Embodiment
<optics 〉
Used for optical part of the present invention is made the parts of image display device; this image display device has optics of the present invention, transparency protected parts and the adhesive phase between these two parts, also has image displaying part in the side opposite to adhesive phase of aforementioned optics.And used for optical part of the present invention is specifically estimated and is used the measured contact angle of bonding agent below setting.Like this; have successively the image display device of image displaying part, optics, adhesive phase and transparency protected parts from image displaying part; have the optics of the present invention of contact angle of setting by employing as aforementioned optics, can be suppressed at the generation of bubble between optics and transparency protected parts.
Optics of the present invention satisfies the condition of following (1):
(1) will be take isoprene copolymer as principal ingredient, the evaluation that contains methacrylic acid dicyclopentenyl oxygen ethyl ester 14 % by weight, benzyl methacrylate 8 % by weight, methyl methacrylate 2 % by weight and Photoepolymerizationinitiater initiater 0.2 % by weight drips on the surface of aforementioned optics with bonding agent 10 μ l after, the aforementioned optics when placing 5 minutes and aforementioned evaluation with the contact angle of bonding agent below 55 °.
Aforementioned evaluation bonding agent is the bonding agent for the contact angle of estimating optics, might not be by the adhesive phase of this bonding agent composing images display device.This is estimated with bonding agent as described above, take isoprene copolymer as principal ingredient, contain methacrylic acid dicyclopentenyl oxygen ethyl ester 14 % by weight, benzyl methacrylate 8 % by weight, methyl methacrylate 2 % by weight and Photoepolymerizationinitiater initiater 0.2 % by weight.Here said Photoepolymerizationinitiater initiater can adopt gorgeous good solid 184(Irgacure 184) etc. known polymerization initiator in the past.Evaluation uses other additives of bonding agent except acetone, 2,4, beyond the polymerization regulator of the solvent of 6-trimethylbenzoic acid and so on, 1-spicy thioalcohol and so on, also can contain diphenylphosphine, but, in fact, except aforementioned essential component, other compositions all or substantially are made of isoprene copolymer.Being made of such composition with bonding agent owing to estimating, is therefore transparent, has viscosity.
Placement is in the time of 5 minutes after splashing into aforementioned evaluation to use bonding agent 10 μ l to its surface for optics of the present invention, and optical component surfaces uses the contact angle of bonding agent below 55 ° with evaluation.Although the mensuration in-service evaluation bonding agent of this contact angle also can be by measuring with the same method of water contact angle, for example, can use the Contact Angle System " OCA30L " of DataPhysics company to measure.
The aforementioned contact angle of optics of the present invention can suppress the generation of aforementioned bubble thus below 55 °.The angle consideration that occurs from suppressing bubble, preferred contact angle is below 50 °.
Optics of the present invention preferably also satisfies the condition of following (2):
(2) will be take isoprene copolymer as principal ingredient, the evaluation that contains methacrylic acid dicyclopentenyl oxygen ethyl ester 14 % by weight, benzyl methacrylate 8 % by weight, methyl methacrylate 2 % by weight and Photoepolymerizationinitiater initiater 0.2 % by weight is applied on the surface of aforementioned optics with bonding agent after, through solidify process and be formed with aforementioned optics in the sample of adhesive phase to the maximum shear stress of aforementioned adhesion agent layer more than 140N.
Here, in conjunction with Fig. 2, the assay method of the maximum shear stress of optics is described.At first, use bonding agent as estimating, use evaluation bonding agent as hereinbefore.Then, after the surface-coated evaluation that is fitted in advance the optics 1 on glass plate 6 is with bonding agent, again glass plate 7 is overlapped and be coated with on the surface of bonding agent, then shine the activation evergy line and be cured processing, form thus adhesive phase 8 between optics 1 and glass plate 7, make to measure and use sample.Afterwards, on making glass plate 6 direction relative with glass plate 7 (direction of arrow in Fig. 2), namely on the direction of pulling open adhesive phase 8 from optics 1 with the certain speed stress application, the maximal value of the power that observes is the maximum shear stress.This maximum shear stress can be measured according to JIS K6868-2.As the device of measuring this maximum shear stress, the Autograph(AG-1 that for example can use Shimadzu Seisakusho Ltd. to produce).The maximum shear stress that records like this means the maximum shear stress of the optics of stipulating in the condition of aforementioned (2).
