CN103777255A - Anti-dazzle film and manufacturing method therefor - Google Patents

Anti-dazzle film and manufacturing method therefor Download PDF

Info

Publication number
CN103777255A
CN103777255A CN201310495269.7A CN201310495269A CN103777255A CN 103777255 A CN103777255 A CN 103777255A CN 201310495269 A CN201310495269 A CN 201310495269A CN 103777255 A CN103777255 A CN 103777255A
Authority
CN
China
Prior art keywords
methyl
resin
antiglare film
dazzle
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310495269.7A
Other languages
Chinese (zh)
Other versions
CN103777255B (en
Inventor
林正树
横山将史
高桥启司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Original Assignee
Daicel Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel Chemical Industries Ltd filed Critical Daicel Chemical Industries Ltd
Publication of CN103777255A publication Critical patent/CN103777255A/en
Application granted granted Critical
Publication of CN103777255B publication Critical patent/CN103777255B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
    • H01L2224/0212—Auxiliary members for bonding areas, e.g. spacers
    • H01L2224/02122—Auxiliary members for bonding areas, e.g. spacers being formed on the semiconductor or solid-state body
    • H01L2224/02163—Auxiliary members for bonding areas, e.g. spacers being formed on the semiconductor or solid-state body on the bonding area
    • H01L2224/022—Protective coating, i.e. protective bond-through coating
    • H01L2224/02215—Material of the protective coating

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Mathematical Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The invention provides an anti-dazzle film with good balance between haze and clearness. When the anti-dazzle film is arranged on a highly-fine display device, the anti-dazzle property can be improved, dazzle can be greatly inhibited, and character indistinction can be prevented. Long and thin projection parts of a total length of greater than 100[mu]m are formed on the surface of an anti-dazzle layer of the anti-dazzle film when various resin constituents are separated from each other. More than one the abovementioned long and thin projection parts exist in every one square millimeter on the surface of the anti-dazzle layer. The abovementioned long and thin projection parts form a joint continuous phase structure, and the average diameter of meshes of the joint continuous phase structure is around from 1[mu]m to 70[mu]m. The anti-dazzle film has a transmission image definition of 70-100%, a haze of 10-40% and a total light transmissivity of 70-100%. The transmission image definition is detected using a mapping measuring instrument of an optical slit 0.5mm wide.

