, 28... of dazzling of film, 3... of dazzling carried on the back lamp
Embodiment
The antidazzle coating composition
Antidazzle coating composition of the present invention is to coat to form anti-composition of dazzling layer on the transparent substrates.At least 2 kinds of compositions that contain the 1st composition and the 2nd composition in this antidazzle coating composition.When being coated on the antidazzle coating composition on the substrate, these the 1st compositions and the 2nd composition have following feature, and promptly because the 1st composition and the 2nd composition rerum natura separately poor, the 1st composition and the 2nd composition are separated.
As the example of the 1st composition and the 2nd composition, it is independent separately, can enumerate a kind or 2 kinds or above combination being selected from monomer, oligomer and the resin.
As the 1st composition and the 2nd composition, for example can use monomer such as multi-functional monomer, in skeleton structure, contain (methyl) acryl resin, the resin of olefin resin, polyether resin, vibrin, urethane resin, polyorganosiloxane resin, polysilane resins, poly-imide resin or fluororesin etc.These resins can be low-molecular-weight so-called oligomer.As multi-functional monomer, for example can use the dealcoholization thing of polyvalent alcohol and (methyl) acrylate, can use dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc. particularly.As the resin that in skeleton structure, contains (methyl) acryl resin, the resin that can enumerate resin that polymerization or copolymerization (methyl) acrylic monomers obtains, (methyl) acrylic monomers and other monomer copolymerizations with ethylenic unsaturated double-bond is obtained etc.As the resin that in skeleton structure, contains olefin resin, can enumerate tygon, polypropylene, ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, ionomer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer etc.The resin that contains polyether resin in skeleton structure for example can be enumerated polyglycol, polypropylene glycol, polytetramethylene glycol etc. for contain the resin of ehter bond in strand.The resin that contains vibrin in skeleton structure for example can be enumerated unsaturated polyester resin, alkyd resin, polyethylene terephthalate etc. for contain the resin of ester bond in strand.The resin that contains urethane resin in skeleton is for containing the resin of ammonia ester bond in strand.The resin that contains polyorganosiloxane resin in skeleton structure is for containing the resin of siloxane bond in strand.The resin that contains polysilane resins in skeleton structure is for containing the resin of silane key in strand.The resin that contains poly-imide resin in skeleton structure is for containing the resin of imine linkage in strand.The resin that contains fluororesin in skeleton structure is the resin of part or all structure that is replaced by fluorine of containing poly hydrogen.
As oligomer and resin, can be the multipolymer that comprises 2 kinds or above above-mentioned skeleton structure, also can be the multipolymer that comprises above-mentioned skeleton structure and other monomers.
The 1st composition among the present invention and the 2nd composition can use oligomer or the resin that contains skeleton structure of the same race, also can use the oligomer or the resin that contain different mutually skeleton structures.And, can also be in the 1st composition and the 2nd composition any one for monomer, another is oligomer or resin.
The 1st composition and the 2nd composition among preferred the present invention have the functional group that reacts to each other respectively.By making this functional group react to each other, can improve the anti-patience of dazzling layer of utilizing coating composition to obtain.As the combination of this functional group, for example can enumerate functional group's (hydroxyl, amino, mercapto, carboxyl etc.) with active hydrogen and epoxy radicals, functional group and isocyanate group, ethylenic unsaturated group and ethylenic unsaturated group (polymerization of ethylenic unsaturated group takes place), silanol group and silanol group (polycondensation of silanol group takes place), silanol group and epoxy radicals, have the functional group of active hydrogen and have the functional group of active hydrogen, active methylene and acryloyl group, azoles quinoline base and carboxyl etc. with active hydrogen.In addition, " functional group that reacts to each other " here only also comprise merely the 1st composition and the 2nd composition mixed and do not react, and by being mixed together the functional group that catalyzer or hardening agent react to each other.Here operable catalyzer can be enumerated for example light trigger, radical initiator, acid base catalysator, metallic catalyst etc.Operable hardening agent can be enumerated melamine hardening agent, (block) isocyanate curing agent, epoxy hardener etc.
When the 1st composition and the 2nd composition have the functional group that reacts to each other respectively, then the 1st composition and the 2nd mixture of ingredients remain to have so-called Thermocurable, the curable of photo-curable (ultra-violet solidified, visible-light curing, infrared ray cured property etc.).
Among the present invention, can preferably use in the skeleton structure resin that contains (methyl) acryl resin as the 1st composition and the 2nd composition.
In addition, for the molecular weight of the 1st composition and the 2nd composition, preferred molecular weight (the 1st composition and the 2nd composition for resin time be weight-average molecular weight) is 100～100000.
, 1st composition that the 1st composition and the 2nd composition are separated as causing and the 2nd composition rerum natura separately poor, the SP value, glass transition temperature (Tg), surface tension, number-average molecular weight that can enumerate each resin etc. has the situation of certain difference.
The SP value is the abbreviation of solubility parameter (solubility parameters), is deliquescent yardstick.The big more then polarity of the numerical value of SP value is high more, and the opposite more little then polarity of numerical value is more little.
For example, the SP value can utilize following method to measure [list of references: SUH, CLARKE, J.P.S.A-1,5,1671～1681 (1967)].
Measure temperature: 20 ℃
Sample: take by weighing the 0.5g resin and put into the 100ml beaker, use no calibrated pipet to add the 10ml good solvent, utilize magnetic stirring apparatus to dissolve.
Solvent:
Good solvent ... two alkane, acetone etc.
Poor solvent ... normal hexane, ion exchange water etc.
Cloud point is measured: use the buret of 50ml to drip poor solvent, the dripping quantity of muddy point takes place.
The SP value δ of resin obtains by following formula.
[several 1]
δ＝(V
ml 1/2δ
ml+V
mh 1/2δ
mh)/(V
ml 1/2+V
mh 1/2)
[several 2]
V
m＝V
1V
2/(φ
1V
2+φ
2V
1)
[several 3]
δ
m＝φ
1δ
1+φ
2δ
2
Vi: the molar volume of solvent (ml/mol)
φ
i: the volume fraction of each solvent during cloud point
δ
i: the SP value of solvent
Ml: low SP poor solvent mixed system
Mh: high SP poor solvent mixed system
When causing that the 1st composition and the 2nd composition are separated, the 1st composition and the 2nd composition the difference of rerum natura being the difference of SP value separately, the difference of the SP value of preferred the 1st composition and the SP value of the 2nd composition be 0.5 or more than.More preferably the difference of this SP value be 0.8 or more than.The upper limit to the difference of this SP value is not particularly limited, be generally 15 or below.The difference of the SP value of the 1st composition and the SP value of the 2nd composition is 0.5 or when above, the mutual intermiscibility of resin is low, causes being separated of the 1st composition and the 2nd composition thus after the coating composition coating.
Antidazzle coating composition of the present invention can also contain organic solvent.And, for the 1st composition that is contained in the antidazzle coating composition, the 2nd composition and organic solvent, be more preferably the SP value (SP of the 1st composition
1), the SP value (SP of the 2nd composition
2) and the SP value (SP of organic solvent
Sol) satisfy following condition:
SP
1＜SP
2, and
SP
1And SP
SolDifference be 2 or below.
Because SP
1And SP
SolDifference be 2 or below, therefore can make low preformed casse degree and antidazzle can the excellent anti-film of dazzling.Be more preferably SP
1And SP
SolDifference be 1 or below, promptly in 0～1 scope.
It should be noted that SP
1And SP
SolAs long as difference be 2 or following.Can be SP
1＜SP
Sol, also can be SP
1＞SP
Sol
As the 1st composition that satisfies following formula relation and an example of the 2nd composition, can enumerate the 1st composition and be oligomer or resin, above-mentioned the 2nd composition is the situation of monomer.The oligomer or the resin that are more preferably the 1st composition are the acrylic copolymer that contains unsaturated double-bond.The monomer that is more preferably the 2nd composition is the multi-functional monomer that contains unsaturated double-bond.It should be noted that " oligomer " is meant the polymkeric substance with repetitive in this instructions, the number of this repetitive is 3～10.