The maximum shear stress of optics is preferably more than 140N.By making this maximum shear stress more than 140N; the adherence of optics transparent transparency protected parts of lamination with clipping bonding agent is improved; for example; in the large image display device of the so transparency protected parts of LCD TV; can prevent the displacement of these parts that the deadweight of transparency protected parts causes; in addition, have the image display device of physical loads when such mobile of personal digital assistant device, can prevent the displacement of these parts of being caused by this physical loads.
Optics of the present invention can be to have tabular, the sheet of aforementioned specific contact angle, membranaceous parts, but as the component parts of image display device, preferred sheet or membranaceous parts.Wherein, the parts of preferably processing through non-glare treated, antireflection processing, dura mater processing, electrostatic prevention processing, primary coat again; as the film through these processing, can be antiglare film, optical diffusion film, antireflection film, polarizer diaphragm or the Polarizer with polariscope diaphragm etc.The below describes these.
Antiglare film is used for giving anti-dazzle function to image display device, can be for example to be formed with the film of anti-dazzle on the surface of transparent base film.Concavo-convex antiglare layer, (c) that has (a) formed regulation from the teeth outwards by disperse the light transmission particulate in translucent resin concavo-convex antiglare layer, (b) to form regulation with metal die etc. on the surface of translucent resin as the suitable example of said anti-dazzle here directly formed concavo-convex anti-dazzle of regulation on the surface of transparent base film.Wherein, consider preferred aforementioned (a) and (b) from the angle of anti-glare, other optical characteristics.
As the transparent material film that is used for antiglare film, so long as have the appropriateness the transparency and the resin molding of physical strength get final product, such as being the TAC(Triafol T) etc. the polyolefin resins such as the polyester resins such as cellulose acetate resinoid, acrylic resin, polycarbonate resin, polyethylene terephthalate, tygon, polypropylene.
Has light transmission as long as consist of the translucent resin of aforementioned antiglare layer, such as the solidfied material that can use the ionizing radiation curable resins such as ultraviolet curing resin, electron ray curing type resin, the solidfied material of thermohardening type resin, thermoplastic resin, metal alkoxide base polymer etc.Wherein, take the solidfied material of ionizing radiation curable resin as good.
As the ionizing ray curable resin, can be by the synthetic multifunctional urethane acrylate such as polyfunctional acrylate, diisocyanate and the polyvalent alcohol of the acrylate of polyvalent alcohol or methacrylate and so on and the hydroxy ester of acrylic or methacrylic acid etc.In addition, except these resins, also can use polyether resin with esters of acrylic acid functional group, vibrin, epoxy resin, alkyd resin, spiral shell acetal resin, polybutadiene, polymercaptan polyene resin etc.
When using ultraviolet curing resin in the ionizing radiation gel-type resin, usually add Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can suitably be selected according to the resin that uses.As Photoepolymerizationinitiater initiater (radical polymerization initiator), can use the benzoins such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzil methyl ketal and its alkyl ether etc.
The solidfied material of thermosetting resin can be the heat curing-type urethane resin that formed by the pure and mild isocyanate prepolymer of acrylic acid multielement, phenolics, urea melamine, epoxy resin, unsaturated polyester resin, silicones etc.
thermoplastic resin can use acetylcellulose, cellulose nitrate, cellulose acetate-butyrate, ethyl cellulose, the cellulose derivatives such as methylcellulose, vinyl acetate and multipolymer thereof, vinyl chloride and multipolymer thereof, the vinyl resins such as vinylidene chloride and multipolymer thereof, polyvinyl formal, the acetal resins such as polyvinyl butyral, acryl resin and multipolymer thereof, the acrylic resin such as methacrylic resin and multipolymer thereof, polystyrene resin, polyamide, linear polyester resin, polycarbonate resin etc.
The metal alkoxide base polymer can use with silanol salt material as silica type matrix of raw material etc.Particularly, the alkoxy silanes such as available tetramethoxy-silicane, tetraethoxysilane form mineral-type or the compound class matrix of organic-inorganic by hydrolysis, dehydrating condensation.
The solidfied material that uses the ionizing radiation curable resin is during as translucent resin, need to be coated with on the transparent material film, the dry ionizing rays such as irradiation ultraviolet radiation, electron ray afterwards.In addition, the solidfied material, metal alkoxide base polymer that uses thermosetting resin will heat after coating, drying during as translucent resin.
The light transmission particulate be such as being inorganic particles such as the organic fine particles such as acryl resin, melamine resin, tygon, polystyrene, organic siliconresin, acrylic acid-styrol copolymer and calcium carbonate, silica, aluminium oxide, barium carbonate, barium sulphate, titanium dioxide, glass etc., can use a kind of in these particulates or be use mixing two or more.In addition, in order to obtain desirable anti-glare or other optical characteristics, as long as the kind of light transmission particulate, particle diameter, refractive index, content etc. are done suitable adjustment.