Description

Antiglare film and manufacture method thereof
Technical field
The present invention relates to be applicable to prevent antiglare film and manufacture method thereof that dazzle on the display surface of various display device and external light source are mirrored.
Background technology
Mirror in order to prevent the outdoor scene on the display surface of liquid crystal indicator, organic field luminescence (EL) display device etc., conventionally prevent normal reflection by the potpourri of particulate and adhesive resin or curable resin being coated on matrix material and at surface formation micro concavo-convex, thereby show anti-glare.But, for the fine fine display device of Pixel Dimensions, with existing concave-convex surface size, can cause that the picture qualities such as dazzle, the character of picture is fuzzy reduce.That is, for the situation of fine display device, existing concave-convex surface size approaches the Pixel Dimensions that fine shows on the order of magnitude, and the lens effect being caused by concave-convex surface can cause dazzle.In addition, owing to cannot the centre of gravity place of the particulate in coating inside and surface structure being controlled, therefore transmitted scattered light is Gaussian distribution centered by directly entering transmitted light.Therefore, under existing particle size, near the scattering of directly entering transmitted light increases, and the profile of pixel thickens and to produce character fuzzy.And the intensity distributions of transmitted scattered light depends on added particle size, as less in particulate, directly to enter transmission scattering of light and reduce, dazzle reduces, as larger in particulate, and directly entering near the scattering of transmitted light increases, and produces dazzle.
In order to solve these problems, attempt reducing the size of added particulate or the particulate of use narrow diameter distribution etc., carry out the concaveconvex shape of control surface.But, in these methods, fuzzy in order to prevent dazzle and character, need to control the centre of gravity place of particulate.In addition, because surperficial concaveconvex shape diminishes, be therefore difficult to take into account sufficient anti-glare, and be in a disadvantageous position aspect cost.
In TOHKEMY 2001-215307 communique (patent documentation 1), a kind of antiglare layer is disclosed, it is that to make mean grain size be that to be included in thickness be the antiglare layer forming in 2 times of above tunicles of above-mentioned mean grain size for transparent particulate below 15 μ m, wherein, in above-mentioned tunicle, above-mentioned transparent particulate is present in unevenly the side contacting with air and forms the fine concaveconvex structure in surface.In the document, also disclose a kind of optical component, its at least one side at polaroid or ellipsoidal polarizing plate possesses above-mentioned antiglare layer.
But, in this antiglare layer, control the intensity distributions of transmitted scattered light by particle size, therefore cannot effectively prevent that dazzle and character on display surface are fuzzy.
In TOHKEMY 2011-13238 communique (patent documentation 2), as the antiglare film with the concave-convex surface shape that can realize anti-glare and high-contrast, the antiglare film that stacked antiglare layer forms on translucent matrix is disclosed, wherein, the mesh size that above-mentioned antiglare layer has horizontal direction is the common Continuum Structure of 10～150 μ m, and above-mentioned antiglare layer at least has first-phase and second-phase.In the document, when masking, make inorganic constituents condense in antiglare layer and form altogether Continuum Structure.In addition, " Continuum Structure altogether " in the document is defined as compared with existing antiglare layer the structure that the inclination of the convex portion of concave-convex surface shape is little and mild.
But the common Continuum Structure of the document is to utilize the convection current of following the aggegation of inorganic constituents and produce to manufacture, owing to being difficult to critically control convection current, therefore cannot make mesh size and net thick (width) there is homogeneity.Thus, concavo-convex concavo-convex the coexisting of large scale with becoming the order of magnitude and strengthen dazzle of the small size of dazzle can be reduced, reduction and the anti-glare of dazzle cannot be realized in essence simultaneously.And, in the situation that mesh size is little, although can reduce dazzle, cannot bring into play sufficient anti-glare.On the other hand, in the situation that mesh size is large, concave-convex surface size approaches Pixel Dimensions on the order of magnitude, therefore cannot reduce dazzle.
On the other hand, also known have the spinodal decomposition (spinodal decomposition) that utilizes incompatible resin composition in the method for surface formation concaveconvex shape, in No. 4377578 communique of Jap.P. (patent documentation 3), a kind of antiglare film that comprises antiglare layer is disclosed, described antiglare layer surface has concaveconvex structure, isotropically transmission scatter incident light, formed by least one polymkeric substance and at least one curable resin precursor, and there is phase separation structure.In the document, recorded: thus by uniform dissolution in the solution that forms of at least one polymkeric substance and at least one curable resin precursor solvent evaporated make in the method for sheet material, be to make under felicity condition its spinodal decomposition, while then making above-mentioned precursor cures, can form that phase spacing has the phase separation structure of systematicness and to surface relief structure that should phase structure; When the antiglare layer that possesses the phase separation structure with such systematicness is installed on to fine display device (concrete as have the liquid crystal indicator of the resolution of 150ppi), dazzle and the character that can effectively eliminate display surface are fuzzy.Particularly, in the document, record: follow the common continuous structure that forms being separated, be separated while further carrying out, form drop phase structure; From the viewpoint of forming surface relief structure and improving skin hardness, the drop phase structure at least with island territory (domain) is favourable, by forming island territory, can after dry, form concaveconvex shape in antiglare layer surface.And, in the document, record: as for bringing out the baking temperature being separated being caused by spinodal decomposition, can for example, from the temperature lower than solvent boiling point (: the scope of 30～200 ℃ of left and right), select preferably 40～80 ℃, in an embodiment, dry at 60 ℃ or 80 ℃.
In TOHKEMY 2008-225195 communique (patent documentation 4), a kind of anti-glare film is disclosed, described anti-glare film is formed by following solidfied material, described solidfied material is by (methyl) acrylic resin of weight-average molecular weight 30000～1000000, weight-average molecular weight 1000～100000 and there is (methyl) acrylic resin of polymerizable group and multi-functional (methyl) acrylate forms, wherein, on this anti-glare film surface, in random direction, disperse to be formed with the rope form protuberance that mean breadth is 0.1～30 μ m, and the area ratio of above-mentioned rope form protuberance is below 50% with respect to total surface.In the document, also record: the drop phase structure at least with island territory is favourable, by forming island territory, after being dried, can form concaveconvex shape on antiglare layer surface.And, in the document, also record: in order to bring out convection current and to be separated, after preferably placing certain hour under normal temperature or room temperature, for example, be dried in the temperature lower than solvent boiling point (: 30～200 ℃, the scope of 40～80 ℃ of left and right particularly preferably), in an embodiment, after at room temperature placing for 10 seconds, in the explosion-proof baking oven dividing at 60 ℃ or 70 ℃, wind speed 3m/, be dried.
But, with regard to the antiglare film of patent documentation 3 and 4, for example, in the fine display device (: liquid crystal indicator or the organic EL display etc. with the above resolution of 200ppi) in resolution higher than 150ppi, cannot in keeping anti-glare, reduce dazzle.Particularly; conventionally exist the distance of display surface and antiglare layer more far more easily to produce the tendency of dazzle; and with regard to the protection or protective film (being pasted on the film of display surface after buying by user) of display device; due to across tack coat etc.; therefore; itself and display surface distant, is difficult to suppress dazzle.And in fine display device, organic EL panel, because the luminous intensity of pixel is high, so easily produce dazzle, is difficult to realize anti-glare and suppresses character fuzzy simultaneously, the antiglare film of patent documentation 3 and 4 can not realize having both of above-mentioned characteristic.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-215307 communique (claims)
Patent documentation 2: TOHKEMY 2011-13238 communique (claims, [0012] [0035] section)
Patent documentation 3: No. 4377578 communique of Jap.P. (claim 1, [0058] [0059] [0071] [0083] section, embodiment)
Patent documentation 4: TOHKEMY 2008-225195 communique (claims, [0068] [0069] [0074] [0075] section, embodiment)
Summary of the invention
The problem that invention will solve
Therefore, the object of the present invention is to provide the balance excellence of a kind of mist degree and distinctiveness, for example, also can improve anti-glare, highly suppress dazzle and can suppress antiglare film and the manufacture method thereof that character is fuzzy even if be arranged at fine display device (: liquid crystal indicator, the organic EL display etc. with the above resolution of 200ppi).
Even if other object of the present invention is to provide a kind of display surface with respect to fine display device such as organic EL panels (or organic EL display) remotely to arrange mutually, also can has both anti-glare and resistance to dazzle and can improve antiglare film and the manufacture method thereof of mar resistance.
The method of dealing with problems
First the inventor etc. inquire into the mechanism of having utilized the existing antiglare film of spinodal decomposition of incompatible resin composition cannot realize anti-glare and resistance to dazzle in fine display device simultaneously.As shown in Figure 1, existing utilization be separated form concaveconvex structure be mainly that droplet-like structure is comparatively periodically arranged the structure forming.Being separated is to follow solvent evaporation to become thermodynamic instability state because being dissolved in equably in coating fluid in the resin compound of Thermodynamically stable state, thereby causes spinodal decomposition and the phenomenon that produces.It is characterized in that, because system entirety reaches thermodynamic instability state simultaneously, being separated of homogeneous occurs in coated surface, therefore form comparatively periodically and the concave-convex surface shape of size uniform.But, if with respect to the Pixel Dimensions corresponding with the above resolution of 200ppi, reduce concave-convex surface geomery to the degree that can suppress dazzle, anti-glare reduces, and extraneous light is mirrored display surface and is caused image quality impaired.On the other hand, if increase the pitch angle of convex form in order to improve anti-glare, mist degree rises, and produces character fuzzy.
It is generally acknowledged, dazzle is caused by lens effect in the situation that the size of concaveconvex structure approaches Pixel Dimensions on the order of magnitude.Although just infer, but generally following phenomenon is regarded as to dazzle: in the situation that concaveconvex shape exists across pixel, the transmitted light of each pixel is refracted to different directions because of the existence of concaveconvex shape, originally should arrive as the colour mixture of RGB that estimator's eye color and brightness change randomly corresponding to the spacing of concaveconvex structure, inclination and evaluated person feels.In the situation that concaveconvex structure is fully less than pixel, even across the concavo-convex existence of pixel, its ratio also less and refraction also little, be therefore difficult for feeling dazzle.On the other hand, in the situation that concaveconvex structure is fully greater than pixel, if the inclination of concaveconvex shape is large, transmitted light is reflected significantly and is produced lens effect, but it is less to tilt, and the refraction of transmitted light is also fewer, is more difficult for feeling dazzle.More easily judge as an example of extreme case example, can predict, if pitch angle is infinitely close to zero, it substantially becomes plane and dazzle is eliminated.
Based on this, the discoveries such as the inventor, existing antiglare film easily produces dazzle owing to having drop phase structure, thereby the inventor etc. pay close attention to common external phase structure (continuous structure or altogether continuous shape phase separation structure altogether).; for the phase separation structure that comprises common external phase structure; need to adjust by Pixel Dimensions, and by being the width that is fully less than pixel by forming the width adjustment of the protuberance of external phase structure altogether, can on Width, avoid producing the factor of dazzle.On the other hand, in length (long continuously) direction of protuberance, except end, there is not in theory inclination, be therefore difficult for producing dazzle yet.Particularly, be not only common external phase structure, drop phase structure is in the case of the length in island territory is larger, and end proportion also can diminish, and therefore is more difficult for producing dazzle.In addition, though the size of Width is little, the island territory portion that external phase structure and length are large is altogether significantly expansion in face direction, is therefore easy to guarantee anti-glare.And altogether external phase structure is the little in fact structure of rake, the factor that therefore produces light scattering is few, and than having and the surface relief structure of the droplet-like of Width same degree size, mist degree is lower, is therefore difficult for producing character fuzzy.
The inventor etc. are based on the recognition, conduct in-depth research in order to solve above-mentioned problem, found that, form and there is branched structure and total length is elongate protuberance more than 100 μ m densely by following being separated of various kinds of resin composition on antiglare layer surface, the balance excellence of mist degree and distinctiveness can be provided, for example, even if (: the liquid crystal indicator with the above resolution of 200ppi be disposed at fine display device, organic EL display etc.) also can improve anti-glare, can highly suppress dazzle, and it is fuzzy to suppress character, thereby complete the present invention.
, antiglare film of the present invention is the antiglare film that comprises surface and have the antiglare layer of elongate protuberance, follows being separated of various kinds of resin composition to form, wherein, described elongate protuberance has branched structure and total length is more than 100 μ m, and, every 1mm of described antiglare layer 2there is 1 the above elongate protuberance in surface.Described elongate protuberance forms common external phase structure, and the mean diameter of the mesh of external phase structure can be 1～70 μ m altogether.On the surface of described antiglare layer, have the elongate protuberance of branched structure and the Length Ratio of other protuberance can for the former/left and right, the latter=100/0～50/50.Antiglare film of the present invention can have 70～100% transmission image vividness, 10～40% mist degree, total light transmittance of 70～100%, and described transmission image vividness is to utilize the reflection measuring instrument of the optical slot that has used wide 0.5mm to measure.Described various kinds of resin composition can: comprise multiple polymers and be selected from least one the curable resin precursor in lower group, described multiple polymers is selected from styrene resin, (methyl) acrylic resin, alicyclic olefin resinoid, polyester resin, aliphatics organic acid cellulose esters and aromatic organic acid cellulose esters, the group of described curable resin precursor comprises: epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate, organosilicon (methyl) acrylate and at least there is the multi-functional monomer of two polymerism unsaturated links, and, at least two kinds of compositions in described polymkeric substance are separated by the spinodal decomposition from liquid phase, and, described curable resin precursor has passed through and has solidified.The viscosity (25 ℃) that described curable resin precursor also can comprise according to JIS Z8803 is the low cementation voltinism resin precursor below 3000mPas.Antiglare film of the present invention can be while being arranged at the display device with 200ppi resolution, even if antiglare layer also can suppress the antiglare film of dazzle apart from distance more than display surface 0.05mm.Described display device can be organic EL display.Antiglare film of the present invention can further comprise hyaline membrane, and described antiglare layer is formed in the one side of this hyaline membrane.In this antiglare film, can form tack coat at the another side of hyaline membrane.Antiglare film of the present invention also can be for being arranged at protection or the protective film of display device (particularly organic EL display) most surface.
In the present invention, also comprise the manufacture method of described antiglare film, the method comprises: the solution that coating comprises various kinds of resin composition also utilizes the spinodal decomposition of following solvent evaporation and occur to form the drying process of phase separation structure.In described drying process, can at the temperature that exceedes 80 ℃, heat.
It should be noted that; in this manual, " (methyl) acryloyl group ", " (methyl) acrylate " and " (methyl) acrylic acid " represent respectively " acryloyl group or methacryl ", " acrylate or methacrylate " and " acrylic or methacrylic acid ".
The effect of invention
In the present invention, on the surface of antiglare layer, follow being separated of various kinds of resin composition and be formed with densely and there is branched structure and total length is elongate protuberance more than 100 μ m, therefore, the balance excellence of mist degree and distinctiveness, for example, also can improve anti-glare even if be disposed at fine display device (: liquid crystal indicator, the organic EL display etc. with the above resolution of 200ppi), can highly suppress dazzle, and it be fuzzy to suppress character.And, even remotely arrange mutually with respect to the display surface of the fine display device such as organic EL panel, also can take into account anti-glare and resistance to dazzle, and can improve mar resistance.Therefore,, even if be used as the diaphragm of the fine display device such as organic EL panel, also can have both above-mentioned characteristic.
Accompanying drawing explanation