The acrylic copolymer that contains unsaturated double-bond can be enumerated the resin that for example polymerization or copolymerization (methyl) acrylic monomers obtain, the resin that copolymerization (methyl) acrylic monomers and other monomers with ethylenic unsaturated double-bond obtain, the resin that (methyl) acrylic monomers and other monomer reactions with ethylenic unsaturated double-bond and epoxy radicals are obtained, make resin that (methyl) acrylic monomers and other monomer reactions with ethylenic unsaturated double-bond and isocyanate group obtain etc.These acrylic copolymers that contain unsaturated double-bond can use a kind separately, also can be with 2 kinds or above mixing use.
As the multi-functional monomer that contains unsaturated double-bond, can use above-mentioned multi-functional monomer, for example the dealcoholization thing of polyvalent alcohol and (methyl) acrylate particularly is dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two-trimethylolpropane four (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc.In addition, can also use polyglycol # 200 diacrylate (production of company of common prosperity society chemistry (strain)) etc. to have the acrylate monomer of polyethylene glycol backbone.These multi-functional monomers that contain unsaturated double-bond can use a kind separately, also can be with 2 kinds or above mixing use.
As the 1st composition that satisfies the following formula relation and other example of the 2nd composition, can enumerate the situation that the 1st composition and the 2nd composition are oligomer or resin.The preferred use in the skeleton structure contained the resin of (methyl) acryl resin as the 1st composition and the 2nd composition.More preferably the 1st composition is the acrylic copolymer that contains unsaturated double-bond, and the 2nd composition is the multi-functional monomer that contains unsaturated double-bond.
Preferred organic solvent when being combinations thereof as the 1st composition and the 2nd composition can be enumerated for example ketones solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; Alcohols solvents such as methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols; Ether solvents such as methyl phenyl ethers anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.These solvents can use a kind separately, also can mix 2 kinds or the use of above organic solvent.When using 2 kinds or above organic solvent, as long as at least a kind in the used organic solvent satisfies above-mentioned " SP
1And SP
SolDifference be 2 or following " condition get final product, all organic solvents that needn't be used all satisfy above-mentioned condition.
When the 1st composition and the 2nd composition were resin, glass transition temperature (Tg) can be by obtaining with the same method of the common Tg assay method that utilizes dynamic viscoelastic.This Tg for example can use RHEOVIBRON MODEL RHEO2000,3000 (trade name, オ リ エ Application テ Star Network company produce) etc. to measure.
When the 1st composition and the 2nd composition are resin, when causing the 1st composition that the 1st composition and the 2nd composition are separated and the 2nd composition the difference of rerum natura be the difference of Tg separately, any one of preferred the 1st composition and the 2nd composition has the Tg of the environment temperature when being lower than the composition coating, and another has the Tg of the environment temperature when being higher than the composition coating.At this moment, can think the resin with the Tg that is higher than environment temperature owing to be the confined vitreousness of molecular motion under this environment temperature, therefore coating back aggegation in coating composition causes being separated of the 1st composition and the 2nd composition thus.
Can enumerate following situation as an example: when the 1st composition and the 2nd composition are resin, environment temperature during the composition coating is 20～150 ℃, the Tg of resin with Tg of the environment temperature that is lower than composition when coating be-70～120 ℃, and the Tg of resin with Tg of the environment temperature when being higher than composition and being coated with is 90～200 ℃.Preferred above-mentioned environment temperature is 40～120 ℃, and the Tg that preferably has the resin of the Tg that is lower than environment temperature is-60～80 ℃, and the Tg that preferably has the resin of the Tg that is higher than environment temperature is 100～150 ℃.At this moment, can be that the resin with Tg of the environment temperature that is lower than composition when coating is the 1st composition, resin with Tg of the environment temperature when being higher than the composition coating is the 2nd composition, also can be opposite situation.
In addition, when in the 1st composition and the 2nd composition any one is monomer, the difference of the Tg of these the 1st compositions and the 2nd composition be 20 ℃ or more than, and the Tg that in the 1st composition and the 2nd composition, preferably has the composition of higher Tg be 20 ℃ or more than.The difference of the Tg of the 1st composition and the 2nd composition be preferably 30 ℃ or more than, more preferably 50 ℃ or more than.The upper limit to the difference of the Tg of the 1st composition and the 2nd composition is not particularly limited, and can enumerate 100 ℃ or following situation etc.At this moment, can think that therefore coating back aggegation in coating composition causes being separated of the 1st composition and the 2nd composition thus owing to the component molecules motion with higher Tg more is limited.
When in the 1st composition and the 2nd composition any one is monomer, can enumerate as an example, have low Tg composition, be that the Tg of monomer is-70～0 ℃, and the Tg with resin of higher Tg is 20～200 ℃ a situation.Environment temperature when being coated with as composition at this moment, can be enumerated and be for example 20～120 ℃ situation etc.The Tg that preferred example can be enumerated the monomer component with low Tg is-60～0 ℃, and the Tg with resin of higher Tg is 30～150 ℃ a situation.At this moment, the environment temperature when being coated with as composition can be enumerated and is for example 20～120 ℃ situation etc.In these cases, monomer can be the 1st composition, also can be the 2nd composition.
It should be noted that when the 1st composition or the 2nd composition are monomer that it is difficult using said method to measure glass transition temperature.Fusing point that it is generally acknowledged the glass transition temperature of monomer and this monomer about equally.In this instructions, when the 1st composition or the 2nd composition are monomer, think that the Tg of this monomer equates with the fusing point of monomer.
When causing the 1st composition that the 1st composition and the 2nd composition are separated and the 2nd composition the difference of rerum natura is the difference of surface tension separately, the difference of the surface tension of the surface tension of preferred the 1st composition and the 2nd composition is 1～70dyn/cm.Being more preferably this difference is 5～30dyn/cm.When the difference of the surface tension of the surface tension of the 1st composition and the 2nd composition was 1～70dyn/cm, the resin with high surfaces tension force had the tendency of aggegation, causes that the 1st composition and the 2nd composition are separated after the composition coating thus.
Surface tension can utilize the static surface tension of ring method mensuration to measure by obtaining ダ イ ノ メ one one that uses PVC Star Network ケ ミ one company to produce.
In the coating composition of the present invention, except above-mentioned the 1st composition and the 2nd composition, can also contain normally used resin.The bright coating composition of this law is characterised in that, by using above-mentioned the 1st composition and the 2nd composition, even resinous particle etc. not also can form and has concavo-convex resin bed.Therefore, the not resinous particle of preferred coating composition of the present invention.
Coating composition of the present invention can be modulated by the 1st composition and the 2nd composition are mixed together with the solvent, catalyzer, the hardening agent that use as required.The 1st composition and the 2nd components in proportions in the coating composition be preferably 1: 99～and 99: 1, more preferably 1: 99～50: 50, more preferably 1: 99～20: 80.When using catalyzer,, can add 0.01～20 weight portion, preferably add 1～10 weight portion with respect to the 1st composition of 100 weight portions and the 2nd composition and other resins (these are called " resinous principle " altogether) of using as required.When using hardening agent,, can add 0.1～50 weight portion, preferably add 1～30 weight portion with respect to the above-mentioned resinous principle of 100 weight portions.When using solvent,, can add 1～9900 weight portion, preferably add 100～900 weight portions with respect to the above-mentioned resinous principle of 100 weight portions.