Forming on the antiglare layer surface with metal die etc. when concavo-convex, as this type of metal die, can use mould tabular or the roller shape.
In order to form these antiglare layer, after the coating fluid that will contain the resin material (ionizing ray curable resin, thermoset resin, metal alkoxide) that forms translucent resin, light transmission particulate is applied on the transparent material film, as required, use metal die to be cured processing.About the coating process of coating fluid, can adopt known method in the past, such as using concave surface rubbing method, nick face rubbing method, print roll coating method, bar type rubbing method, scraper for coating method, air knife coating, kiss-coating method, some glue rubbing method etc.
Then, make curing of coating by ionizing ray and/or heat.To the kind of ionizing ray without particular restriction, can suitably select from ultraviolet ray, electron ray, near ultraviolet ray, visible light, near infrared ray, infrared ray, X ray etc. according to the kind of translucent resin, but preferred ultraviolet ray, electron ray, from easy and simple to handle, easily obtain high-octane angle and consider, especially preferred ultraviolet ray.
Optical diffusion film as purpose, makes the light diffusion from image display device take the visual angle that enlarges image display device etc., can be for example to have the optical diffusion film that makes the light diffusion layer that the light transmission microparticulate forms in translucent resin on transparent base film surface.Here, as transparent base film, translucent resin, light transmission particulate, can use and transparent base film cited in aforementioned antiglare film, translucent resin, material that the light transmission particulate is identical.When consisting of light diffusion layer, consider from the angle of giving desirable light diffusing, as long as the thickness of the kind of the kind of the kind of transparent base film, translucent resin, light transmission particulate, particle diameter, refractive index, content, light diffusion layer etc. is done suitable adjustment.
Antireflection film be a kind of be used to preventing incident image display device surface external light reflection, improve the film of image display device display quality, for example, be to have the film of low-index layer in the outside of transparent base film.In addition, also hard membrane layer, high refractive index layer, middle index layer can be set between such transparent base film and low-index layer, also can be provided for giving at outermost layer the hard membrane layer of mar resistance.
Said transparent base film can use and the identical film of the film shown in example of passing the imperial examinations at the provincial level of antiglare film in front herein.
The example of low-index layer has the layer that contains adhesive stroma and inorganic particles.As the material that forms adhesive stroma, for example can be by the potpourri that contains ionizing radiation curable resin and polymerization initiator be shone ionizing ray, make its polymerization, curing and obtain, also can carry out dehydrating condensation by the hydrolysate to alkoxy silane and obtain.
As ionizing radiation curable resin, polymerization initiator, can use at the material identical with cited ionizing radiation curable resin, polymerization initiator in aforementioned antiglare film.On the other hand, as inorganic particulate, can be for example LiF(refractive index 1.4), MgF(refractive index 1.4), 3NaFAlF(refractive index 1.4), AlF(refractive index 1.4), Na
3AlF
6Low refraction particulate or hollow silica particulates such as (refractive indexes 1.33).
Hard membrane layer can by to containing the potpourri irradiation ionizing ray of ionizing radiation curable resin and polymerization initiator, make its polymerization, be solidified to form.As ionizing ray curable resin, polymerization initiator, can use the material identical with cited ionizing radiation curable resin, the polymerization initiator in front.
Material as consisting of high refractive index layer without particular restriction, can use inorganic material and organic material.As inorganic material, such as being the particulates such as zinc paste, titanium dioxide, cerium oxide, aluminium oxide, silicyl oxide, tantalum oxide, yttria, ytterbium oxide, zirconia, antimony oxide, tin indium oxide (back is also referred to as ITO).In addition, also can give antistatic performance by forming this high refractive index layer.
Polarizer consists of by the polarizer made from polyvinyl alcohol (PVA) with for the protection of the polarizer diaphragm of this polarizer.As long as optics of the present invention satisfies aforementioned contact angle condition, can be both Polarizer, can be also the polarizer diaphragm.As the polarizer diaphragm; can be the TAC(Triafol T) etc. the polyolefin resins such as the polyester resins such as cellulose acetate resinoid, acrylic resin, polycarbonate resin, polyethylene terephthalate, tygon, polypropylene, but preferably the surface of these resins was carried out the adhesion promotion such as Corona discharge Treatment, glow discharge processing, primary coat processing, acid treatment, alkali treatment, ultraviolet treatment with irradiation and was processed.Wherein, consider polyester resin, polyolefin resin, acrylic resin, the polycarbonate resin more preferably processed through adhesion promotion from the angle of aforementioned the maximum shear stress.