Fig. 1 is the laser reflection microphotograph on the antiglare layer surface of the existing antiglare film (antiglare film obtaining in comparative example 2) of having utilized the spinodal decomposition of incompatible resin composition.
Fig. 2 is the laser reflection microphotograph on the antiglare layer surface of the antiglare film that obtains in embodiment 1.
Fig. 3 is the laser reflection microphotograph on the antiglare layer surface of the antiglare film that obtains in embodiment 2.
Embodiment
[antiglare layer]
Antiglare film of the present invention comprises antiglare layer, and this antiglare layer surface has elongate (or strip) protuberance of following being separated of various kinds of resin composition and form, can show anti-glare by the surface relief structure being formed by elongate protuberance.Particularly, in the present invention, because this elongate protuberance has branched structure and has total lengths more than 100 μ m, form common external phase structure on antiglare layer surface with high density state simultaneously, therefore the balance excellence of mist degree and distinctiveness, even if be disposed at fine display device, also can in the situation that not destroying anti-glare, suppress to heavens dazzle, and it is fuzzy to suppress character.
(elongate protuberance)
Elongate protuberance follows being separated of various kinds of resin composition to form by method described later, and on the surface of antiglare layer, elongate (rope form or wire) protuberance is formed as roughly mesh-shape.Therefore, for example can observe on the surface of antiglare layer, with two-dimension netted areolation (just like mesh-shape pattern of the crust of netted melon), the i.e. irregular multiple ring-type (: the ring-type of continuous annular or part shortcoming) of being formed with.
Particularly, with regard to antiglare layer, the every 1mm needing only on its surface 2there is 1 elongate protuberance that there is above branched structure and there is the total length of 100 μ m above (preferably 200 μ m above, further preferably more than 500 μ m).It should be noted that, above-mentioned elongate protuberance also can have multiple, but is that the in the situation that of being total to external phase structure, the length with the above-mentioned elongate protuberance of branched structure becomes endless whole of antiglare layer, measure in any region, it exists number to be 1.Described " total length " of elongate protuberance refers to, by the total length that the length phase adduction of each of branch has occurred and obtain on continuous elongate protuberance.
The branched structure of elongate protuberance at least has a branch, but preferred elongated shape protuberance branches into mesh-shape, forms external phase structure (continuous structure or altogether external phase isolating construction altogether) altogether.In this manual, described " external phase structure altogether " refers to that the droplet-like male structure of the conduct origin producing in manufacture process is connected and the continuous structure (or areolation) of formation in phase separation.
It should be noted that, it is to be all total to external phase structure that elongate protuberance does not need, also can comprise the droplet-like male structure (, not thering is the non-elongated shape protuberances such as the elongate protuberance of branch and circular protuberance, oval protrusion) as origin.In the present invention, by having such elongate protuberance, compared with the island protuberance of drop phase structure (or island structure), end proportion reduces, and can suppress dazzle and character is fuzzy.And, follow the also less structure of inclination that common external phase structure that being separated of resinous principle is formed is end, therefore can suppress dazzle and character is fuzzy.
On the surface of above-mentioned antiglare layer, the Length Ratio with the elongate protuberance of branched structure and other protuberance (as the droplet-like protuberance of origin) for example can be selected from: the former/scope of left and right, the latter=100/0～10/90, be for example 100/0～30/70 (for example, 99/1～30/70), (be for example preferably 100/0～50/50,95/5～50/50), more preferably 100/0～70/30 (particularly 100/0～90/10) left and right, be particularly preferably roughly 100% (for example, whole is to be total to external phase structure).Preferred above-mentioned elongate protuberance shared ratio in protuberance is higher, conventionally, is more than 50% (for example, 50～90%) with respect to protuberance total length (summation of the length of above-mentioned elongate protuberance and the length of other protuberance).Therefore as improve anti-glare if Length Ratio is little, the ratio of elongate protuberance with branched structure is very few, and the ratio of drop phase structure becomes many,, easily produces dazzle, character is fuzzy.
The common external phase structure being formed by elongate protuberance is arranged with irregularly shaped by the mesh with same degree diameter conventionally.The mean diameter of each mesh of external phase structure (is the anisotropy shapes such as ellipse or rectangle at each mesh of common external phase structure altogether, for the mean value of major diameter and minor axis) can for 1～70 μ m for example (for example, 1～40 μ m), (be for example preferably 2～50 μ m, 3～30 μ m), more preferably 5～20 μ m (particularly 10～20 μ m) left and right.As excessive in mesh diameter, easily produce dazzle, character is fuzzy, as too small, easily cause anti-glare to reduce.
The shape (two-dimensional shapes on antiglare layer surface) of each elongate protuberance is generally the rope form (wire or fibrous) partly or entirely with curve part, the mean breadth of elongate protuberance is 0.1～30 μ m, as long as select and be adjusted into the less width that can suppress dazzle corresponding to the pixel of display device from above-mentioned scope, be for example 0.1～20 μ m, be preferably 0.1～15 μ m, more preferably 0.1～10 μ m (particularly m) left and right of 0.1～5 μ.As excessive in width, easily produce dazzle and character is fuzzy, as too small, anti-glare reduces.It should be noted that, droplet-like protuberance can make surface configuration towards the optimized direction of surface tension is changed when connected, therefore, droplet-like protuberance be connected and the width of the elongate protuberance of the common external phase structure that forms not necessarily with droplet-like protuberance measure-alike as origin.
The average height of elongate protuberance, for for example 0.05～10 μ m, is preferably 0.07～5 μ m, more preferably 0.09～3 μ m (particularly m) left and right of 0.1～2 μ.The pitch angle of elongate protuberance, for for example below 10 °, is preferably 0.5～5 °, more preferably 1～3 ° of left and right.The height of protuberance is high, tilt when large, easily produces dazzle, character is fuzzy.
On antiglare layer surface, for example, for for example 10～99.9% (, 30～99.8%), (be for example preferably 50～99.5% with respect to the area ratio of whole protuberances on whole surface, 80～99%), more preferably 90～99% (particularly 95～98%) left and right.If the area between elongate protuberance is too small, easily cause anti-glare to reduce, if excessive, easily produce dazzle, character is fuzzy.
It should be noted that, in this manual, the size of elongate protuberance or shape (having or not branch etc.), area can the two-dimensional shapes based on observing on microphotograph be measured or evaluate.In addition, mean value is the mean value of the value measured more than any 10 places.In addition, the Length Ratio of elongate protuberance and other protuberance can be at 1mm 2region in measure each length and trying to achieve.Particularly, for the elongate protuberance in the present invention (or being total to syndeton), because meeting is connected and is formed continuous structure by drop phase structure, therefore in the time carrying out microscopic examination, ridge shape (the mountain crest line shape) part that the shape of each elongate protuberance can be formed by connecting based on protuberance summit is identified.In addition, in this manual, the length that the length of elongate protuberance can be made as to above-mentioned ridge part is measured, and the mesh diameter of external phase structure can be tried to achieve based on above-mentioned ridge part altogether.Specifically measure by the method for recording in aftermentioned embodiment.It should be noted that, the pitch angle of elongate protuberance can utilize the surface roughometer (for example, accurate " SURFCOM " manufacturing of (strain) Japan) based on JIS standard to measure.
(resinous principle)
Antiglare layer comprises the various kinds of resin composition that can be separated, and the phase separation structure of this antiglare layer is by forming from liquid phase generation spinodal decomposition (wet type spinodal decomposition).As resinous principle, as long as comprise the resinous principle that can be separated, but from the viewpoint of forming above-mentioned elongate protuberance and can improve mar resistance, preferably comprise component of polymer and curable resin precursor.
(component of polymer)
As component of polymer, conventionally use thermoplastic resin.As thermoplastic resin, can illustrate: styrene resin, (methyl) acrylic resin, organic acid vinyl ester resinoid, vinyl ether resinoid, halogen-containing resin, olefine kind resin (comprising alicyclic olefin resinoid), polycarbonate resin, polyester resin, polyamide-based resin, thermoplastic polyurethanes resin, polysulfones resin (polyethersulfone, polysulfones etc.), polyphenylene oxide resinoid (2, the polymkeric substance of 6-xylenols etc.), cellulose derivative (cellulose esters, cellulose carbamate class, cellulose ethers etc.), organic siliconresin (dimethyl silicone polymer, PSI etc.), rubber or elastic body (polybutadiene, the polydienes such as polyisoprene, Styrene-Butadiene, acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, organic silicon rubber etc.) etc.These thermoplastic resins can be used singly or in combination more than two kinds.
Styrene resin comprises the homopolymer of styrene monomer or the multipolymer of multipolymer (polystyrene, styrene-α-methylstyrene multipolymer, styrene-ethylene base toluene multipolymer etc.), styrene monomer and other polymerizable monomer [(methyl) acrylic monomer, maleic anhydride, maleimide monomer, dienes etc.] formation etc.As styrene copolymer, for example can enumerate: multipolymer [styrene-methylmethacrylate copolymer, styrene-methyl methacrylate-(methyl) acrylate copolymer, styrene-methyl methacrylate-(methyl) acrylic copolymer etc.], styrene-maleic anhydride copolymer etc. that styrene-acrylonitrile copolymer (AS resin), styrene and (methyl) acrylic monomer form.Preferred styrene resin comprises the multipolymer [multipolymer take styrene and methyl methacrylate as principal ingredient such as styrene-methylmethacrylate copolymer], AS resin, Styrene-Butadiene of polystyrene, styrene and the formation of (methyl) acrylic monomer etc.
As (methyl) acrylic resin, can use: the multipolymer that the homopolymer of (methyl) acrylic monomer or multipolymer, (methyl) acrylic monomer and co-polymerized monomer form etc.In (methyl) acrylic monomer, for example, can illustrate: (methyl) acrylic acid; (methyl) acrylic acid C such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA 1-10arrcostab; (methyl) acrylic acid aryl esters such as (methyl) phenyl acrylate; (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid hydroxy propyl ester; (methyl) glycidyl acrylate; N, N-dialkyl aminoalkyl (methyl) acrylate; (methyl) vinyl cyanide; Tristanes etc. have alicyclic alkyl (methyl) acrylate etc.In co-polymerized monomer, can illustrate: above-mentioned styrene monomer, vinyl ester monomer, maleic anhydride, maleic acid, fumaric acid etc.These monomers can be used singly or in combination more than two kinds.
As (methyl) acrylic resin, for example, can enumerate: polymethylmethacrylate etc. gather (methyl) acrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylic styrene copolymer (MS resin etc.) etc.As preferred (methyl) acrylic resin, can enumerate: poly-(methyl) acrylic acid C such as poly-(methyl) methyl acrylate 1-6arrcostab, particularly take methyl methacrylate as principal ingredient the methyl methacrylate resinoid of (50～100 % by weight, preferably 70～100 about % by weight).
As organic acid vinyl esters resinoid, can enumerate: multipolymer (vinyl-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, vinyl acetate-(methyl) acrylate copolymer etc.) or their derivant that the homopolymer of vinyl ester monomer or multipolymer (polyvinyl acetate, polyvinyl proprionate etc.), vinyl ester monomer and co-polymerized monomer form.The derivant of vinyl esters resinoid comprises polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer, polyvinyl acetal resin etc.
As vinyl ether resinoid, can enumerate: the vinyl C such as methoxy ethylene, ethyl vinyl ether, vinyl propyl ether, the tertiary butyl ether of vinyl 1-10the homopolymer of alkyl ether or multipolymer, vinyl C 1-10the multipolymer (vinyl alkyl ethers-copolymer-maleic anhydride etc.) that alkyl ether and co-polymerized monomer form.
As halogen-containing resin, can enumerate: Polyvinylchloride, Kynoar, vinyl chloride vinyl acetate copolymer, vinyl chloride-(methyl) acrylate copolymer, vinylidene chloride-(methyl) acrylate copolymer etc.
In olefine kind resin, for example, can enumerate: the homopolymer of the alkene such as tygon, polypropylene, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethene-(methyl) acrylic copolymer, ethene-multipolymers such as (methyl) acrylate copolymer.As alicyclic olefin resinoid, can illustrate: the multipolymer (ethylene-norbornene copolymer, propylene-norbornene copolymer etc.) that the homopolymer of cyclic olefin (norborene, dicyclopentadiene etc.) or multipolymer (for example, three-dimensional and upright and outspoken tristane etc. has the polymkeric substance of alicyclic alkyl etc.), above-mentioned cyclic olefin and co-polymerized monomer form etc.Alicyclic olefin resinoid for example can obtain with the form of the commodity of the commodity of trade name " ARTON ", trade name " ZEONEX " etc.
Comprise fatty poly-ester carbonate such as aromatic copolycarbonate, diethylene glycol diene propyl carbonate take bisphenols (bisphenol-A etc.) as matrix etc. at polycarbonate resin.
In polyester resin, can illustrate: aromatic polyester [the poly terephthalic acid C such as polyethylene terephthalate, polybutylene terephthalate that uses the aromatic dicarboxylic acid such as terephthalic acid (TPA) 2-4alkylene ester or poly-naphthalenedicarboxylic acid C 2-4alkylene ester etc. all polyester, comprise aromatic acid C 2-4alkylene ester unit (terephthalic acid (TPA) C 2-4alkylene ester and/or naphthalenedicarboxylic acid C 2-4alkylene ester unit) for example, as copolyesters of principal ingredient (, more than 50 % by weight) etc.].As copolyesters, comprising: poly-aromatic acid C 2-4in the structural unit of alkylene ester, C 2-4a part for aklylene glycol is by polyoxy C 2-4aklylene glycol, C 6-10aklylene glycol, alicyclic diol (cyclohexanedimethanol, hydrogenated bisphenol A etc.), there is the copolyesters that the replacement such as glycol (having 9 of Fluorenone side chain, two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes of 9-, bisphenol-A, bisphenol-A-alkylene oxide adducts etc.) of aromatic ring forms; A part for aromatic dicarboxylic acid is by aliphatics C such as the asymmetric aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, hexane diacids 6-12the copolyesters that the replacements such as dicarboxylic acid form.Polyester resin also comprises: polyarylate resinoid, used homopolymer or the multipolymer of the lactone such as aliphatic polyester, 6-caprolactone of the aliphatic dicarboxylic acids such as hexane diacid.Preferred polyester resin is conventionally for example, as amorphism copolyesters (, aromatic acid C 2-4alkylene ester class copolyesters etc.) etc. be like that amorphism.
As polyamide-based resin, can enumerate: the fatty polyamides such as nylon 46, nylon 6, nylon 66, NYLON610, nylon 612, nylon 11, nylon 12; The polyamide such as, such as, being obtained by dicarboxylic acid (terephthalic acid (TPA), isophthalic acid, hexane diacid etc.) and diamines (hexamethylene diamine, m-xylene diamine) etc.Polyamide-based resin can be homopolymer or the multipolymer of the lactams such as epsilon-caprolactams, also can be not limited to homopolyamide and is copolyamide.
In cellulose derivative, as cellulose esters, for example, can illustrate: the aliphatics organic acid esters (cellulose ethanoate such as cellulose diacetate, cellulose triacetate; The C such as cellulose propionate, cellulose butyrate, cellulose-acetate propionate, cellulose acetate-butyrate 1-6organic acid esters etc.), the aromatic organic acid ester (C such as cellulose phthalic acid ester, cellulose benzoate 7-12aromatic carboxylic acid esters), inorganic acid ester class (for example, cellulose phosphate, sulfate cellulose etc.), can be also the mixed acid esters such as cellulose nitrate acetate ester.In cellulose derivative, also comprise: cellulose carbamate class (for example, cellulose carbanilate etc.), cellulose ethers (for example, cyanethyl cellulose; The hydroxyl such as hydroxyethyl cellulose, hydroxypropyl cellulose C 2-4alkylcellulose; The C such as methylcellulose, ethyl cellulose 1-6alkylcellulose; Carboxymethyl cellulose or its salt, benzylcellulose, acetyl group alkylcellulose etc.).
As preferred thermoplastic resin, for example, can enumerate: styrene resin, (methyl) acrylic resin, vinyl acetate esters resin, vinyl ether resinoid, halogen-containing resin, alicyclic olefin resinoid, polycarbonate resin, polyester resin, polyamide-based resin, cellulose derivative, silicone based resin and rubber or elastic body etc.As resin, conventionally can use as amorphism and dissolve in the resin of organic solvent (particularly can dissolve the general solvent of multiple polymers and curability compound).Particularly preferably formability or masking, the transparency, resin that weatherability is high, for example: styrene resin, (methyl) acrylic resin, alicyclic olefin resinoid, polyester resin, cellulose derivative (cellulose esters etc.) etc.
As component of polymer, also can use the polymkeric substance with the functional group (or the functional group that can react with curability compound) that participates in curing reaction.Above-mentioned polymkeric substance can have functional group on main chain, also can on side chain, have functional group.Above-mentioned functional group can be imported into main chain by copolymerization, cocondensation etc., but is conventionally imported into side chain.As such functional group, can enumerate: condensation group, reactive group are (for example, hydroxyl, anhydride group, carboxyl, amino or imino group, epoxy radicals, glycidyl, isocyanate group etc.), polymerizable group (for example, the C such as vinyl, propenyl, isopropenyl, butenyl group, allyl 2-6the C such as alkenyl, ethinyl, propinyl, butynyl 2-6the C such as alkynyl, ethenylidene 2-6alkylene group or there is group ((methyl) acryloyl group etc.) of these polymerizable groups etc.) etc.In these functional groups, preferred polymeric group.
As the method that polymerizable group is imported to side chain, for example, can adopt: make to there is reactive group, the thermoplastic resin of the functional group such as condensation group and there is the method for reacting with the polymerizable compound of the reactive group of above-mentioned functional group reactions.