Solvent in the coating composition that uses among the present invention is not particularly limited, can considers the 1st composition and the 2nd composition, become the material of part of coat substrates and coating process of composition etc. and suitably select.The object lesson of solvent for use has for example aromatic solvent such as toluene, dimethylbenzene; Ketones solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; Ether solvents such as ether, isopropyl ether, tetrahydrofuran, two alkane, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, methyl phenyl ethers anisole, phenetol; Esters solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene acetate; Amide solvents such as dimethyl formamide, diethylformamide, N-Methyl pyrrolidone; Cellosolve kind solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; Alcohols solvents such as methyl alcohol, ethanol, propyl alcohol; Halogen such as methylene chloride, chloroform solvent etc.These solvents can use separately also can be with 2 kinds or above merging use.Preferred esters solvent, ether solvent, alcohols solvent and the ketones solvent of using in these solvents.
Antidazzle coating composition of the present invention also can add various adjuvants as required.As this adjuvant, can enumerate typical additives such as antistatic agent, plastifier, surfactant, antioxidant and ultraviolet light absorber.
The anti-film of dazzling
The anti-film of dazzling of the present invention has transparent substrates and the anti-layer of dazzling.Should anti-dazzle layer is formed by above-mentioned antidazzle coating composition.
Transparent substrates can be used various transparent plastic films, transparent plastic sheet and glass etc.As transparent plastic film, can use for example triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose (ジ ア セ チ レ Application セ Le ロ one ス) film, cellulose acetate-butyrate film, polyethersulfone film, polyacrylic acid based resin film, polyurethanes resin film, mylar, polycarbonate film, polysulphone film, polyethers film, poly-methyl pentene film, polyetherketone film, (methyl) vinyl cyanide film etc.Transparent substrates is preferably used triacetyl cellulose.The refractive index of triacetyl cellulose is about 1.48.Because triacetyl cellulose is widely used as the diaphragm of the polarization photosphere of protection polarized light piece, therefore the anti-film of dazzling that uses triacetyl cellulose to obtain as transparent substrates directly can be used as protective film.The thickness that it should be noted that transparent substrates can suitably be selected according to purposes, uses usually about 25～1000 μ m.
The anti-layer of dazzling can form by be coated with the above-mentioned antidazzle coating composition of portion on transparent substrates.The coating process of coating composition can suitably be selected according to the situation of coating composition and painting process, for example can utilize dip coated method, airblade coating method, curtain coating method, print roll coating method, metal bar rubbing method, intaglio plate roll-type rubbing method, extrusion coated method (No. 2681294 instructionss of United States Patent (USP)) etc. to be coated with.
Anti-thickness of dazzling layer is not particularly limited, can considers that various factors suitably selects.For example, can make dry film thickness reach 0.01～20 μ m by the coating composition composition.
Can will coat the directly curing of filming that transparent substrates obtains, also can it is separated with dried coating film before it is solidified.When before making curing of coating, carrying out drying, can 30～200 ℃, more preferably 40～150 ℃ dry 0.1～60 minute down, more preferably dry 1～30 minute, solvent is removed, it is separated in advance.When the 1st composition and the 2nd mixture of ingredients are photo-curable, before curing, make its drying, it is separated, have like this and can remove the anti-concavo-convex advantage of dazzling the solvent in the layer and required size can be set effectively.
Additive method as being separated before it is solidified also can use the method that it is separated to the irradiates light of filming.As the light of irradiation, for example can using, exposure is 0.1～1.5J/cm
2Light, preferably use 0.5～1.5J/cm
2Light.This irradiation light wavelength is not particularly limited, can uses irradiates light that for example has 360nm or following wavelength etc.When for example using 2-methyl isophthalic acid [4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone etc. as light trigger, preferred irradiation has near the irradiates light of the wavelength 310nm, and more preferably irradiation has near the light of the wavelength 360nm.This light can use high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc. to obtain.By such irradiates light, be separated and solidify.By irradiates light it is separated, has and to avoid because the advantage that the uneven drying of contained solvent is spared caused surface configuration speckle in the coating composition.
By make by coating composition coating obtained films or the dry curing of coating that obtains, form the anti-layer of dazzling.When the 1st composition and the 2nd mixture of ingredients are Thermocurable, can by 40～280 ℃, more preferably 80～250 ℃ of down heating 0.1～180 minute, more preferably heat and made its curing in 1～60 minute.When the 1st composition and the 2nd mixture of ingredients are photo-curable, can make its curing by the light source irradiation light that uses the light of launching required wavelength.It should be noted that as mentioned above rayed can be that purpose is used to be separated also.
So the anti-cross section schematic diagram of film of dazzling that forms is in Fig. 1.The anti-film 1 of dazzling has anti-layer 3 and the transparent substrates 5 of dazzling.Because anti-the concavo-convex of film surface of dazzling of the present invention spontaneously determines concavo-convex configuration, so can form irregular concaveconvex shape on the surface of resin bed.
Anti-concave-convex surface shape of dazzling layer can be used R
Z JIS94The parameter of (10 mean roughness) is estimated.Here, R
Z JIS94It is standardized parameter in appendix 1 table 1 of JIS B0601.This R
ZJIS94It is the index of height roughness concavo-convex on the presentation surface.Fig. 2 is a parameters R
Z JIS94Key diagram.Among this figure, block curve is represented anti-cross section of dazzling layer.10 mean roughness (R
Z JIS94) can use super degree of depth measuring shape microscope that (strain) キ one エ Application ス produces etc., measure according to the appendix 1 of JIS B0601.It should be noted that JIS B0601 is translation ISO4287, does not change technology contents and standard pattern and the Japanese Industrial Standards made.
The anti-preferred R of film that dazzles of the present invention
Z JIS94Be 1.0 μ m or following.R
Z JIS94When surpassing 1.0 μ m, the preformed casse degree takes place sometimes uprise, produce white blur etc. and be not suitable for anti-problem of dazzling purposes.More preferably R
Z JIS94Be 0.8 μ m or following, 0.5 μ m or following more preferably.Preferred lower limit is 0.1 μ m.
Of the present invention anti-dazzle the preferred all-optical transmittance of film be 90% or more than, more preferably 95% or more than.Especially for the present invention, owing to do not contain resin particle, therefore can reach high all-optical transmittance as described above.All-optical transmittance (T
t(%)) can be by measuring with respect to the anti-incident intensity (T of film that dazzles
0) and the anti-total transmissivity light intensity (T of film that dazzles of transmission
1), utilize following formula to obtain.The diagrammatic illustration of all-optical transmittance is illustrated in Fig. 3.
[several 4]
Tt(％)＝T
1/T
0×100
The mensuration of all-optical transmittance for example can use preformed casse degree analyzer (production of ス ガ testing machine company) to measure.
Of the present inventionly anti-dazzle the preferred preformed casse degree of film less than 20%, more preferably 18% or below, more preferably 15% or below, be preferably especially 10% or below.As mentioned above, can make the anti-film of dazzling that the preformed casse degree is low and antidazzle is excellent according to the present invention with premium properties.The advantage that the preformed casse degree is low has: in the time will preventing that dazzling film is arranged at liquid crystal indicator, do not damage the distinctiveness of shown image, be difficult to take place white blur etc.Low anti-of this preformed casse degree dazzled the advantage that film has the distinctiveness of not damaging the shown image of high-resolution liquid crystal indicator especially.
The preformed casse degree can be calculated by following formula according to JIS K7105.
[several 5]
H(％)＝T
d/T
t×100
H: preformed casse degree (mist value) %
T
d: diffusion transmittance (%)
T
t: all-optical transmittance (%)
The mensuration of preformed casse degree for example can be used, and preformed casse degree analyzer (production of ス ガ testing machine company) carries out.