Preferred its surface of optics of the present invention is the antifouling processing through carrying out with levelling agent etc.If passed through antifouling processing, exist the contact angle of aforementioned optics to become large tendency.
<transparency protected parts 〉
Transparency protected parts are to be configured in image display device to look and recognize the most surperficial transparent component of side, are used for physically protecting image display device.As this transparency protected parts, can use general glass plate.
<bonding agent 〉
Bonding agent described herein is used between optics of the present invention and aforementioned transparency protected parts, can use and in the past identical bonding agent.Wherein, preferably contain at least a polymkeric substance, (methyl) acrylic ester monomer and the Photoepolymerizationinitiater initiater that is selected from acrylic resin, hydriding terpene resinoid, xylene resin, butadiene polymer and isoprene copolymer.
As aforementioned acrylic resin, be preferably the carboxylate of polyurethane (methyl) acrylate, polyisoprene class (methyl) acrylate, polyisoprene class (methyl) acrylate.on the other hand, as aforementioned (methyl) acrylic monomer, it can be for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid hydroxy butyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy propyl ester, (methyl) glycidyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl oxygen ethyl ester etc.Wherein, preferred (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid dicyclopentenyl oxygen ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid 2-hydroxyl butyl ester.These compounds can be separately or be used in combination more than another.
In addition, can contain Photoepolymerizationinitiater initiater, solvent, polymerization regulator etc. in bonding agent.
Said bonding agent can be also aforementioned evaluation bonding agent herein.
As form the method for adhesive phase between optics of the present invention and transparency protected parts; can be for example after the surface-coated bonding agent of this optics; transparency protected parts are overlapped on this surface, then shine the method that the activation evergy line is cured processing.As the activation evergy line, can suitably select from ultraviolet ray, electron ray, near ultraviolet ray, visible light, near infrared ray, infrared ray, X ray etc., wherein preferred ultraviolet ray.
<image display device 〉
Like this, can make the unit that comprises optics of the present invention, transparency protected parts and the adhesive phase between between these two parts.And, have image displaying part by the side opposite to adhesive phase at this optics, can form image display device.At this, be Fig. 1 in conjunction with the schematic diagram of image display device of the present invention, image display device is described.As shown in Figure 1, image display device 5 comprises image displaying part 4, optics 1, adhesive phase 3 and transparency protected parts 2 successively.At this, transparency protected parts 2 become looking of image display device 5 and recognize side, and image displaying part 1 becomes the light source side (not shown) in image display device 5.
As image displaying part 1, such as being liquid crystal panel, EL panel, PDP etc.
Image display device 5 is in the situation of liquid crystal indicator, also disposes rear side Polarizer, prism plate, light diffusing sheet, back lighting device (all not shown in the diagram) in the light source side of image displaying part 4.
Embodiment
Further the present invention is described in detail with embodiment for the below, but the present invention is not limited to these embodiment.
<estimate and use bonding agent
Used the evaluation bonding agent that carries out following analysis with vapor-phase chromatography.
Principal ingredient: isoprene copolymer
Methacrylic acid dicyclopentenyl oxygen ethyl ester: 14 % by weight
Benzyl methacrylate: 8 % by weight
Methyl methacrylate: 2 % by weight
Photoepolymerizationinitiater initiater (gorgeous good solid 184): 0.2 % by weight
Other additives: (methyl) acrylic ester monomer 0.8 % by weight, acetone, 2,4,6-trimethylbenzoic acid, 1-spicy thioalcohol, diphenylphosphine are (although these compounds observe the peak in gas chromatographic analysis, below quantitation limit.)
The mensuration of<contact angle 〉
Drip as the surface of the membranaceous optics of determination object the commentary valency of going forward with bonding agent 5ml after, placed 5 minutes, then, the Contact Angle System " OCA30L " that produces with DataPhysics company has measured the contact angle of this optics and this evaluation use bonding agent.
The mensuration of<the maximum shear stress 〉
After the aforementioned evaluation of the surface-coated that is fitted in advance the optics on glass plate is with bonding agent, then glass plate is overlapped on the surface that has been coated with bonding agent.At this, make the length of bonding agent coated film of the direction of stress application be about 12.5mm, the thickness of bonding agent coated film is adjusted into approximately 150 μ m.
Then, use UV irradiation unit (Shinko chemical company product), with accumulated light 5000mJ/cm
2Carry out the ultraviolet ray irradiation, the aforementioned adhesion agent is solidified, form adhesive phase.