As the thermoplastic resin with functional group, can illustrate: (for example there is the thermoplastic resin of carboxyl or its anhydride group, (methyl) acrylic resin, polyester resin, polyamide-based resin etc.), (for example there is the thermoplastic resin of hydroxyl, (methyl) acrylic resin, polyurethanes resin, cellulose derivative, polyamide-based resin etc.), (for example there is amino thermoplastic resin, polyamide-based resin etc.), (for example there is the thermoplastic resin of epoxy radicals, there is (methyl) acrylic resin of epoxy radicals, polyester resin etc.) etc.In addition, can be also in the thermoplastic resins such as styrene resin, olefine kind resin, alicyclic olefin resinoid, to import the resin that above-mentioned functional group obtains by copolymerization, graft polymerization.
As polymerizable compound, for the situation of thermoplastic resin with carboxyl or its anhydride group, can use: there is the polymerizable compound of epoxy radicals, hydroxyl, amino, isocyanate group etc. etc.For the situation of thermoplastic resin with hydroxyl, can enumerate: there is the polymerizable compound of carboxyl or its anhydride group or isocyanate group etc. etc.For the situation with amino thermoplastic resin, can enumerate: there is the polymerizable compound of carboxyl or its anhydride group or epoxy radicals, isocyanate group etc. etc.For the situation of thermoplastic resin with epoxy radicals, can enumerate: there are carboxyl or its anhydride group or amino etc. polymerizable compound etc.
In above-mentioned polymerizable compound, as the polymerizable compound with epoxy radicals, for example, can illustrate: the epoxy basic ring C such as epoxide ring hexenyl (methyl) acrylate 5-8alkenyl (methyl) acrylate, (methyl) glycidyl acrylate, allyl glycidyl ether etc.As the compound with hydroxyl, for example, can illustrate: (methyl) acrylic acid hydroxyl C such as (methyl) acrylic acid hydroxy propyl ester 1-4the C such as Arrcostab, ethylene glycol list (methyl) acrylate 2-6aklylene glycol (methyl) acrylate etc.As thering is amino polymerizable compound, for example, can illustrate: (methyl) acrylic-amino C such as (methyl) acrylic-amino ethyl ester 1-4the C such as Arrcostab, allyl amine 3-6the aminobenzene vinyl such as alkenyl amine, 4-aminobenzene ethene, diaminobenzene ethene etc.As the polymerizable compound with isocyanate group, for example, can illustrate: (gathering) carbamate (methyl) acrylate, isocyanic acid vinyl acetate etc.As the polymerizable compound with carboxyl or its anhydride group, for example, can illustrate: insatiable hunger carboxylic acid or its acid anhydrides etc. such as (methyl) acrylic acid, maleic anhydride.
As representative example, can enumerate: there is the thermoplastic resin of carboxyl or its anhydride group and containing the combination, particularly (methyl) acrylic resin ((methyl) acrylic acid-(methyl) acrylate copolymer etc.) of epoxy compounds with containing the combination of (methyl) acrylate (epoxy radicals cycloalkenyl (methyl) acrylate, (methyl) glycidyl acrylate etc.) of epoxy radicals.Particularly, can use: on the part carboxyl of (methyl) acrylic resin, import the polymkeric substance that polymerism unsaturated group forms, for example: make the part carboxyl and 3 of (methyl) acrylic acid-(methyl) acrylate copolymer, thus (methyl) acrylic polymers that the epoxy reaction of 4-epoxide ring hexenyl methacrylate forms at side chain lead-in light polymerism unsaturated group etc.
With respect to thermoplastic resin 1kg, the functional group's (particularly polymerizable group) that participates in curing reaction is 0.001～10 mole with respect to the import volume of thermoplastic resin, is preferably 0.01～5 mole, more preferably 0.02～3 mole of left and right.
These polymkeric substance can appropriately combinedly use., polymkeric substance also can be made up of multiple polymers.Multiple polymers also can be separated by liquid phase spinodal decomposition.In addition, multiple polymers also can objectionable intermingling.The in the situation that of combination multiple polymers, the combination of the first resin and the second resin is not particularly limited, and can adopt mutual exclusive multiple polymers, for example mutual exclusive two kinds of polymkeric substance appropriately combined use near processing temperature.For example, in the situation that the first resin is styrene resin (polystyrene, styrene-acrylonitrile copolymer etc.), the second resin can be cellulose derivative (for example, the cellulose esters such as cellulose-acetate propionate), (methyl) acrylic resin (polymethylmethacrylate etc.), alicyclic olefin resinoid (polymkeric substance take norborene as monomer etc.), polycarbonate resin, polyester resin (above-mentioned poly-aromatic acid C 2-4alkylene ester class copolyesters etc.) etc.In addition, for example the first polymkeric substance be cellulose derivative (for example, the cellulose esters such as cellulose-acetate propionate) situation under, the second polymkeric substance can be styrene resin (polystyrene, styrene-acrylonitrile copolymer etc.), (methyl) acrylic resin, alicyclic olefin resinoid (polymkeric substance take norborene as monomer etc.), polycarbonate resin, polyester resin (above-mentioned poly-aromatic acid C 2-4alkylene ester class copolyesters etc.) etc.In the combination of various kinds of resin, can at least use cellulose esters (for example, the cellulose C such as cellulose diacetate, cellulose triacetate, cellulose-acetate propionate, cellulose acetate-butyrate 2-4alkyl carboxylic ester).
It should be noted that, there is final solidifying by active ray (ultraviolet ray, electron beam etc.), heat etc. in the phase separation structure generating by spinodal decomposition, thereby form cured resin.Thus, antiglare layer can be given with mar resistance, permanance can be improved.
The viewpoint of the mar resistance from solidifying is considered, preferably in multiple polymers, at least one polymkeric substance, for example, a kind of polymkeric substance (by the first resin and the second resin combination in the situation that, particularly two kinds of polymkeric substance) in mutual exclusive polymkeric substance for side chain have can with the polymkeric substance of the functional group of curable resin precursors reaction.
The ratio (weight ratio) of the first polymkeric substance and the second polymkeric substance is for example selected from: the former/the latter=1/99～99/1, preferably 5/95～95/5, the further preferred scope of 10/90～90/10 left and right, is generally 20/80～80/20 left and right, is in particular 30/70～70/30 left and right.
It should be noted that, as the polymkeric substance that is used to form phase separation structure, except above-mentioned inconsistent two kinds of polymkeric substance, also can comprise above-mentioned thermoplastic resin or other polymkeric substance.
The glass transition temperature of polymkeric substance is selected from for example-100 ℃～250 ℃, preferably-50 ℃～230 ℃, the further preferred scope of 0～200 ℃ of left and right (for example, 50～180 ℃ of left and right).It should be noted that, consider from the viewpoint of skin hardness, glass transition temperature is 50 ℃ above (for example, 70～200 ℃ of left and right), preferably for example, comparatively favourable when 100 ℃ above (100～170 ℃ of left and right).The weight-average molecular weight of polymkeric substance is for example selected from below 1,000,000, the preferred scope of 1,000～500,000 left and right.
(curable resin precursor)
As curable resin precursor, can use: there is the compound of the functional group of reacting by heat, active energy ray (ultraviolet ray, electron beam etc.) etc., thereby can be cured or the crosslinked various curability compounds that form resin (particularly solidifying or cross-linked resin) by heat, active energy ray etc.As above-mentioned resin precursor, for example, can illustrate: heat-curable compounds or resin [have epoxy radicals, polymerizable group, isocyanate group, alkoxysilyl, the low molecular weight compound of silanol group etc. (for example, epikote, unsaturated polyester esters resin, ammonia esters resin, silicone based resin etc.) etc.], photocurable compound (the photo-curable monomer that can be cured by active ray (ultraviolet ray etc.), the ultra-violet solidified compound such as oligomer etc.) etc., photocurable compound can be also EB (electron beam) curability compound etc.It should be noted that, also by photo-curable monomer, oligomer or be optionally that the photocurable compounds such as low-molecular-weight light-cured resin are referred to as " light-cured resin ".
Photocurable compound comprises for example monomer, oligomer (or resin, particularly low-molecular-weight resin), as monomer, for example, can illustrate: simple function monomer [(methyl) acrylic monomer such as (methyl) acrylate, the vinyl monomers such as vinyl pyrrolidone, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester etc. has (methyl) acrylic acid of endocyclic alkyl etc.], at least there is multi-functional monomer [ethylene glycol bisthioglycolate (methyl) acrylate of two polymerism unsaturated links, propylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, aklylene glycol two (methyl) acrylate such as hexanediol two (methyl) acrylate, (gathering) oxyalkylene glycol two (methyl) acrylate such as diethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyoxy tetramethylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, diamantane two (methyl) acrylate etc. have two (methyl) acrylate of endocyclic alkyl, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc. have the multi-functional monomer of the polymerism unsaturated link of 3～6 left and right].
As oligomer or resin, can illustrate: (methyl) acrylate of bisphenol-A-alkylene oxide adducts, epoxy (methyl) acrylate (bisphenol type epoxy (methyl) acrylate, phenolic varnish type epoxy (methyl) acrylate etc.), polyester (methyl) acrylate (for example, aliphatic polyester type (methyl) acrylate, aromatic polyester type (methyl) acrylate etc.), (gathering) carbamate (methyl) acrylate (polyester urethane (methyl) acrylate, polyether-type carbamate (methyl) acrylate etc.), organosilicon (methyl) acrylate etc.These photocurable compounds can be used singly or in combination more than two kinds.
Preferred curable resin precursor be can be curing at short notice photocurable compound, for example: ultra-violet solidified compound (monomer, oligomer or be optionally low-molecular-weight resin etc.), EB curability compound.Particularly, being conducive to practical resin precursor is uv curing resin.In addition,, in order to improve the patience such as mar resistance, preferably photocurable compound (light-cured resin) is for having the compound of 2 above (preferably 2～15, further preferably 4～10 left and right) polymerism unsaturated links in molecule.Particularly, preferably epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate, organosilicon (methyl) acrylate, at least there is the multi-functional monomer of two polymerism unsaturated links.
As the molecular weight of curable resin precursor, consider the compatibility of itself and polymkeric substance, be below 5000, be preferably below 2000, more preferably left and right below 1000.
The viscosity of curable resin precursor (based on the viscosity at 25 ℃ of JIS Z8803) can be selected from the scope of 100～10000mPas (particularly 500～8000mPas) left and right.From the viewpoint of the above-mentioned elongate protuberance of easy formation, particularly preferably curable resin precursor at least comprises the low cementation voltinism resin precursor with the following viscosity of 3000mPas.The viscosity of low cementation voltinism resin precursor (based on the viscosity at 25 ℃ of JIS Z8803) is for example 100～3000mPas, be preferably 300～2800mPas, more preferably 500～2500mPas (particularly 1000～2300mPas) left and right.If the viscosity of low cementation voltinism resin precursor is too high, be difficult to form above-mentioned elongate protuberance.The mechanism that easily forms above-mentioned elongate protuberance by comprising low cementation voltinism resin precursor is still not clear, but can infer this is to improve because: low cementation voltinism resin precursor makes the degree of freedom of the melt fluidity of coating fluid in drying process, the particularly above-mentioned thermoplastic resin that is separated, promote thus spinodal decomposition, thereby promote the transformation of drop phase structure to common external phase structure.
The ratio of low cementation voltinism resin precursor is with respect to all resins composition, the scope that can be selected from 1～50 % by weight left and right for example, is 3～40 % by weight, be preferably 5～35 % by weight, more preferably 10～30 % by weight (particularly 15～25 % by weight) left and right.If the ratio of low cementation voltinism resin precursor is too much, follow being separated of spinodal decomposition and the concavo-convex formation of initial stage that occurs is suppressed, protuberance reduces because of the connected chance of melting, so be difficult to form elongate protuberance; If the ratio of low cementation voltinism resin precursor is very few, because the melt fluidity of coating fluid declines, thereby be difficult to form elongate protuberance.
Curable resin precursor also can comprise hardening agent according to its kind.For example, for thermoset resin, the hardening agent of amine, polybasic carboxylic acid class etc. can be comprised, for light-cured resin, Photoepolymerizationinitiater initiater can be comprised.As Photoepolymerizationinitiater initiater, can illustrate: usual composition, for example: acetophenones or phenylpropyl alcohol ketone, benzil class, benzoyl class, benzophenone, thioxanthene ketone, acylphosphine oxide (ア シ Le ホ ス Off ィ Application オ キ シ De) class etc.The content of the hardening agent such as light curing agent is 0.1～20 weight portion with respect to curable resin precursor 100 weight portions, be preferably 0.5～10 weight portion, more preferably 1～8 weight portion (particularly 1～5 weight portion) left and right can be also 3～8 weight portion left and right.
Further, curable resin precursor also can comprise curing accelerator.For example, for light-cured resin, can comprise photocuring promoter, for example: tertiary amines (dialkyl amido benzoic ether etc.), phosphine class photopolymerization promoter etc.
In at least one polymkeric substance and at least one curable resin precursor, can be with near at least two kinds of compositions that are used in combination that are separated each other processing temperature.As the combination being separated, for example, can enumerate: the combination that between the multiple curable resin precursor of combination, (c) that combination, (b) the polymkeric substance concurrent looks incompatible with curable resin precursor that (a) between multiple polymers, the concurrent looks of objectionable intermingling separates separates, the concurrent looks of objectionable intermingling separates etc.In these combinations, the preferably combination of combination, (b) polymkeric substance and the curable resin precursor between (a) multiple polymers conventionally, the particularly preferably combination between (a) multiple polymers.In the case of both compatibility that is separated is high, with so that in the dry run of solvent evaporation, both can not be separated effectively, as the function reduction of antiglare layer.
It should be noted that, thermoplastic resin and curable resin precursor (or cured resin) be objectionable intermingling conventionally.In the situation that polymkeric substance concurrent looks incompatible with curable resin precursor separates, as polymkeric substance, also can use multiple polymers.In the situation that using multiple polymers, at least one polymkeric substance is incompatible with respect to resin precursor (or cured resin), and other polymkeric substance can be compatible with above-mentioned resin precursor.
In addition, also can make mutual exclusive two kinds of thermoplastic resins and curability compound (particularly thering is monomer or the oligomer of multiple curability functional group) combination.And, the viewpoint consideration of the mar resistance from solidifying, a kind of polymkeric substance (particularly two kinds of polymkeric substance) in above-mentioned inconsistent thermoplastic resin can be for having the thermoplastic resin of the functional group's (participating in the curing functional group of above-mentioned curable resin precursor) that participates in curing reaction.
The in the situation that of being separated forming polymkeric substance by mutual exclusive multiple polymers, can be used in combination at least one polymkeric substance in curable resin precursor and inconsistent multiple polymers with compatible with each other near processing temperature., for example, in the situation that mutual exclusive multiple polymers is made up of the first resin and the second resin, at least one in curable resin precursor and the first resin or the second resin is compatible, also can be preferably compatible with two kinds of component of polymer.Compatible with two kinds of component of polymer in the situation that, be separated as at least two-phase, described at least two-phase is the potpourri take the first resin and curable resin precursor as the potpourri of principal ingredient with take the second resin and curable resin precursor as principal ingredient.
In the case of the compatibility of selected multiple polymers is high, with so that in the dry run of solvent evaporation, can not effectively be separated between polymkeric substance, reduce as the function of antiglare layer.The being separated property of multiple polymers can be judged as follows: use the solvent that is good solvent with respect to two kinds of compositions to prepare uniform solution, making in the process of solvent slow evaporation, confirm that by range estimation whether residual solid composition produces gonorrhoea, can judge thus easily.
In addition, conventionally, polymkeric substance and resin precursor solidify and refractive index between solidifying of generating or cross-linked resin is different.In addition, the refractive index of multiple polymers (the first resin and the second resin) is also different.Polymkeric substance with solidify or the specific refractivity of the specific refractivity of cross-linked resin, multiple polymers (the first resin and the second resin) can be for example 0.001～0.2, be preferably 0.05～0.15 left and right.
The ratio (weight ratio) of polymkeric substance and curable resin precursor is not particularly limited, for example, can be selected from the former/scope of left and right, the latter=5/95～95/5, consider from the viewpoint of skin hardness, be preferably 5/95～60/40 left and right, more preferably 10/90～50/50, be particularly preferably 10/90～40/60 left and right.
[antiglare film]
Antiglare film of the present invention is at least made up of antiglare layer, and the thickness of antiglare layer for example can be formed by antiglare layer separately, but conventionally further comprises hyaline membrane, can in the one side of this hyaline membrane, be formed with antiglare layer.
In antiglare layer, also usual adjuvant can be comprised in the scope of not damaging antiglare layer optical characteristics, for example: organic or inorganic particle, stabilizing agent (antioxidant, ultraviolet light absorber etc.), surfactant, water soluble polymer, filling agent, crosslinking chemical, coupling agent, colorant, fire retardant, lubricant, wax, antiseptic, viscosity modifier, tackifier, levelling agent, defoamer etc.