The anti-preferred R of film that dazzles of the present invention
Z JISBe 1.5 μ m or following.Here, R
Z JISBe meant the maximum height roughness of roughness curve, be predetermined parameter in JIS B0601-2001.More preferably R
Z JISBe 1.0 μ m or following, 0.7 μ m or following more preferably.Lower limit is preferably 0.1 μ m.Of the present inventionly anti-dazzle film and be characterised in that, not containing particle such as resin particle can modulate.Use when formations such as resin particle is anti-dazzles concavo-convex on the film aggegation of the resin particle that in the making of preventing dazzling film, mostly occurs.Because this aggegation causes R
Z JISIt is big that the value of (maximum height roughness) becomes.The anti-R of film that dazzles
Z JISWhen the value of (maximum height roughness) surpassed 1.5 μ m, the problem that the anti-image distinctiveness of dazzling film of transmission reduces, produces white blur might take place.
Of the present invention anti-to dazzle the preferred Sm of film be 100 μ m or following, more preferably 50 μ m or following.Lower limit is preferably 5 μ m.Here, Sm is meant the average length of surfaceness curve element, is commonly referred to as the peak valley equispaced or the concavo-convex equispaced of coarse curve.Sm for example can use the super degree of depth measuring shape microscope of (strain) キ one エ Application ス production etc., measures according to JIS B0633.It should be noted that JIS B0633 is translation ISO4288, does not change technology contents and standard pattern and the Japanese Industrial Standards made.
It is of the present invention that anti-to dazzle the anti-configuration of dazzling the surface imperfection concaveconvex shape of layer of film be spontaneous decision.And, of the present inventionly anti-dazzle film and preferably do not have maximal value with respect to the scattered light intensity of scattering angle.From with respect to anti-dazzle the normal direction of pellicular front, during promptly with respect to the right angle orientation irradiates light of pellicular front, transmitted light at the direct direct of travel of this irradiates light, be that scattering angle is maximum on 0 ° the direction.And irradiates light is by the anti-thin films scattering, light also transmission on the direction of off-normal direction certain angle thus of dazzling.The light of this scattering is scattered light (transmitted scattered light).Of the present inventionly anti-dazzle film and preferably do not have maximal value with respect to the scattered light intensity of this scattering angle.When this scattered light had maximal value, scattered light was assembled with respect to special angle, and therefore interference of light takes place sometimes.Because the generation of interference of light might cause the anti-reduction of dazzling the image distinctiveness of film of transmission, and is therefore not preferred.
Of the present inventionly anti-dazzle film and also can have low-index layer.Low-index layer is made of low refractive index resin.By forcing down index layer, with regard to optical component etc., when being configured for the most surperficial mode, can prevent effectively that light (external light source etc.) from the outside is in the reflection of antidazzle film surface according to low-index layer on the anti-upper strata of one side at least of dazzling layer.And,, can further reduce anti-preformed casse degree of dazzling film by disposing for the most surperficial mode with low-index layer.By being configured for the most surperficial mode according to low-index layer, promptly on transparent substrates, form the anti-layer of dazzling, further form low-index layer on the layer this anti-dazzling, can further reduce the anti-preformed casse degree of dazzling film of gained.
The refractive index of low refractive index resin is for example 1.35～1.39, is preferably 1.36～1.39, more preferably about 1.38～1.39.
The thickness of low-refraction is for example 0.05～2 μ m, is preferably 0.1～1 μ m (for example 0.1～0.5 μ m), more preferably about 0.1～0.3 μ m.
As low refractive index resin, can enumerate for example methylpentene resin, two (carbonic acid propyl diester) resins of diglycol, Kynoar (PVDF), polyvinyl fluoride fluororesin such as (PVF) etc.In addition, low-index layer preferably contains fluorochemicals usually.By using fluorochemicals, can reduce the refractive index of low-index layer as required.
Fluorochemicals can be enumerated the functional group's (curable groups such as crosslinkable groups or polymerizable group etc.) that has fluorine atom and react by heat, active energy ray (ultraviolet ray or electron beam etc.) etc., and the fluorine resin precursor of fluorine resin (particularly solidifying or cross-linked resin) can take place to solidify or be cross-linked to form by heat, active energy beam.This fluorine resin precursor for example can be enumerated, and the Thermocurable compound or the resin of contain fluorine atoms [have reactive group (epoxy radicals when having fluorine atom; isocyanate group; carboxyl; hydroxyl etc.); polymerizable group (vinyl; allyl; (methyl) acryloyl group etc.) etc. low molecular weight compound]; by activation light (ultraviolet ray etc.) contain fluorine atoms photocurable compound that can solidify or resin (ultra-violet solidified compounds such as photo-curable fluorochemical monomer or oligomer etc.) etc.
The Thermocurable compound of contain fluorine atoms or resin for example can be enumerated the low-molecular-weight resin that uses fluorine-containing at least monomer and obtain, and for example use fluorine-containing polyvalent alcohol (particularly glycol) to replace part or all and the epoxies fluorine resin that obtains as the polyol component that constitutes monomer; Equally, use contain fluorine atoms polyvalent alcohol and/or contain fluorine atoms poly carboxylic acid composition to replace part or all of polyvalent alcohol and/or poly carboxylic acid composition and the unsaturated polyester (UP) class fluorine resin that obtains; The ammonia ester class fluorine resin that uses contain fluorine atoms polyvalent alcohol and/or polyisocyanate composition to replace part or all of polyvalent alcohol and/or polyisocyanate composition and obtain etc.These Thermocurable compounds or resin can use separately, also can make up two kinds or above use.
In the contain fluorine atoms photocurable compound, comprise for example monomer, oligomer (or resin, particularly low-molecular-weight resin), as monomer can enumerate with at the above-mentioned anti-simple function monomer enumerated in the layer and the corresponding contain fluorine atoms monomer of the multi-functional monomer [monofunctional monomers such as ethene base system monomer such as contain fluorine atoms (methyl) acrylic monomer, fluoroolefins class such as (methyl) acrylic acid fluorinated alkyl esters of dazzling; 1-fluoro-1,2-two (methyl) acryloxy ethylidene etc. is fluoridized two (methyl) acrylate of aklylene glycol etc.].In addition, oligomer or resin can use with at above-mentioned anti-oligomer or corresponding contain fluorine atoms oligomer of resin or the resin of enumerating in the layer etc. of dazzling.These light hardness compounds can use or make up two kinds or above use separately.
The curable precursor of fluorine resin can obtain with the form of solution (coating fluid) shape, and this coating fluid can use " TT1006A " and " JN7215 " of for example Japanese synthetic rubber (strain) production, " the デ イ Off エ Application サ TR-330 " of big Japanese ink chemical industry (strain) production etc.
Of the present inventionly anti-dazzle film and can use low-index layer, dazzle layer and low-index layer constitutes by anti-as transparent substrates.Antidazzle film of the present invention can also by transparent substrates, on this transparent substrates, form successively anti-dazzle the layer and low-index layer constitute.
Polarized light piece
Antidazzle antireflective film of the present invention can be used for the polarized light piece of liquid crystal indicator (LCD).The cross section schematic diagram of having used anti-polarized light piece of dazzling film of the present invention is in Fig. 4.Being constructed as follows of polarized light piece 10 shown in Figure 4: on the one side (side above being) of polarization photosphere (polarization element) 12, be provided with the above-mentioned anti-film 1 of dazzling in Fig. 4.
Polarization photosphere 12 is laminated between 2 layers of transparent substrates 5,14.Can use the TAC film as transparent substrates 5,14.This polarization photosphere 12 is a 3-tier architecture, and the 1st layer and the 3rd layer is included in the film that is added with iodine in the polyvinyl alcohol (PVA) (PVA), and middle the 2nd layer comprises the PVA film.Should anti-dazzle constituting of film 1 and be pressed with the anti-layer 3 of dazzling on transparent substrates 5 upper stratas.