To the mensuration sample of making like this, the Autograph(AG-1 that uses company of Shimadzu Seisakusho Ltd. to produce) make on direction relative between glass plate, namely on the direction of pulling open adhesive phase from optics with certain speed (5mm/min) stress application, obtain the maximum shear stress.
The evaluation that<bubble occurs 〉
To having or not bubble to carry out following evaluation between optics and transparency protected parts.
At first, use glass plate as transparency protected parts.Then, aforementioned evaluation is acted on the bonding agent conversion bonding agent that forms the adhesive phase between between optics and transparency protected parts.
Particularly, after the surperficial central portion coating adhesive of the optics of indulging 9cm * horizontal 9cm, glass plate is overlapped on it, estimate the expansion situation of bonding agent.Do not launch good to be designated as zero with entraining into bubble, bonding agent, with being designated as of entraining into that part bubble, bonding agent well do not launch *.If do not entrain into bubble, bonding agent and launch well overlapping the glass plate stage, even be cured processing, also still have good outward appearance, and if entrain into bubble, even be cured processing, bubble still can be residual, bad order.
<sample estimates 1 〉
Contact angle, the maximum shear stress to membranaceous optics (sample No.1~12) with following formation are estimated.The results are shown in table 1.
(sample No.1)
The membranaceous optics that has mainly the antiglare layer that is formed by tetramethylol methane tetraacrylate (following title PETA), dipentaerythritol acrylate (hereinafter referred to as DPHA) on Triafol T (hereinafter referred to as TAC) base material film.
(sample No.2)
The membranaceous optics that has mainly the antiglare layer that is formed by PETA on the TAC base material film.
(sample No.3)
The membranaceous optics that has mainly the antiglare layer that is formed by PETA, IPDI on the TAC base material film.With TOF-SIMS, the surface of this optics is analyzed, do not found the existence of fluorochemicals.
(sample No.4)
The membranaceous optics that has mainly the antiglare layer that is formed by PETA, organosiloxane on the TAC base material film.
(sample No.5)
The membranaceous optics that has mainly the hard membrane layer that is formed by PETA, hexamethylene diisocyanate (hereinafter referred to as HDI) on the TAC base material film.
(sample No.6)
The membranaceous optics that has mainly the hard membrane layer that is formed by PETA, DPHA, three (2-acrylyl oxy-ethyl) isocyanuric acid ester (hereinafter referred to as TAIC), IPDI on the TAC base material film.
(sample No.7)
Have mainly by PETA, DPHA, IPDI on the TAC base material film, 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) is that form and the membranaceous optics of antiglare layer that contain antistatic agent.
(sample No.8)
The membranaceous optics that has antistatic backing on the TAC base material film and have mainly the antiglare layer that is formed by PETA, DPHA, IPDI, HEMA, TAIC on this antistatic backing.With TOF-SIMS, the surface of this optics is analyzed, found to exist PFPE.
(sample No.9)
The membranaceous optics that has antistatic backing on the TAC base material film and have mainly the antiglare layer that is formed by PETA, DPHA, IPDI, HEMA, TAIC on this antistatic backing.With TOF-SIMS, the surface of this optics is analyzed, found to exist PFPE.
(sample No.10)
The membranaceous optics that has mainly the antiglare layer that is formed by PETA, IPDI on the TAC base material film.With TOF-SIMS, the surface of this optics is analyzed, found to exist PFPE.
(sample No.11)
The membranaceous optics that has main and antiglare layer that contain antistatic agent that form by PETA, DPHA, IPDI on the TAC base material film.With TOF-SIMS, the surface of this optics is analyzed, found to exist PFPE.
Table 1
Embodiment and comparative example
Sample No.3 has been carried out aforementioned bubble estimated, consequently, do not entrained into bubble, bonding agent launches good.On the other hand, sample No.9 has also been carried out aforementioned bubble estimated, consequently, entrained into the part bubble, bonding agent does not launch well.
<sample estimates 2 〉
It is that 25 °, the maximum shear stress are that the adhesion promotion of 160N is processed that the surface of PET base material film can make contact angle.
Estimate if aforementioned optics is carried out aforementioned bubble, it is expected to not entrain into bubble, bonding agent launches good.
Reference example
The maximum shear stress of TAC base material film is 55N.
Symbol description
1: optics
2: transparency protected parts
3: adhesive phase
4: image displaying part
5: image display device
6,7: glass plate
8: by estimating the adhesive phase that forms with bonding agent