The thickness of antiglare layer can be for example 0.3～20 μ m, and (for example, 1～10 μ is left and right m), is generally 2～10 μ m (particularly m) left and right of 3～7 μ to be preferably 1～15 μ m.It should be noted that, in the situation that antiglare film is made up of separately antiglare layer, the thickness of antiglare layer can be selected from 1～100 μ m for example, the preferred scope of 3～50 μ m left and right.
(hyaline membrane)
As hyaline membrane (transparent supporting body or matrix material sheet), can illustrate: glass, pottery and resin sheet.As the resin that forms hyaline membrane, can use the resin identical with above-mentioned antiglare layer.As preferred hyaline membrane, can enumerate: transparent polymer film, for example: by cellulose derivative [cellulose triacetate (TAC), the cellulose ethanoates such as cellulose diacetate etc.], polyester resin [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate resinoid etc.], polysulfones resin [polysulfones, polyethersulfone (PES) etc.], polyetherketone resinoid [polyetherketone (PEK), polyetheretherketone (PEEK) etc.], polycarbonate resin (PC), polyolefin resin (tygon, polypropylene etc.), cyclic polyolefin hydrocarbon resin [ARTON, ZEONEX etc.], halogen-containing resin (Vingon etc.), (methyl) acrylic resin, styrene resin (polystyrene etc.), the film that vinyl acetate or vinyl alcohol resin (polyvinyl alcohol (PVA) etc.) etc. form.
Hyaline membrane can pass through single shaft or biaxial stretch-formed, but is preferably optical isotropy.The support membrane that preferred hyaline membrane is low birefringence.As optically isotropic hyaline membrane, can illustrate: unstretching film, for example, can illustrate: by polyester (PET, PBT etc.), cellulose esters, particularly cellulose ethanoate class (the cellulose ethanoate C such as cellulose ethanoate, cellulose-acetate propionate, cellulose acetate-butyrate such as cellulose diacetate, cellulose triacetate 3-4organic acid esters) etc. the film that forms.
The thickness of the hyaline membrane of two-dimensional structure can be selected from 5～2000 μ m for example, preferably 15～1000 μ m, the further preferred scope of 20～500 μ m left and right.
(other optical layers)
Antiglare film of the present invention not only anti-glare is high, and light scattering is also very high.Particularly, can be isotropically increasing the scattering strength within the scope of special angle in transmission scattering transmitted light.And the distinctiveness of transmission image is also very high.Therefore, antiglare film of the present invention also can for example, form optical component with other optical layers (, polaroid, polarizer, light guide plate, antireflection plate, low-index layer etc. are disposed in the various optical elements in light path) combination., can at least one light path face of optical element, arrange or stacked above-mentioned antiglare film.For example, can, in the folded antiglare film at least one side upper strata of above-mentioned polarizer, also can on the exit facet of light guide plate, arrange or stacked antiglare film.
Particularly, the antiglare film that antiglare layer has been endowed mar resistance can be used as diaphragm performance function.Therefore; at least a slice diaphragm in two diaphragms of the suitable replacement polaroid of antiglare film of the present invention and as using the duplexer (optical component) of antiglare film; the duplexer (optical component), forming in the folded antiglare film at least one side upper strata of polaroid.In the case of the diaphragm on the two sides as polaroid uses, can prevent display surface dazzle, can give optical element (polaroid etc.) with high mar resistance simultaneously.
It should be noted that, these optical layers can replace above-mentioned hyaline membrane to use, also can be in further stacked optical layers beyond hyaline membrane.
(tack coat)
Antiglare film of the present invention can form tack coat at least a portion of the another side of above-mentioned hyaline membrane.The antiglare film that is formed with tack coat at the another side of the hyaline membrane of antiglare layer can also be as the diaphragm of the various contact panel display device including smart mobile phone, dull and stereotyped PC etc.
Tack coat is formed by usual translucent adhesive.As cementing agent, for example, can illustrate: rubber-like cementing agent, acrylic adhesive, olefines cementing agent (modified olefin class cementing agent etc.), silicone based cementing agent etc.
As rubber-like cementing agent, for example can enumerate: the combination of rubber constituent (natural rubber, synthetic rubber, thermoplastic elastomer etc.) and tackifier (terpene resin, rosin based resin, petroleum resin, modified olefin resinoid etc.) etc.
As acrylic adhesive, for example, can use: by with acrylic acid C such as ethyl acrylate, butyl acrylate, 2-EHAs 2-10arrcostab is the cementing agent that the acrylic copolymer of principal ingredient forms.As the co-polymerized monomer of acrylic copolymer, for example, can enumerate: (methyl) acrylic monomer [for example, (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid hydroxy propyl ester, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) glycidyl acrylate, acrylamide, N hydroxymethyl acrylamide etc.], polymerism nitrile compound [for example, (methyl) vinyl cyanide etc.], unsaturated dicarboxylic or derivatives thereof (for example, maleic anhydride, itaconic acid etc.), vinyl ester (for example, vinyl acetate, propionate etc.), aromatic vinyl base class (for example, styrene etc.) etc.
As olefines cementing agent, for example, can enumerate: the partly-hydrolysed thing of ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylic acid 2-hydroxy methacrylate multipolymer, ethene-(methyl) glycidyl acrylate multipolymer, ethane-acetic acid ethyenyl ester-(methyl) acrylic copolymer, ethene-(methyl) ethyl acrylate-maleic acid (acid anhydride) multipolymer, vinyl-vinyl acetate copolymer etc.
As silicone based cementing agent, for example, can use: by organic silicon rubber composition [by the R of simple function 3siO 1/2(in formula, R represents the aryl such as alkyl, phenyl such as methyl etc.; Lower with) and the SiO of four senses 2the MQ resin forming etc.] and the organic siliconresin composition (R of two independent senses 2the R of SiO or two senses 2the R of SiO and simple function 3siO 1/2the oily combining or glue (gum) shape composition etc.) be dissolved in organic solvent and the cementing agent obtaining etc.Above-mentioned organic silicon rubber composition also can pass through crosslinked.
In these cementing agents, from the viewpoint of optical characteristics and reprocessing property etc., preferred silicone based cementing agent.
The thickness of tack coat, for for example 1～150 μ m, is preferably 10～100 μ m, more preferably 20～70 μ m (particularly m) left and right of 25～50 μ.
Tack coat can be formed at whole of another side, also can be formed at a part (for example, circumference) for another side.Further, in the situation that being formed at circumference, in order to improve for bonding operability, also can forming frame shape parts (for example, at circumference laminated plastic sheet) at the circumference of antiglare film, and form tack coat on frame shape parts.
(characteristic of antiglare film)
Antiglare film of the present invention is formed with the fine concaveconvex structure corresponding to phase separation structure in a large number on the surface of antiglare layer.Therefore, can suppress to mirror because of the outdoor scene that surface reflection causes, can improve anti-glare.In addition, with regard to the evaluation of anti-glare, can evaluate mirroring of fluorescent light by range estimation, and use glossmeter to evaluate according to JIS K7105.60 ° of gloss of antiglare film of the present invention (antiglare layer) can be more than 30, for example, can be 30～80, are preferably 40～70, more preferably 50～60 (particularly 52～55) left and right.As too small in gloss, easily produce dazzle or character is fuzzy.
In addition, the evaluation that dazzle and character are fuzzy can be used the fine liquid crystal indicator of resolution 200ppi left and right to evaluate, and more simply, can use the fine smart mobile phone of 300ppi left and right to evaluate by range estimation.Antiglare film of the present invention in the time being disposed at the display device with 200ppi resolution, even antiglare layer leave 0.05mm apart from display surface more than (particularly about 0.1～0.4mm) also can suppress dazzle.
In addition, for antiglare film of the present invention, as realize the optical characteristics of avoiding such characteristic that the minimizing of the guaranteeing of anti-glare, dazzle and character are fuzzy with optimum level, preferred transmission image vividness, mist degree and total light transmittance are adjusted in particular range.
In the case of using the optical slot of wide 0.5mm, the transmission image vividness of antiglare film can be selected from the scope of 70～100% left and right, be preferably 75～100% (for example, 75～95%), more preferably 80～100% (particularly 80～90%) left and right.If transmission image vividness is too small, the fuzzy change of transmitted light is many, and during for fine display device, the soft edge of pixel, therefore easily produces character fuzzy.
Described transmission image vividness is the yardstick that quantification is carried out in the fuzzy and distortion (askew body) of the light to having seen through film.Transmission image vividness is the value of measuring after by optical slot and being calculated by the light quantity of the light and shade portion of optical slot, and described optical slot is used for the mobile transmitted light from film.That is, in the situation that film thickens transmitted light, on optical slot, the image of the slit of imaging can become thick, and therefore the light quantity of transmissive portions is below 100%, on the other hand, at transmissive portions not, produces light leak, is therefore more than 0%.The value C of transmission image vividness defines by following formula, and wherein, M is the transmitted light maximal value of optical slot hyalomere, the transmitted light minimum value m that m is opaque portion.
C(%)=[(M-m)/(M+m)]×100
That is, the value of C more approaches 100%, image blurring less [list of references: palpus is congratulated, three Tian Cun, application techniques, in the July, 1985 number] being caused by antiglare film.
As the determinator of measuring above-mentioned transmission image vividness, the reflection measuring instrument ICM-IDP that can use Suga Test Instruments (strain) to manufacture.As optical slot, can use the optical slot of width 0.125～2mm.
The mist degree of antiglare film of the present invention is for example 10～40%, is preferably 12～35%, more preferably 15～30% (particularly 20～30%) left and right.As too high in mist degree, easily produce dazzle and character is fuzzy, as too small in mist degree, anti-glare reduces.
Total light transmittance of anti-glare film of the present invention is for example 70～100%, is preferably 80～100%, and more preferably 85～100% (for example, 85～95%) are particularly preferably 90～100% (for example, 90～99%) left and right.
Mist degree and total light transmittance can be according to JIS K7105, and the NDH-5000W mist degree instrument that uses Japanese electric look industry (strain) to manufacture is measured.
The pencil hardness (750g load) of anti-glare film of the present invention (antiglare layer), according to JIS K5400, can, for for example H above (particularly more than 2H), can be also for example H～4H, is preferably 2H～3H left and right.
(manufacture method of antiglare film)
Antiglare film of the present invention is that the manufacture method by comprising drying process obtains, described drying process is upper at supporter (particularly hyaline membrane) by the solution coat that contains various kinds of resin composition, utilizes the spinodal decomposition of following solvent evaporation and occur to form phase separation structure.In the situation that comprising curable resin precursor, antiglare film of the present invention is further passed through the curing process that above-mentioned curable resin precursor is cured and is obtained.
Specifically, in drying process, use by the resin combination of various kinds of resin composition (particularly polymkeric substance and curable resin precursor) and solvent formation fluid composition or mixed liquors such as (particularly) homogeneous solutions, waiting evaporation or remove in the process of desolventizing by dry from the liquid phase (or homogeneous solution or its coating) of this resin combination, follow the concentrated of concentration, caused and be separated by spinodal decomposition, phase spacing (spacing or mesh diameter) can form more regular phase separation structure.External phase structure can be made by drying condition or the formula of setting the melt fluidity that can improve the rear resin combination of solvent evaporation altogether.
More specifically, above-mentioned wet type spinodal decomposition conventionally can be by the mixed liquor that comprises at least one polymkeric substance, at least one curable resin precursor and solvent or resin combination (uniform solution) are coated on supporter, and make solvent from coating evaporation and carry out.In the situation that using fissility supporter as above-mentioned supporter, by peeling off antiglare layer from supporter, the antiglare film that can obtain being formed separately by antiglare layer, by using non-fissility supporter (preferably clear supporter) as supporter, can obtain the antiglare film of the stepped construction being formed by supporter and antiglare layer.In addition,, by improving the evaporating temperature of solvent or using the part of low viscosity composition as resin, can make the connected common external phase structure forming of phase separation structure.Become the reason of common external phase structure for concaveconvex structure, be conventionally presumably because resinous principle after solvent evaporation also can not lose flowability, concaveconvex structure is connected because of heat melting and they.
In the present invention, while there is spinodal decomposition, follow the carrying out being separated and form common external phase structure, be separated and further carry out and when coarsening, external phase is because of self capillary existence discontinuum, can become drop phase structure (island structure of the independent phase such as spherical, just spherical, discoid or ellipsoid shaped).Therefore,, according to the degree being separated, also can form the intermediate structure (by above-mentioned altogether external phase to the phase structure in drop phase transition process) of common external phase structure and drop phase structure.In the present invention, the phase separation structure of antiglare layer can be island structure (drop phase structure or is independent or isolated phase structure mutually), be total to external phase structure (or eyed structure) in dry initial stage process, also can be for external phase structure and drop phase structure are mixed the intermediate structure existing altogether.By these phase separation structures, can be after solvent seasoning form on antiglare layer surface fine concavo-convex.In addition, in dry run, also can guarantee the degree of mobility and/or comprise low viscosity composition as resinous principle up to resin combination after solvent seasoning by making baking temperature, can make surperficial micro concavo-convex melting and be connected, even if be originally that continuous altogether structure can mutation be also the concaveconvex structure that continuity further increases.
In wet type spinodal decomposition, solvent can be selected according to kind and the dissolubility of above-mentioned polymkeric substance and curable resin precursor, as long as the solvent of dissolved solid composition (multiple polymers and curable resin precursor, reaction initiator, other adjuvant) at least equably.As such solvent, for example, can illustrate: ketone (acetone, MEK, methyl isobutyl ketone, cyclohexanone etc.), ethers (two
Figure BDA0000398980040000231
alkane, tetrahydrofuran etc.), aliphatic hydrocarbon (hexane etc.), alicyclic hydro carbons (cyclohexane etc.), aromatic hydrocarbon based (toluene, dimethylbenzene etc.), halogenated hydrocarbon (methylene chloride, ethylene dichloride etc.), ester class (methyl acetate, ethyl acetate, butyl acetate etc.), water, alcohols (ethanol, isopropyl alcohol, butanols, cyclohexanol etc.), cellosolve class (methyl cellosolve, ethyl cellosolve etc.), cellosolve acetate class, sulfoxide type (dimethyl sulfoxide etc.), amide-type (dimethyl formamide, dimethyl acetamide etc.) etc.In addition, solvent can be also mixed solvent.
As the preferred form of above-mentioned resin combination (mixed liquor), can use the composition that comprises above-mentioned thermoplastic resin, photocurable compound, Photoepolymerizationinitiater initiater and can dissolve the solvent of above-mentioned thermoplastic resin and photocurable compound, as other preferred form, also can use the composition that comprises above-mentioned mutual exclusive multiple polymers, photocurable compound, Photoepolymerizationinitiater initiater and solvent.
In the scope that the concentration of solute in mixed liquor (polymkeric substance and curable resin precursor, reaction initiator, other adjuvant) can be separated in generation and the scope of not damaging curtain coating and coating etc., select, for example, it is 1～80 % by weight, be preferably 5～60 % by weight, more preferably 15～40 % by weight (particularly 20～40 % by weight).
As curtain coating or coating process, can enumerate conventional process, for example: spraying, roller coat, airblade coating, blade coating, rod are coated with, are coated with (comma coater), dipping-extruding roller coat, mould painting, intaglio plate coating, the coating of nick version, silk screen rubbing method, infusion process, spray-on process, spin-coating method etc. against roller coat cloth, the coating of coiling rod, funny point type.In these methods, the excellent rubbing method of conventional coiling, intaglio plate rubbing method etc.
In curtain coating or after being coated with above-mentioned mixed liquor, by making solvent evaporation, can bring out being separated that spinodal decomposition causes.With regard to solvent evaporation, from the viewpoint of easily forming elongate protuberance on antiglare layer surface, preferably heat drying.Baking temperature (for example for example can be selected from 30～200 ℃, 40～150 ℃) left and right scope, from easy formation external phase structure aspects consideration altogether, can be by make its dry evaporation of carrying out solvent at the temperature that exceedes 80 ℃, for example 82～120 ℃, preferably 85～110 ℃, further preferably 88～105 ℃ (particularly 90～100 ℃) left and right temperature.For for example 1～60 minute, be preferably 1.2～50 minutes drying time, more preferably 1.5～30 minutes (particularly 1.8～10 minutes) left and right.As too low in baking temperature or the time is too short, the heat of giving resinous principle becomes insufficient, and the melt fluidity of resinous principle reduces, and is difficult to form elongate protuberance.On the other hand, as too high in baking temperature or overlong time, the temporary transient elongate protuberance forming causes highly reducing because further flowing, but structure is kept.Therefore,, as changing the method for highly adjusting anti-glare and sliding, can utilize baking temperature and drying time.