Use the TAC film when being located at the transparent substrates in 12 liang of outsides of above-mentioned polarization photosphere, owing to there is not birefringence, polarized light can scattering, though therefore with PVA that becomes polarization element and PVA+ iodine film laminating, polarized light can scattering yet.Therefore, use this polarized light piece 10 can access the liquid crystal indicator that shows the grade excellence.
The polarization element that constitutes the polarization photosphere 12 of above-mentioned polarized light piece 10 has: on the PVA film that forms that dyes and stretch with iodine or dyestuff, and polyvinyl formal film, polyvinyl acetal film, vinyl-vinyl acetate copolymer class saponification film etc.
It should be noted that when lamination constitutes each film of polarization photosphere 12,, can implement saponification to above-mentioned transparent substrates and handle in order to increase cohesive and to prevent static.
Liquid crystal indicator
Antidazzle antireflective film of the present invention can be used for liquid crystal indicator (LCD).Fig. 5 has used anti-cross section skeleton diagram of dazzling the transmission display unit of film of the present invention.
Liquid crystal indicator 20 shown in Figure 5 is in lamination in turn and above-mentioned polarized light piece 10 same polarized light piece 22, liquid crystal panel 24 and polarized light piece 26, has disposed the transparent type liquid crystal indicator of back of the body lamp 28 on the back side of polarized light piece 26 1 sides.
The liquid crystal panel 24 employed liquid crystal modes of above-mentioned liquid crystal indicator 20 can be any of twisted nematic (TN), super-twist nematic (STN), phase transformation type (PC), high-molecular dispersed (PDLC) etc.
The liquid crystal drive pattern can be any one of simple matrix type, active array type, during for active array type, adopts type of drive such as TFT, MIM.Liquid crystal panel 24 can be any in color-type or the monochromatic type.
Antidazzle antireflective film of the present invention can also be used for Plasmia indicating panel (PDP), electroluminescent display (ELD), cathode tube display device image display devices such as (CRT) except can be used for liquid crystal indicator.With the anti-film of dazzling of the present invention when being used for liquid crystal indicator, can on the transparent substrates surface of the side of dazzling layer of not setting up defences, bonding coat etc. be set, be disposed at the most surperficial of display.Also can further carry out antireflection processing etc. anti-anti-dazzling on the layer of dazzling film of the present invention.
Embodiment
Further specify the present invention by the following examples, but the present invention is not subjected to the qualification of these embodiment.Only it should be noted that otherwise specify that " part " represents weight portion.
The modulation of modulation example 1 siloxane acrylic block copolymers
With 243.9g VPS-1001N (contain that the pure pharmaceutical worker's industry of the polysiloxane compound of azo group and light company produces, the molecular weight of polysiloxane chain is 10,000, solid constituent is 50%) with contain the potpourri mixing of 144.0g cyclohexyl methacrylate, 43.7g styrene, 52.3g hydroxyethyl methylacrylate and 343.3g butyl acetate.Evenly this mixed solution is dropped in the butyl acetate that is heated to 120 ℃ under the nitrogen atmosphere gas of 270.0g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel with 3 hours, mix down at 120 ℃ thereafter and reacted in 30 minutes.With at the uniform velocity dripping the solution that 15.0g contains the butyl acetate of 0.60g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester in 30 minutes, under 120 ℃, mix again then and reacted in 1 hour, obtain number-average molecular weight and be 34,000, weight-average molecular weight is 125,000 siloxane acrylic block copolymers.The Sp value of this resin: 10.8, Tg:69 ℃, surface tension: 16dyn/cm.
Modulation example 2 contains the modulation of the siloxane acrylic block copolymers of unsaturated double-bond
With 243.9g VPS-1001N (contain that the pure pharmaceutical worker's industry of the polysiloxane compound of azo group and light company produces, the molecular weight of polysiloxane chain is 10,000, solid constituent is 50%) with contain the potpourri mixing of 68.2g cyclohexyl methacrylate, 103.9g styrene, 44.3g glycidyl methacrylate and 343.3g butyl acetate.Evenly this mixed solution is dropped in the butyl acetate that is heated to 120 ℃ under the nitrogen atmosphere gas of 270.0g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel with 3 hours, thereafter 120 ℃ of reactions 30 minutes down.With at the uniform velocity dripping the solution that 15.0g contains the butyl acetate of 0.60g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester in 30 minutes, then 120 ℃ of reactions 1 hour down.In this reactant liquor, drip 10g and contain the butyl acetate solution of 3.12g bromination tert-butyl group ammonium and 0.2g quinhydrones, on one side the bubbling air bubble, on one side at 120 ℃ down with at the uniform velocity dripping 23.6g acrylic acid in 5 hours.Further 120 ℃ of down reactions 1 hour, obtain number-average molecular weight and be 19,000, weight-average molecular weight is 83,000 the siloxane acrylic block copolymers that contains unsaturated double-bond.The Sp value of this resin: 10.6, Tg:76 ℃, surface tension: 18dyn/cm.
The modulation of modulation example 3 acrylic copolymers
The potpourri that will contain 280.8g isobornyl methacrylate, 4.2g methyl methacrylate, 15.0g methacrylic acid and 340.0g propylene glycol monomethyl ether mixes.Evenly this mixed liquor is dropped in the propylene glycol monomethyl ether that is heated to 110 ℃ under the nitrogen atmosphere gas of 200g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel with 3 hours, thereafter 110 ℃ of reactions 30 minutes down.With at the uniform velocity dripping the propylene glycol monomethyl ether solution that 120g contains 3.0g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester in 30 minutes, and then with dripping the propylene glycol monomethyl ether solution that 25.5g contains 0.3g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester in 30 minutes, obtaining number-average molecular weight is 6,400, weight-average molecular weight is 14,800 acrylic copolymer.The Sp value of this resin: 9.9, Tg:113 ℃, surface tension: 29dyn/cm.
Modulation example 4 contains the modulation of the acrylic copolymer of unsaturated double-bond
The potpourri that will contain 187.2g isobornyl methacrylate, 2.8g methyl methacrylate, 10.0g methacrylic acid and 160.0g propylene glycol monomethyl ether mixes.The propylene glycol monomethyl ether solution that evenly this mixed liquor and 80.0g was contained tert-butyl hydroperoxide-2 ethyl hexanoic acid ester with 3 hours drops in the propylene glycol monomethyl ether that is heated to 100 ℃ under the nitrogen atmosphere gas of 200.0g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel simultaneously, then 100 ℃ of reactions 1 hour down.Then, drip the propylene glycol monomethyl ether solution that contains 0.2g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, reacted 1 hour down at 100 ℃.In this reaction solution, add the propylene glycol monomethyl ether solution that 5.0g contains 1.5g Tetrabutylammonium bromide and 0.2g quinhydrones, bubbling air steeps on one side, dripped 17.3g glycidyl methacrylate and 5g propylene glycol monomethyl ether solution with 1 hour on one side, reacted again thereafter 5 hours.Obtain number-average molecular weight and be 8,800, weight-average molecular weight is 18,000 the acrylic copolymer that contains unsaturated double-bond.The Sp value of this resin: 9.8, Tg:113 ℃, surface tension: 31dyn/cm.
Modulation example 5 contains the modulation of the acrylic copolymer of unsaturated double-bond
The potpourri that will contain 147.2g isobornyl methacrylate, 2.8g methyl methacrylate, 4.0g hydroxy acrylic acid ethyl ester, 10.0g methyl acrylate and 160.0g propylene glycol monomethyl ether mixes.The propylene glycol monomethyl ether solution that evenly this mixed liquor and 80.0g was contained 2g tert-butyl hydroperoxide-2-Octyl Nitrite with 3 hours drops in the propylene glycol monomethyl ether that is heated to 110 ℃ under the nitrogen atmosphere gas of 200.0g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel simultaneously, then 110 ℃ of reactions 30 minutes down.Drip 17g then and contain the propylene glycol monomethyl ether solution of 0.2g tert-butyl hydroperoxide 2 ethyl hexanoic acid ester, 110 ℃ of reactions 30 minutes down.In this reaction solution, add the propylene glycol monomethyl ether solution that 5.0g contains 1.5g Tetrabutylammonium bromide and 0.1g quinhydrones, bubbling air steeps on one side, dripped 17.3g glycidyl methacrylate and 5g propylene glycol monomethyl ether solution with 1 hour on one side, reacted again thereafter 5 hours.Obtain number-average molecular weight and be 8,800, weight-average molecular weight is 18,000 the acrylic copolymer that contains unsaturated double-bond.The Sp value of this resin: 9.9, Tg:55 ℃, surface tension: 27dyn/cm.