In the present invention, by dry appropriate time under such higher temperature, can give the heat that is enough to make resinous principle melt-flow.Therefore, by the spinodal decomposition of following solvent to occur, can easily form above-mentioned elongate protuberance and be total to external phase structure, and can give systematicness or periodicity for the mean distance between the territory of phase separation structure.
In curing process, for the phase separation structure forming by spinodal decomposition, can the immobilization immediately by making precursor cures.According to the kind of curable resin precursor, can carry out solidifying of precursor by the combination of heating, illumination etc. or these methods.With regard to heating-up temperature, as long as there is above-mentioned phase separation structure, can select from proper range, for example, 50～150 ℃ of left and right, also can select from the temperature range identical with the above-mentioned operation that is separated.
Illumination can be selected according to being light-cured into the kind of grading, and conventionally can utilize ultraviolet ray, electron beam etc.Conventional exposure source is generally ultraviolet lamp.In addition, as required, can in inert atmosphere, carry out illumination.
As light source, for example, for ultraviolet situation, can use Deep UV lamp, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, Halogen lamp LED, LASER Light Source (He-Cd laser, the light sources such as excimer laser) etc.Irradiate light quantity (irradiation energy) according to coating thickness and difference for example, can be 50～10000mJ/cm 2, be preferably 70～7000mJ/cm 2, 100～5000mJ/cm more preferably 2left and right.
Further form in the situation of tack coat, can for example, by using conventional process, above-mentioned curtain coating or coating process to coat the another side of hyaline membrane.
[display device]
Antiglare film of the present invention there is hard painting and anti-glare high.In addition, can, in isotropically transmission scattering transmitted light, improve the light scattering intensity within the scope of special angle.And, the distinctiveness excellence of transmission image, the character on display surface is fuzzy few.Therefore, antiglare film of the present invention can for example, for various display device: liquid crystal display (LCD) device, organic EL show (OLED) device, plasma scope, with display device such as the display device of contact panel.Particularly, even if antiglare film of the present invention can be as can be because of dazzle and the fuzzy parts that destroy image quality of character in the fine display device of (particularly more than 300ppi) more than 200ppi yet.Therefore, antiglare film of the present invention can be preferred for the multiplex device of making fine display device in these display device, for example: liquid crystal indicator (comprise and can be used as the liquid crystal indicator with the display device of contact panel), organic EL display (comprising the organic El device can be used as with the display device of contact panel).
Liquid crystal indicator can be the reflection-type liquid-crystal display device that utilizes extraneous light to throw light on to possessing the display unit of liquid crystal cells, also can be for possessing the transmissive liquid crystal display device of the back light unit for display unit is thrown light on.In above-mentioned reflection-type liquid-crystal display device, can import from outside incident light via display unit, thereby by the transmitted light illumination display unit of reflection part reflection and transmission display unit.In reflection-type liquid-crystal display device, above-mentioned antiglare film, optical component (the particularly duplexer of polaroid and antiglare film) can be set in the light path in the front of above-mentioned reflection part.For example, can be between reflection part and display unit, the arranging or stacked antiglare film of the present invention above etc. of display unit.
In transmissive liquid crystal display device, back light unit also can possess for by a sidepiece incident from the light of light source (point source of light such as tubular light source, light emitting diode such as cold-cathode tube etc.) and for example, by the light guide plate (light guide plate that, section is wedge shape) of exit facet outgoing above.In addition, as required, can also prismatic lens be set in the front face side of light guide plate.It should be noted that, be conventionally provided with at the back side of light guide plate for reflexing to the reflection part of exit facet side from the light of light source.In such transmissive liquid crystal display device, conventionally, above-mentioned antiglare film, optical component can be set in the light path in light source front.For example, can be between light guide plate and display unit, the arranging above etc. or stacked above-mentioned antiglare film, optical component of display unit.
Antiglare film of the present invention is effective especially to organic EL display.Light emitting diode (LED) that organic EL is made up of organic compound luminescent layer forms, and utilizes by being injected into the luminous in conjunction with the exciton (exciton) producing again of electronics in organic compound and hole.Luminescent material for luminescent layer can be macromolecular material, can be also low molecular material.In addition, organic EL forms light-emitting component in each pixel, and this light-emitting component forms conventionally on the substrate such as negative electrode/electron injecting layer/electron transfer layer/luminescent layer/hole transmission layer/hole injection layer/anode/glass plate or transparent plastic sheet.
In addition, organic EL has heterojunction, and other layer is enclosed respectively in electronics and hole.Above-mentioned heterojunction can be also double heterojunction.
As electrode, conventionally use the metal oxides such as ITO as anode, use the metals such as Al, Mg, Ag, Li alloy as negative electrode.As layers of material, conventionally use the organism such as diamines, anthracene, metal complex etc.Specifically, hole transmission layer can be by the formation such as diazole/triazole.Hole blocking layer can be formed by phenanthrene derivative etc.Dopant material can be DCM2[4-(dicyano methylene)-2-methyl-6-(to dimethylamino styryl-4H-pyrans], coumarin 6,
Figure BDA0000398980040000262
deng.Between electrode, the thickness of each layer is for number nm is to hundreds of nm, and entirety has the thickness of the following left and right of 1 μ m.
As type of drive, can adopt: by the active components such as TFT (thin film transistor (TFT)) be disposed at driven with active matrix mode that each pixel drives or by the strip electrode to orthogonal periodically circulating current to drive successively any one type of drive in the passive matrix type of drive of each pixel of its intersection point.
Can be used for the reason of organic EL as antiglare film of the present invention, can infer this is because the pixel luminous intensity of organic EL is high and pixel self is luminous, can not pass through as the chromatic filter of liquid crystal and so on.That is, can infer: because the light of organic EL does not have directive property, easily dazzle, therefore, in the time adopting existing antiglare film to suppress the dazzle of organic EL, anti-glare reduces.
In addition, be that Pentile arranges liquid crystal indicator or the organic EL display (particularly organic EL display) of (formed a pixel and alternately spread and fill out the arrangement forming by GR or two kinds of colors of GB) for Pixel arrangement, antiglare film of the present invention also can suppress dazzle, therefore can preferably utilize.
And; with regard to antiglare film of the present invention; even if its antiglare layer, away from display surface, also can suppress dazzle, therefore also can be preferably used as for prevent display device impaired towards protection or protective film (the particularly diaphragm of organic EL display) after sale.Particularly; even due to antiglare film of the present invention its antiglare layer and display surface spaced apart also can suppress dazzle while arranging; the diaphragm that mode was used that to be therefore specially adapted to the distance apart from display surface (distance of display surface and antiglare layer) be more than 0.05mm (particularly 0.1～0.4 left and right) (owing to being arranged at most surface and interval tack coat, thereby apart from the larger film of the distance of display surface) particularly useful.
Embodiment
Below, based on embodiment, the present invention is described in more detail, but the present invention is not limited to the examples.With project below, the antiglare film obtaining in embodiment and comparative example is evaluated.
[size of elongate protuberance and area]
Reflection-type laser microscope photo based on film surface, observes every 1mm 2whether the existence of middle elongate protuberance, meanwhile, for the mean diameter of the mesh of common external phase structure, obtains the mean value at any 10 positions.In addition, at 1mm 2region in, measure and there is the elongate protuberance of branched structure and the Length Ratio of other protuberance.
[(strain) Ryoka Systems system " VertScan " is measured protuberance area to use noncontact surface/layer section shape measuring system.In this system, can utilize interference of light effects on surface shape to carry out three-dimensional measurement, thereby try to achieve protuberance area with image processing method formula.
[viscosity]
Use Brookfield viscometer (Tokyo gauge (strain) system " BL type "), according to JIS Z8803, the viscosity at having measured 25 ℃.
[mist degree and total light transmittance]
Use mist degree instrument (Japanese electric look (strain) system, trade name " NDH-5000W "), measure according to JIS K7136.
[transmission image (reflection) vividness]
Use reflection measuring instrument (Suga Test Instruments (strain) system, trade name " ICM-1T "), based on JIS K7105 so that the masking direction mode parallel with the slit direction of optical slot of film film is set and carried out blooming reflection vividness measure.In the optical slot of reflection measuring instrument, measure the reflection vividness under the optical slot of wide 0.5mm.
[60 ° of gloss]
According to JIS K7105, use glossmeter (hole field makes institute's (strain) system " lG-320 ") to evaluate.
[pencil hardness]
According to JIS K5400, measure pencil hardness with the load of 750g.
[anti-glare]
With regard to the judgement of anti-glare, will, without the naked fluorescent lamp of shading grid (louver) in antiglare film, pass through the dazzling degree of its normal reflection light of visual assessment according to standard below.
◎: do not feel dazzling
Zero: micro-ly feel dazzling
×: feel dazzling.
[dazzle]
With regard to the dazzle on display surface is judged, thering is the upper antiglare film obtaining that arranges of the smart mobile phone that resolution is the OLED display of 315ppi (Samsung's (strain) system " GALAXY NEXUS "), evaluate by range estimation according to standard below.
◎: do not feel dazzle
Zero: micro-ly feel dazzle
×: feel dazzle.
[character is fuzzy]
With regard to the character fuzzy judgement on display surface, thering is the upper antiglare film obtaining that arranges of the smart mobile phone that resolution is the OLED display of 315ppi (Samsung's (strain) system " GALAXY-NEXUS "), evaluate by range estimation according to standard below.
◎: do not feel that character is fuzzy
Zero: micro-ly feel that character is fuzzy
×: feel that character is fuzzy.
Embodiment 1
Acryl resin side chain to polymerism unsaturated group [makes the part carboxyl addition 3 of (methyl) acrylic acid-(methyl) acrylate copolymer, the compound that 4-epoxide ring hexenyl methacrylate forms, (strain) Daicel system " CYCLOMER P (ACA) 320M ", solid constituent are 49.6 % by weight] 5.65 weight portions, (degree of acetylation=2.5%, propionyl degree=46%, polystyrene conversion number-average molecular weight are 75000 to cellulose-acetate propionate, Eastman company system " CAP-482-20 ") 1.2 weight portions, (Daicel-Cytec (strain) makes " DPHA " to multifunctional acrylic compounds UV curability compound, viscosity 5250mPas) 4 weight portions, (Daicel-Cytec (strain) makes " PETlA " to acrylic compounds UV curability compound, viscosity 1100mPas) 2.77 weight portions, and light trigger (BASF AG's system " IRGACURE907 ") 0.53 weight portion is dissolved in the mixed solvent of MEK (MEK) 25 weight portions and n-butyl alcohol 12.15 weight portions.Use wire-wound rod #24 by after this solution casting is to the PET film (Japan's weaving (strain) system " A4300 ") of thickness 100 μ m, in the baking oven of 95 ℃, place 2 minutes, make solvent evaporation, formed the coating of thickness approximately 7 μ m.Then, irradiate approximately 10 seconds of ultraviolet ray from high-pressure mercury-vapor lamp (Eyegraphics company system) to coating, carried out UV and solidified processing.
Observe by reflection-type laser microscope, result as shown in Figure 2, has formed continuous shape phase separation structure altogether on the whole surface of coating., every 1mm 2be formed with a continuous mesh-shape elongate protuberance, in whole protuberances, the ratio with the elongate protuberance of branched structure is roughly 100%.In this surface structure, the mean diameter of the mesh of external phase structure is approximately 5 μ m altogether, is formed with protuberance in more than half regions on whole surface (approximately 98%).
In addition, paste the sheet material obtaining on the display of the organic EL smart mobile phone of fine, result is not felt the dazzle showing.In addition, indoor fluorescent light is not mirrored, and anti-glare is also excellent, does not also feel that character is fuzzy.
Embodiment 2
Side chain is there are to acryl resin [CYCLOMER P (ACA) 320M] 5.65 weight portions of polymerism unsaturated group, cellulose-acetate propionate (CAP-482-20) 1.2 weight portions, multifunctional acrylic compounds UV curability compound (DPHA) 6 weight portions, (Daicel-Cytec (strain) makes " EB1360 " to the acrylic compounds UV curability compound that contains siloxane, viscosity is 2100mPas) 0.77 weight portion, and light trigger (IRGACUR907) 0.53 weight portion is dissolved in the mixed solvent of MEK25 weight portion and n-butyl alcohol 12.15 weight portions.The PET film (A4300) that uses wire-wound rod #24 to be 100 μ m by this solution casting to thickness is placed 2 minutes after going up in the baking oven of 90 ℃, makes solvent evaporation, and having formed thickness is the coating of approximately 7 μ m.Then, irradiate approximately 10 seconds of ultraviolet ray from high-pressure mercury-vapor lamp (Eyegraphics company system) to coating, carried out UV and solidified processing.
Observe by reflection-type laser microscope, result as shown in Figure 3, has formed the common continuous shape phase separation structure with droplet-like phase separation structure (drop phase structure) on the part surface of coating., every 1mm 2be formed with a continuous mesh-shape elongate protuberance, have the elongate protuberance of branched structure and the Length Ratio of other protuberance for the former/left and right, the latter=80/20.In this surface structure, the mean diameter of the mesh of external phase structure is approximately 4 μ m altogether, is formed with protuberance in more than half regions on whole surface (approximately 89%).
In addition, paste the sheet material obtaining on the organic EL smart mobile phone of fine, result is not felt the dazzle showing.In addition, indoor fluorescent light is not mirrored, and anti-glare is also very excellent.
Comparative example 1
Except making baking temperature is 70 ℃, by having made the coating after UV solidifies with the identical method of embodiment 1.Observe by transmissive optical microscope, result coating has droplet-like phase separation structure.
In addition, paste the sheet material obtaining on the organic EL smart mobile phone of fine, result room fluorescent lights does not mirror, and anti-glare is also very excellent, and also NULI character is fuzzy, but has felt the dazzle showing.
Comparative example 2
Acryl resin [CYCLOMER P (ACA) 320M] 5.65 weight portions, cellulose-acetate propionate (CAP-482-20) 1.2 weight portions, multifunctional acrylic compounds UV curability compound (DPHA) 6.77 weight portions, light trigger (IRGACUR907) 0.53 weight portion at side chain with polymerism unsaturated group are dissolved in the mixed solvent of MEK25 weight portion and n-butyl alcohol 12.15 weight portions.Use wire-wound rod #24 by after this solution casting is on the PET film (A4300) of thickness 100 μ m, in the baking oven of 90 ℃, place 2 minutes, make solvent evaporation, formed the coating of thickness approximately 7 μ m.Then, irradiate approximately 10 seconds of ultraviolet ray from high-pressure mercury-vapor lamp (Eyegraphics company system) to coating, carried out UV and solidified processing.
Observe by reflection-type laser microscope, result, has droplet-like phase separation structure as shown in Figure 1 in coating.
In addition, paste the sheet material obtaining on the organic EL smart mobile phone of fine, result room fluorescent lights does not mirror, and anti-glare is also very excellent, does not feel the dazzle of demonstration, but character is fuzzy significantly.
The evaluation result of the antiglare film obtaining in embodiment and comparative example is shown in to table 1.
[table 1]
? Embodiment 1 Embodiment 2 Comparative example 1 Comparative example 2
Structure Continuous shape altogether Continuous shape altogether Droplet-like Droplet-like
Total light transmittance (%) 91 91 91 89
Mist degree (%) 18 28 21 42
Transmission image vividness (%) 75 85 63 80
60 ° of gloss 51 54 48 41
Pencil hardness 2H 2H 2H 2H
Anti-glare ◎ ○ ◎ ◎
Dazzle ○ ◎ × ◎
Character is fuzzy ◎ ◎ ◎ ×
Result by table 1 can be clear and definite, and the anti-dazzle excellence of antiglare film of embodiment, can also suppress dazzle and character is fuzzy, and on the other hand, the antiglare film of comparative example has produced dazzle or character is fuzzy.
Industrial applicibility
Antiglare film of the present invention can be by the antiglare film that acts on various display device, and described display device for example comprises: liquid crystal display (LCD) device, CRT display, organic or inorganic electroluminescence (EL) display, Field Emission Display (FED), surface-conduction-electron emission display (SED), rear-projection TV display, plasma scope, with display device of contact panel etc.
Wherein, antiglare film of the present invention for the various displays including PC display, TV of great use, for fine display device, can realize anti-glare and resistance to dazzle simultaneously and suppress character fuzzy, therefore as the displays such as display, smart mobile phone, tablet PC (PC) for auto navigation and particularly useful with the antiglare film of the display device of contact panel.
Particularly; with regard to the film that comprises curable resin precursor with regard to antiglare layer; excellent scratch resistance; and in the high display device of fineness (for example, more than 300PPi); even spaced apart with demonstration; also can keep above-mentioned optical characteristics, therefore particularly useful as the diaphragm (protective film) towards after sale of liquid crystal indicator, organic EL display (particularly organic EL display).