Modulation example 6 contains the modulation of the acrylic copolymer of unsaturated double-bond
The potpourri that will contain 171.6g isobornyl methacrylate, 2.6g methyl methacrylate, 9.2g methyl acrylate mixes.The propylene glycol monomethyl ether solution that evenly this mixed liquor and 80.0g was contained 1.8g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester with 3 hours drops in the propylene glycol monomethyl ether that is heated to 110 ℃ under the nitrogen atmosphere gas of 330.0g in having the 1000ml reaction vessel of agitator, nitrogen ingress pipe, condenser pipe and addition funnel simultaneously, then 110 ℃ of reactions 30 minutes down.Drip 17.0g then and contain the propylene glycol monomethyl ether solution of 0.2g tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, add 5.0g again and contain the propylene glycol monomethyl ether solution of 1.4g Tetrabutylammonium bromide and 0.1g quinhydrones, bubbling air steeps on one side, dripped the solution of 22.4g4-hydroxyl butylacrylic acid ester glycidol ether and 5.0g propylene glycol monomethyl ether with 2 hours on one side, and then reacted 5 hours.Obtain number-average molecular weight and be 5,500, weight-average molecular weight is 18,000 the acrylic copolymer that contains unsaturated double-bond.The Sp value of this resin: 10.0, Tg:92 ℃, surface tension: 31dyn/cm.
With the acrylic copolymer (the Sp value of this resin: 9.9, Tg:113 ℃) of the siloxane acrylic block copolymers (the Sp value of this resin: 10.8, Tg:69 ℃) of 32 weight portions modulation example 1,48 weight portions modulation example 3,20 weight portions as the melamine hardening agent of thermal curing agents, 6 weight portions as the p-toluenesulfonic acid of thermal curing catalyst, oligomer that 0.1 weight portion contains perfluoroalkyl in solvent benzol methyl ether (Sp value: mixing 9.5), preparation solution makes the nonvolatile component ratio reach 23 weight %.Under 23 ℃ of environment temperatures, with the rotating speed of 800rpm the gained solution film is coated on the triacetylcellulose film substrate 10 seconds of coating by the rotary coating machine.Under 100 ℃, be that the coated film of 5 μ m carries out being heating and curing in 10 minutes, obtain the anti-film of dazzling thickness.
Gained is anti-, and to dazzle the evaluation and the anti-concavo-convex evaluation of dazzling laminar surface of film as described below.The results are shown in table 2 by what these evaluation methods obtained.
10 mean roughness (R
Z JIS94)
The super degree of depth measuring shape microscope that uses キ one エ Application ス to produce is measured the surface according to the appendix 1 of JIS-B0601 and is gone up 10 concavo-convex mean roughness (R
Z JIS94), obtain R
Z JIS94Value.
Maximum height roughness (the R of roughness curve
Z JIS)
The super degree of depth measuring shape microscope that uses キ one エ Application ス to produce is measured the maximum height roughness (R that concavo-convex roughness curve is gone up on the surface according to JIS-B0601
Z JIS), obtain R
Z JISValue.It should be noted that the maximum height roughness (R of this roughness curve
Z JIS) only in embodiment 4 and embodiment 5, measure.
All-optical transmittance
Use preformed casse degree analyzer (production of ス ガ testing machine company), measure with respect to the anti-incident intensity (T of film that dazzles
0) and the anti-total transmissivity light intensity (T of film that dazzles of transmission
1), obtain all-optical transmittance (T according to following formula
t(%)).
[several 6]
Tt(％)＝T
1/T
0×100
White blur
The outer light scattered reflection that anti-surperficial convex-concave of dazzling layer is caused brings the white casse sense (white blur) of vision and carries out visual assessment.Range estimation is not judged as when having the white casse sense and is evaluated as zero, is evaluated as △ slightly during the muddy sense of adularescent, be evaluated as in the time of can be obviously by the sense of Visual Confirmation white casse *.
The average length (Sm) of the roughness curve key element on surface
The super degree of depth measuring shape microscope that uses キ one エ Application ス to produce, the average length (Sm) according to JIS-B0633 measures the roughness curve key element on surface obtains the Sm value.
Preformed casse degree (mist value)
Use preformed casse degree analyzer (production of ス ガ testing machine company), measure the anti-diffusion transmittance (T of film that dazzles
d(%)) and above-mentioned all-optical transmittance (T
t(%)), obtain the preformed casse degree.
[several 7]
H(％)＝T
d/T
t×100
H: preformed casse degree (mist value) %
T
d: diffusion transmittance (%)
T
t: all-optical transmittance (%)
The 3-D view that should anti-dazzle the concavo-convex state of laminar surface that utilizes super degree of depth measuring shape microscope to obtain has shown island structure as shown in Figure 6.Anti-film does not have fluorescence under fluorescent light extra reflection, the antidazzle excellence of dazzling of gained.
With the siloxane acrylic block copolymers that contains unsaturated double-bond (the Sp value of this resin: 10.6, Tg:76 ℃) of 40 weight portions modulation example 2, the acrylic copolymer that contains unsaturated double-bond (the Sp value of this resin: 9.8, Tg:113 ℃) that 60 weight portions are modulated example 4,5 weight portions as 2 of light trigger; 4; the oligomer that 6-trimethylbenzoyl diphenyl phosphine oxide, 0.1 weight portion contain perfluoroalkyl mixes in the methyl phenyl ethers anisole as solvent; preparation solution makes the nonvolatile component ratio reach 20 weight %.Under 23 ℃ of environment temperatures, by the rotating speed of rotary coating machine this solution was coated with for 10 seconds on the triacetylcellulose film substrate with 1000rpm, then, it is diffusing solvent to be waved in 10 minutes 120 ℃ of following heating, makes thickness reach 8 μ m.To this film irradiation ultraviolet radiation, exposure makes ultraviolet energy reach 1J/cm under extra-high-pressure mercury vapour lamp
2Dazzle film and prevent that dazzling the concavo-convex of laminar surface estimates gained is anti-similarly to Example 1.Evaluation result is shown in table 2.
Utilize the 3-D view that anti-to dazzle the concavo-convex state of laminar surface of super degree of depth measuring shape measurement microscope to show island structure as shown in Figure 7.Anti-film does not have fluorescent light under fluorescent light extra reflection, the antidazzle excellence of dazzling of gained.
At 75 weight portions 12.1), the acrylic copolymer that contains unsaturated double-bond (the Sp value of this resin: 9.9, Tg:55 ℃) of modulation example 5,5 weight portions be as 2 of light trigger as the multi-functional dipentaerythritol acrylate that contains the monomer of unsaturated double-bond (the Sp value of this monomer:; 4; (the SP value: 10.1) as solvent, modulation makes the nonvolatile component ratio reach 23 weight % to add propylene glycol monomethyl ether in the oligomer that contains perfluoroalkyl of 6-trimethylbenzoyl diphenyl phosphine oxide, 0.1 weight portion.Use rod coater (No.18) that this solution rod is coated on the triacetylcellulose film substrate down 23 ℃ of environment temperatures, heat down to remove to desolvate in 10 minutes at 50 ℃ and carry out drying, making thickness is 6 μ m.Under extra-high-pressure mercury vapour lamp, this film is reached 1J/cm with ultraviolet energy then
2Expose, form the anti-layer of dazzling.Dazzle film and prevent that dazzling the concavo-convex of laminar surface estimates gained is anti-similarly to Example 1.Evaluation result is shown in table 2.
Utilize the 3-D view that anti-to dazzle the concavo-convex state of laminar surface of super degree of depth measuring shape measurement microscope to show island structure as shown in Figure 8.Anti-film does not have fluorescent light under fluorescent light extra reflection, the antidazzle excellence of dazzling of gained.
Embodiment 4
With the acrylic copolymer that contains unsaturated double-bond (the Sp value of this resin: 10.0, Tg:92 ℃) of 20 weight portions modulation example 6,90 weight portions as the multi-functional pentaerythritol triacrylate that contains the monomer of unsaturated double-bond (the Sp value of this monomer: 12.7), 7 weight portions as 2-methyl isophthalic acid [4-(methyl mercapto) the phenyl]-2-morpholino propane-1-ketone of light trigger in solvent isobutyl alcohol (SP value: be mixed and made into solution 11.3), make the nonvolatile component ratio reach 40 weight %.Use rod coater (No.12) that this solution rod is coated on the triacetylcellulose film substrate down 23 ℃ of environment temperatures, heat down to remove to desolvate in 1 minute at 60 ℃ and carry out drying, make thickness reach 6 μ m, form the anti-layer of dazzling.Then,, make to reach 1J/cm to this film ultraviolet exposure with extra-high-pressure mercury vapour lamp
2Energy, make its curing.Dazzle film and prevent that dazzling the concavo-convex of laminar surface estimates gained is anti-similarly to Example 1.Evaluation result is shown in table 2.
The acrylic copolymer that contains unsaturated double-bond (the Sp value of this resin: 10.0 with 5 weight portions modulation example 6, Tg:92 ℃), 50 weight portions are as multi-functional pentaerythritol triacrylate (the Sp value of this monomer: 12.7) that contains the monomer of unsaturated double-bond, 50 weight portion polyglycol # 200 diacrylate (the Sp values of this monomer: 13.6), 13 weight portions as 2-methyl isophthalic acid [4-(methyl mercapto) the phenyl]-2-morpholino propane-1-ketone of light trigger in solvent methylisobutylketone (SP value: be mixed and made into solution 8.3), make the nonvolatile component ratio reach 60 weight %.Use rod coater (No.5) that this solution rod is coated on the triacetylcellulose film substrate down 23 ℃ of environment temperatures, heat down to remove to desolvate in 3 minutes at 80 ℃ and carry out drying, make thickness reach 4 μ m.With extra-high-pressure mercury vapour lamp this film is exposed then, make ultraviolet energy reach 1J/cm
2, form and prevent dazzling layer, make its curing.Dazzle film and prevent that dazzling the concavo-convex of laminar surface estimates gained is anti-similarly to Example 1.Evaluation result is shown in table 2.
Comparative example 1 (based on the reference example of patent documentation 1)
100 parts of uv curing resins (Japanese chemical drug system PETA), 1.7 weight portion triacetyl celluloses (production of バ イ エ Le company), 5 weight portion trigger for optical solidification (production of チ バ ガ イ ギ one company, イ Le ガ キ ユ ア 1) and 20 parts by weight of styrene pearls (always grinding chemical production, particle diameter 2.5 μ m) are mixed.Using toluene to be adjusted to solid constituent is 40%, uses the rotary coating machine to be coated on the triacetylcellulose film substrate down for 23 ℃ in environment temperature, makes dry film thickness reach 3.5 μ m.Heat 10 minutes dry solvents down at 80 ℃, (superscript: 2) ultraviolet ray forms the anti-layer of dazzling then to shine 200mJ/cm.Similarly to Example 1 the anti-film of dazzling of gained is estimated with the anti-layer of dazzling.Evaluation result is shown in table 2.
Comparative example 2 (based on the reference example of patent documentation 3)
Use the rotary coating machines to be mixed with the solution coat of the epoxy resin that imported fluorine and acryl resin on the triacetylcellulose film substrate down 23 ℃ of environment temperatures with 2: 1 ratios.80 ℃ of following heat treated of temperature 90 minutes, make the resin solidification of coating, form the anti-layer of dazzling of convex-concave surface shape.Estimate anti-film and the anti-layer of dazzling of dazzling of gained similarly to Example 1.Evaluation result is shown in table 2.Should anti-dazzle laminar surface and show island structure.Gained is anti-dazzles film does not have extra reflection under fluorescent light, but all-optical transmittance is low, is 80%, and white blur be evaluated as *.
Table 1
| Table 1 | | | | Embodiment 4 | | Comparative example 1 | Comparative example 2 | |
| The 1st composition | Acrylic copolymer | Acrylic copolymer | The acrylic copolymer that contains unsaturated double-bond | The acrylic copolymer that contains unsaturated double-bond | The acrylic copolymer that contains unsaturated double-bond | |||
| Tg | 113 | 113 | 55 | 92 | 92 | |||
| SP 1 | 9.9 | 9.8 | 9.9 | 10.0 | 10.0 | |||
| Surface tension (dyn/cm) | 29 | 31 | 27 | 31 | 31 | |||
| The 2nd composition | The siloxane acrylic block copolymers | The siloxane acrylic block copolymers | The multi-functional monomer that contains unsaturated double-bond | The multi-functional monomer that contains unsaturated double-bond | The multi-functional monomer that contains unsaturated double-bond | |||
| Tg | 69 | 76 | - | - | - | |||
| SP 2 | 10.8 | 10.6 | 12.1 | 12.7 | 12.7 13.6 | |||
| Surface tension (dyn/cm) | 16 | 18 | - | - | - | |||
| Organic solvent | Methyl phenyl ethers anisole | Methyl phenyl ethers anisole | Propylene glycol monomethyl ether | Isobutyl alcohol | Methylisobutylketone | N.D . | N.D . | |
| SP sol | 9.5 | 9.5 | 10.1 | 11.3 | 8.3 | N.D . | N.D . | |
| SP solAnd SP 1Poor | 0.4 | 0.3 | 0.2 | 1.3 | 1.7 | - | - | |
| Environment temperature during coating (℃) | 23 | 23 | 23 | 23 | 23 | 23 | 23 | |
Table 2
| Table 2 | | | | Embodiment 4 | | Comparative example 1 | Comparative example 2 |
| 10 mean roughness (R z JIS94) (μm) | 1.9 | 0.8 | 1.4 | 0.6 | 0.9 | 0.3 | 0.8 |
| Maximum height roughness (the R of roughness curve z JIS) (μm) | 0.8 | 1.3 | |||||
| All-optical transmittance Tt (%) | 98 | 96 | 97 | 90 | 91 | 88 | 80 |
| White blur | ○ | ○ | ○ | ○ | ○ | × | × |
| Sm (μm) | 29 | 29 | 43 | 70 | 70 | N.D. | N.D. |
| Preformed casse degree (mist value) H (%) | 68 | 16 | 39 | 6 | 7 | N.D. | N.D. |
The foregoing description can confirm, anti-ly dazzled film and utilizes comparing of comparative example by what coating composition of the present invention formed, and it is high and do not have an excellent properties of white blur etc. to have an all-optical transmittance.In addition, can confirm, can modulate by the present invention that to have a preformed casse degree low and all-optical transmittance is high and do not have the anti-film of dazzling of excellent properties such as white blur by embodiment 4 and embodiment 5.
Claims (23)
1. antidazzle coating composition, it is to coat to form anti-antidazzle coating composition of dazzling layer on the transparent substrates,
This antidazzle coating composition contains the 1st composition and the 2nd composition,
After being coated on this antidazzle coating composition on the substrate, because the rerum natura of the 1st composition and the 2nd composition is poor, the 1st composition and the 2nd composition are separated, and form on the surface to have random concavo-convex resin bed.