Claims (13)

1. an antiglare film, it comprises surface and has the antiglare layer of elongate protuberance, and described elongate protuberance follows being separated of various kinds of resin composition to form,
Wherein, described elongate protuberance has branched structure and total length is more than 100 μ m,
And, every 1mm of described antiglare layer 2there is 1 the above elongate protuberance in surface.
2. antiglare film according to claim 1, wherein, elongate protuberance forms common external phase structure, and the mean diameter of the mesh of external phase structure is 1～70 μ m altogether.
3. antiglare film according to claim 1 and 2, wherein, have the elongate protuberance of branched structure and the Length Ratio of other protuberance for the former/the latter=100/0～50/50.
4. according to the antiglare film described in any one in claim 1～3, it has 70～100% transmission image vividness, 10～40% mist degree, total light transmittance of 70～100%, and described transmission image vividness is to utilize the reflection measuring instrument of the optical slot that has used wide 0.5mm to measure.
5. according to the antiglare film described in any one in claim 1～4, wherein, various kinds of resin composition comprises multiple polymers and is selected from least one the curable resin precursor in lower group, described multiple polymers is selected from styrene resin, (methyl) acrylic resin, alicyclic olefin resinoid, polyester resin, aliphatics organic acid cellulose esters and aromatic organic acid cellulose esters, the group of described curable resin precursor comprises: epoxy (methyl) acrylate, carbamate (methyl) acrylate, polyester (methyl) acrylate, organosilicon (methyl) acrylate and at least there is the multi-functional monomer of two polymerism unsaturated links,
And at least two kinds of compositions in described polymkeric substance are by being separated from liquid phase generation spinodal decomposition,
And described curable resin precursor through and having solidified.
6. antiglare film according to claim 5, wherein, the viscosity that curable resin precursor comprises at 25 ℃ based on JIS Z8803 is the low cementation voltinism resin precursor below 3000mPas.
7. according to the antiglare film described in any one in claim 1～6, wherein, while being arranged at the display device with 200ppi resolution, even if the distance that antiglare layer has more than 0.05mm apart from display surface also can suppress dazzle.
8. antiglare film according to claim 7, wherein, display device is organic EL display.
9. according to the antiglare film described in any one in claim 1～8, it also comprises hyaline membrane, and antiglare layer is formed in the one side of this hyaline membrane.
10. according to the antiglare film described in any one in claim 1～9, wherein, at least a portion of the another side of hyaline membrane, be formed with tack coat.
11. according to the antiglare film described in any one in claim 1～10, and it is protection or the protective film that is arranged at the most surface of display device.
The manufacture method of 12. 1 kinds of antiglare film, it is the method for the antiglare film described in manufacture claim 1, the method comprises following drying process: on supporter, utilize the spinodal decomposition of following solvent evaporation and occur to form phase separation structure the solution coat that contains various kinds of resin composition.
13. manufacture methods according to claim 12 wherein, in drying process, heat at the temperature that exceedes 80 ℃.
CN201310495269.7A 2012-10-19 2013-10-21 Antiglare film and its manufacture method Active CN103777255B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-231496 2012-10-19
JP2012231496A JP6190581B2 (en) 2012-10-19 2012-10-19 Antiglare film and method for producing the same