2. the described antidazzle coating composition of claim 1, wherein said the 1st composition and the 2nd composition are independent separately, for being selected from a kind or 2 kinds or above combination in monomer, oligomer and the resin.
3. claim 1 or 2 described antidazzle coating compositions, wherein the difference of the SP value of the SP value of the 1st composition and the 2nd composition be 0.5 or more than.
4. the described antidazzle coating composition of claim 3, it is for also containing the antidazzle coating composition of organic solvent,
SP value (the SP of the 1st composition
1), the SP value (SP of the 2nd composition
2) and the SP value (SP of organic solvent
Sol) satisfy following condition:
SP
1＜SP
2, and
SP
1And SP
SolDifference be 2 or below.
5. claim 3 or 4 described antidazzle coating compositions, wherein said the 1st composition is oligomer or resin, described the 2nd composition is a monomer.
6. the described antidazzle coating composition of claim 5, wherein said the 1st composition is the acrylic copolymer that contains unsaturated double-bond, described the 2nd composition is the multi-functional monomer that contains unsaturated double-bond.
7. claim 3 or 4 described antidazzle coating compositions, wherein said the 1st composition is the siloxane acrylic block copolymers, described the 2nd composition is an acrylic copolymer.
8. claim 1 or 2 described antidazzle coating compositions, wherein said the 1st composition and the 2nd composition are resin, in the 1st composition and the 2nd composition any has the Tg of the environment temperature when being lower than the composition coating, and another has the Tg of the environment temperature when being higher than the composition coating.
9. each described antidazzle coating composition of claim 1～3, any of wherein above-mentioned the 1st composition or the 2nd composition is monomer,
The difference of the Tg of the 1st composition and the 2nd composition be 20 ℃ or more than, and
The Tg that has the composition of higher Tg in the 1st composition and the 2nd composition be 20 ℃ or more than.
10. each described antidazzle coating composition of claim 1～9, it also contains hardening agent.
11. each described antidazzle coating composition of claim 1～10 is characterized in that not resinous particle.
12. the anti-film of dazzling, it is to have transparent substrates and the anti-anti-film of dazzling of dazzling layer, and this anti-layer of dazzling is formed by each described antidazzle coating composition of claim 1～11.
13. the described anti-film of dazzling of claim 12 is wherein prevented dazzling the preformed casse degree of film less than 20%.
14. the described anti-film of dazzling of claim 12, the wherein anti-R of film that dazzles
Z JIS94(10 mean roughness) is 1.0 μ m or following.
15. the described anti-film of dazzling of claim 12, wherein anti-average length (Sm) of dazzling the rough surface curve element of film is 100 μ m or following.
16. the described anti-film of dazzling of claim 12 does not wherein have maximal value with respect to anti-scattered light intensity of dazzling the thin films scattering angle.
17. an anti-manufacture method of dazzling film, this method comprises:
On transparent substrates the painting process of coating claim 1～11 each described antidazzle coating composition and
Make the curing process of gained curing of coating.
18. an anti-manufacture method of dazzling film, this method comprises:
On transparent substrates the painting process of coating claim 1～11 each described antidazzle coating composition,
The gained dried coating film is made its drying process that is separated, and
Make the curing process of dry curing of coating.
19. an anti-manufacture method of dazzling film, this method comprises:
On transparent substrates the painting process of coating claim 1～11 each described antidazzle coating composition and
To the gained irradiation process that irradiates light is separated it and solidifies of filming.
20. the anti-film of dazzling, it obtains by each described anti-manufacture method of dazzling film of claim 17～19.
21. polarized light piece, it is to have each described anti-polarized light piece of dazzling film and polarization element of claim 12～16, prevent dazzling film surface and polarization element surface lamination in opposite directions, the described anti-anti-relative face of layer of dazzling that film surface is and is located at transparent substrates of dazzling.
22. a transmission display unit, it has plane light transmission display body, from the light supply apparatus of this light transmission display body of back side illuminaton be laminated to each described anti-film of dazzling of claim 12～16 on this light transmission display body surface.
23. a liquid crystal indicator, it is with each described anti-top layer that film is used for display of dazzling of claim 12～16.
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|---|---|---|---|
| JP021805/2004 | 2004-01-29 | ||
| JP2004021805 | 2004-01-29 |
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|---|---|
| JP (1) | JP3998697B2 (en) |
| KR (1) | KR101154807B1 (en) |
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| JPH11199798A (en) | 1998-01-19 | 1999-07-27 | Nikko Kagaku Kenkyusho:Kk | Multiphase-structure-forming coating agent, method for forming multiphase-structure film, and optical-path conversion film |
| JP2000193808A (en) * | 1998-12-25 | 2000-07-14 | Asahi Glass Co Ltd | Surface side substrate and manufacture of the same, and reflection display element |
| TW525033B (en) * | 1999-03-15 | 2003-03-21 | Toppan Printing Co Ltd | An electrode substrate for reflected type liquid crystal display device, and reflected type liquid crystal display device |
| TWI300150B (en) * | 2000-02-16 | 2008-08-21 | Toshiba Matsushita Display Tec | Reflective-type display element, reflector and method of producing the same |
| KR100949870B1 (en) * | 2001-12-17 | 2010-03-25 | 다이셀 가가꾸 고교 가부시끼가이샤 | Anti-glare film, and optical member and liquid crystal display device using same |
| JP2004008840A (en) * | 2002-06-04 | 2004-01-15 | Nitto Denko Corp | Method for manufacturing coating film sheet, method for manufacturing antireflection sheet, antireflection sheet, optical element, and image display apparatus |
| JP4217097B2 (en) * | 2003-04-03 | 2009-01-28 | ダイセル化学工業株式会社 | Anti-glare film |
-
2005
- 2005-01-28 TW TW094102672A patent/TW200537127A/en unknown
- 2005-01-28 WO PCT/JP2005/001217 patent/WO2005073763A1/en active Application Filing
- 2005-01-28 KR KR1020067015219A patent/KR101154807B1/en active IP Right Grant
- 2005-01-28 CN CNA2005800037429A patent/CN1914523A/en active Pending
- 2005-01-28 JP JP2005517515A patent/JP3998697B2/en not_active Expired - Lifetime
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| TWI453120B (en) * | 2007-11-15 | 2014-09-21 | Jsr Corp | A raw film of a raw ice sheet having a hard coat layer and a method for producing a raw ethylidene resin film having a hard coat layer |
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| CN106707605A (en) * | 2017-02-28 | 2017-05-24 | 合肥鑫晟光电科技有限公司 | Display panel and display equipment comprising same |
| CN116324365A (en) * | 2020-10-02 | 2023-06-23 | 大日本印刷株式会社 | Correction method, comparison method, and comparison device of glare contrast, method of manufacturing electronic display, and method of manufacturing antiglare layer |
| CN112433278A (en) * | 2020-11-27 | 2021-03-02 | 宁波东旭成新材料科技有限公司 | Preparation method of novel light diffusion film |
| CN112433278B (en) * | 2020-11-27 | 2022-07-29 | 宁波东旭成新材料科技有限公司 | Preparation method of light diffusion film |
| CN114231158A (en) * | 2021-12-24 | 2022-03-25 | 惠州合益创光学材料有限公司 | Composition for high-precision anti-dazzle coating and high-precision anti-dazzle film thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060129331A (en) | 2006-12-15 |
| KR101154807B1 (en) | 2012-06-18 |
| JP3998697B2 (en) | 2007-10-31 |
| JPWO2005073763A1 (en) | 2007-09-13 |
| TW200537127A (en) | 2005-11-16 |
| WO2005073763A1 (en) | 2005-08-11 |
| TWI350387B (en) | 2011-10-11 |
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