Publications (2)

Publication Number Publication Date
CN103777255A true CN103777255A (en) 2014-05-07
CN103777255B CN103777255B (en) 2017-03-01

Family

ID=50569713

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310495269.7A Active CN103777255B (en) 2012-10-19 2013-10-21 Antiglare film and its manufacture method

Country Status (4)

Country Link
JP (1) JP6190581B2 (en)
KR (1) KR102022917B1 (en)
CN (1) CN103777255B (en)
TW (1) TWI607232B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109313288A (en) * 2016-06-06 2019-02-05 株式会社大赛璐 Optical diffusion film and its manufacturing method and display device
CN111032750A (en) * 2017-10-25 2020-04-17 株式会社大赛璐 Touch film, method for producing same, molded body, and method for improving finger sliding property
CN111051399A (en) * 2017-10-25 2020-04-21 株式会社大赛璐 Low friction film, method for producing same, molded body, and method for improving finger sliding property
CN111433640A (en) * 2017-12-11 2020-07-17 株式会社大赛璐 Anti-glare film, and method for producing same and use thereof
CN112578576A (en) * 2020-12-02 2021-03-30 明月镜片股份有限公司 Resin lens with high-hardness film layer structure and preparation method thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6163384B2 (en) * 2013-08-19 2017-07-12 日立Ｇｅニュークリア・エナジー株式会社 LASER WELDING APPARATUS, METHOD FOR MAINTENANCE OF FUEL STRUCTURE OF NUCLEAR PLANT, AND LASER PROCESSING APPARATUS
JP2016075807A (en) * 2014-10-07 2016-05-12 エルジー ディスプレイ カンパニー リミテッド Display film, display and their production method
JP6924202B2 (en) * 2016-11-01 2021-08-25 アルプスアルパイン株式会社 Optical panel and its manufacturing method, equipment and transfer body and its manufacturing method
JP6901292B2 (en) 2017-03-15 2021-07-14 株式会社Adeka A water-soluble composition, a method for producing a cured product thereof, a cured product thereof, and an acylphosphinate.
CN110720058B (en) 2017-08-04 2022-06-21 株式会社大赛璐 Anti-glare film
KR102304117B1 (en) * 2017-08-04 2021-09-23 주식회사 다이셀 anti-glare film
KR102282272B1 (en) 2017-08-04 2021-07-28 주식회사 다이셀 anti-glare film
KR102282055B1 (en) 2017-08-04 2021-07-28 주식회사 다이셀 anti-glare film
WO2019026471A1 (en) 2017-08-04 2019-02-07 株式会社ダイセル Anti-glare film
JP7372904B2 (en) 2018-02-16 2023-11-01 株式会社Adeka Radical polymerization initiator, composition containing same, cured product thereof, manufacturing method thereof, and compound
JP2019203931A (en) * 2018-05-21 2019-11-28 株式会社ダイセル Anti-glare film, and manufacturing method and application of the same
JP2019207381A (en) * 2018-05-30 2019-12-05 株式会社ダイセル Anti-glare laminate and manufacturing method and application for the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040196558A1 (en) * 2003-04-03 2004-10-07 Hiroshi Takahashi Anti-glare film
JP2011013238A (en) * 2009-06-01 2011-01-20 Tomoegawa Paper Co Ltd Antiglare film and display using the same
CN101981472A (en) * 2008-03-25 2011-02-23 大赛璐化学工业株式会社 Antiglare film and process for producing the same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661618A (en) * 1969-06-30 1972-05-09 Firestone Fire And Rubber Co T Process for the preparation of pressure sensitive adhesives
JP2001215307A (en) 2000-01-31 2001-08-10 Nitto Denko Corp Anti-glare layer and optical member
KR100949870B1 (en) * 2001-12-17 2010-03-25 다이셀 가가꾸 고교 가부시끼가이샤 Anti-Glare Film, and Optical Member and Liquid Crystal Display Apparatus Using the Same
JP4377578B2 (en) 2001-12-17 2009-12-02 ダイセル化学工業株式会社 Antiglare film, optical member using the same, and liquid crystal display device
JP4739719B2 (en) * 2004-10-01 2011-08-03 ダイセル化学工業株式会社 Anti-glare film
JP5015462B2 (en) * 2006-01-11 2012-08-29 株式会社ダイセル Anti-glare film and method for producing the same
JP5038748B2 (en) * 2007-03-14 2012-10-03 株式会社ダイセル Antiglare film and method for producing the same
JP2009244382A (en) * 2008-03-28 2009-10-22 Sharp Corp Functional film and display apparatus
JP2010066470A (en) * 2008-09-10 2010-03-25 Daicel Chem Ind Ltd Antiglare film and method for manufacturing the same
US20110096403A1 (en) * 2009-10-22 2011-04-28 Lin Cheng Anti-glare optical module and method for manufacturing the same
JP5593125B2 (en) * 2010-06-03 2014-09-17 株式会社巴川製紙所 Optical laminate, polarizing plate and display device
JP5707856B2 (en) * 2010-10-27 2015-04-30 コニカミノルタ株式会社 Method for producing antiglare film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040196558A1 (en) * 2003-04-03 2004-10-07 Hiroshi Takahashi Anti-glare film
CN101981472A (en) * 2008-03-25 2011-02-23 大赛璐化学工业株式会社 Antiglare film and process for producing the same
JP2011013238A (en) * 2009-06-01 2011-01-20 Tomoegawa Paper Co Ltd Antiglare film and display using the same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109313288A (en) * 2016-06-06 2019-02-05 株式会社大赛璐 Optical diffusion film and its manufacturing method and display device
CN111032750A (en) * 2017-10-25 2020-04-17 株式会社大赛璐 Touch film, method for producing same, molded body, and method for improving finger sliding property
CN111051399A (en) * 2017-10-25 2020-04-21 株式会社大赛璐 Low friction film, method for producing same, molded body, and method for improving finger sliding property
CN111032750B (en) * 2017-10-25 2022-10-11 株式会社大赛璐 Touch film, method for producing same, molded body, and method for improving sliding properties of fingers
CN111051399B (en) * 2017-10-25 2023-02-17 株式会社大赛璐 Low friction film, method for producing same, molded body, and method for improving sliding properties of fingers
TWI795452B (en) * 2017-10-25 2023-03-11 日商大賽璐股份有限公司 Method for Improving Finger Slidability of Film
TWI843462B (en) * 2017-10-25 2024-05-21 日商大賽璐股份有限公司 Low friction film, method for producing the same, and molded body
CN111433640A (en) * 2017-12-11 2020-07-17 株式会社大赛璐 Anti-glare film, and method for producing same and use thereof
CN112578576A (en) * 2020-12-02 2021-03-30 明月镜片股份有限公司 Resin lens with high-hardness film layer structure and preparation method thereof
CN112578576B (en) * 2020-12-02 2023-12-05 明月镜片股份有限公司 Resin lens with high-hardness film structure and preparation method thereof

Also Published As

Publication number Publication date
CN103777255B (en) 2017-03-01
JP6190581B2 (en) 2017-08-30
KR102022917B1 (en) 2019-09-20
TWI607232B (en) 2017-12-01
KR20140050551A (en) 2014-04-29
JP2014085371A (en) 2014-05-12
TW201418757A (en) 2014-05-16

Similar Documents

Publication Publication Date Title
CN103777255A (en) Anti-dazzle film and manufacturing method therefor
JP5015912B2 (en) Anti-glare film
TWI431330B (en) An optical film and a method for manufacturing the same, an antiglare film, an optical layer polarizing element, and a display device
CN101308220B (en) Anti-dazzling optical laminate
CN101981472A (en) Antiglare film and process for producing the same
JP5015462B2 (en) Anti-glare film and method for producing the same
TW200831952A (en) Lens sheet, planar light source device and liquid crystal display device
TW200827764A (en) Scratch-resistant thin film
JP5343492B2 (en) Optical sheet
TW201437699A (en) Polarizing plate, image display device, and method for improving light-place contrast in image display device
CN101122642A (en) Substrate film for optical sheets, optical sheet, and liquid crystal display module
JP6700215B2 (en) Antiglare film and manufacturing method thereof
US9891352B2 (en) Anti-glare film and process for producing the same
CN105190370A (en) Optical film and surface light emitting body
TW201222020A (en) Optical diffusion film and process therefor, optical diffusible polarizing plate, and liquid crystal display device
JP2010224251A (en) Lens sheet, surface light source device, and liquid crystal display device
TW202302734A (en) Anti-glare film, method for producing same, and use of same
CN101290423A (en) Light altering film possessing incontinuous coating
TW201037368A (en) Anti-glare film
JP2013238867A (en) Optical film and manufacturing method therefor, anti-glare film, polarizing element with optical layer, and display device
JP2009198749A (en) Light beam control member
CN107003556A (en) The design method of liquid crystal display cells, liquid crystal display device and liquid crystal display cells
KR20180111345A (en) Visibility improvement film for display panel and display device comprising the same
TWI827243B (en) Display
KR100804060B1 (en) Light-diffusion film for right below backlight

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant