WO2011037035A1 - 表示装置の製造方法および表示装置 - Google Patents
表示装置の製造方法および表示装置 Download PDFInfo
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- WO2011037035A1 WO2011037035A1 PCT/JP2010/065762 JP2010065762W WO2011037035A1 WO 2011037035 A1 WO2011037035 A1 WO 2011037035A1 JP 2010065762 W JP2010065762 W JP 2010065762W WO 2011037035 A1 WO2011037035 A1 WO 2011037035A1
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- resin composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1062—UV-curable materials
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- 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
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/239—Complete cover or casing
Definitions
- the present invention relates to a method for manufacturing a display device in which a display device is protected by a transparent surface material.
- a resin layer seals between the display surface of the display device and a protective plate made of a transparent surface material disposed on the display surface so as to protect the display surface. It has been stopped.
- a display device in which a protective plate made of a transparent surface material is installed on a display device having a thin substrate on the display surface side of the display device and insufficient mechanical strength. The following are well known as display devices.
- Liquid crystal display device A device that operates liquid crystal using a planar active element such as TFT, a device that drives liquid crystal sandwiched between dot matrix electrodes in a line-sequential manner, and a liquid crystal sandwiched between segmented electrodes statically Those that drive, those that exhibit one liquid crystal alignment when no voltage is applied to the liquid crystal, and those that are memory type that exhibit at least two liquid crystal alignments when no voltage is applied. Since a liquid crystal device is not a self-luminous type, a transmissive liquid crystal device can visually recognize a display using illumination (backlight) provided on the back surface, and a reflective liquid crystal device is incident on a display surface. The display can be visually recognized using outside light or illumination (front light). Some display contrast is obtained by using a polarizing plate together, and some display contrast can be obtained without using a polarizing plate by a light reflection function (selective reflection) by liquid crystal alignment and an incident light modulation function of transmission-light scattering.
- a planar active element such as TFT
- -EL electroluminescence
- Self-emission is obtained by applying a voltage to the light-emitting layer made of thin-film organic matter (OLED) or inorganic material sandwiched between the electrodes formed in a dot matrix or segment. That forms the display.
- OLED thin-film organic matter
- Plasma display device Forming a display by emitting phosphors on the inner surface of the display surface side substrate by discharging rare gas such as Xe filled in the space sandwiched between electrodes arranged in a dot matrix. What to do.
- Electronic ink type devices such as electrophoretic devices that change color of display ink by applying voltage, or those that generate color by moving toner by electrostatic force or dyes using electrophoresis, etc. It has been known.
- the following method is known as a manufacturing method of a display device in which a display device is protected by a transparent surface material.
- a liquid raw material is poured onto a resin protective plate and cured to form a bonding resin, or a roll sheet-shaped bonding resin is pasted in a deaerated state on a resin protective plate, and then a liquid crystal A method of manufacturing a display device by closely contacting a cell from one end in a deaerated state (Patent Document 1).
- a liquid resin material is injected into the space formed between the protective plate and the display panel in a reduced pressure state. And manufacturing the display device by curing (Patent Documents 2 and 3).
- the method (1) has the following problems. -Since the formation of the bonding resin on the protective plate and the attachment of the liquid crystal cell to the formed bonding resin are performed in separate steps, the manufacturing tends to be complicated. ⁇ Because it is necessary to use a plate-shaped protective plate with a side wall at the periphery, it is necessary to process the protective plate separately, and since the protective plate is limited to the size of the liquid crystal cell, the protective plate is installed. The method is very limited. -Bubbles may be generated in the liquid raw material at the time of injection in forming the bonding resin on the protective plate.
- the method (2) has the following problems.
- the positioning of the liquid crystal panel to the protective plate must be temporarily fixed, and the liquid resin material must be injected into the space between the protective plate and the liquid crystal panel in separate steps, and the manufacturing tends to be complicated.
- it may take time to inject the liquid resin material and the degree of decompression at the time of injection is 1.33 ⁇ 10 4 to 6.67 ⁇ 10 4 Pa.
- the interfacial adhesive force between the resin layer obtained by curing the curable resin composition and the display device, or the interfacial adhesive force between the resin layer and the protective plate of the display device is decreased.
- the emitted light or reflected light from the display device may be disturbed by the bubbles, and the quality of the display image may be greatly impaired.
- the display device of the display device is not displaying an image, the air bubbles remaining in the resin layer through the protective plate are easily visually recognized, which may greatly impair the product quality.
- the present invention makes it difficult for the display device to break, can increase the interfacial adhesive force between the resin layer and the display device and the interfacial adhesive force between the resin layer and the transparent surface material, and bubbles are generated by the liquid curable resin composition.
- a method of manufacturing a display device in which a display device is sufficiently protected by a transparent surface material is provided.
- the display device manufacturing method of the present invention includes a first face material and a second face material, one of which is a display device and the other is a transparent face material, and a first face material and a second face material.
- a method of manufacturing a display device having a resin layer sandwiched between and a seal portion surrounding the resin layer A method of manufacturing a display device having the following steps (a) to (d) in which a display device is protected by a transparent surface material.
- a step of forming a seal portion on the peripheral portion of the surface of the first face material (however, when the first face material is a display device, the seal portion is provided on the peripheral portion of the surface on the image display side) Form).
- (B) A step of supplying a liquid curable resin composition to a region surrounded by the seal portion of the first face material.
- (C) In a reduced pressure atmosphere of 100 Pa or less, the second face material is stacked on the curable resin composition supplied on the first face material, and the first face material and the second face Step of obtaining a laminated precursor in which a curable resin composition is sealed with a material and a seal part (however, when the second face material is a display device, the surface on which the image is displayed is the curable resin composition) To be side by side).
- (D) A step of forming a resin layer by curing the curable resin composition in a state where the lamination precursor is placed in a pressure atmosphere of 50 kPa or more.
- the display device is preferably a liquid crystal display device.
- a light shielding printing part may be provided on the outer peripheral part of the transparent face material.
- the transparent face material is preferably a glass plate.
- An antireflection layer may be formed on one side of the transparent face material.
- the pressure atmosphere of 50 kPa or more is preferably an atmospheric pressure atmosphere.
- the curable resin composition is preferably a photocurable resin composition.
- the photocurable resin composition preferably contains at least one compound having 1 to 3 groups per molecule selected from acryloyloxy groups and methacryloyloxy groups, and a photopolymerization initiator.
- the photocurable resin composition comprises an oligomer having a molecular weight of 1,000 or more having an average of 1.8 to 4 curable functional groups each consisting of one or both of an acryloyloxy group and a methacryloyloxy group, and one hydroxyl group.
- the photocurable resin composition preferably further contains an alkyl methacrylate having an alkyl group having 8 to 22 carbon atoms.
- the photocurable resin composition has an alkyl group having an alkyl group having 8 to 22 carbon atoms, which is higher than the content of a hydroxyalkyl methacrylate having a hydroxyalkyl group having 3 to 8 carbon atoms and having 1 or 2 hydroxyl groups.
- it contains methacrylate.
- the photocurable resin composition of the laminated precursor is cured by irradiation with light in a state of being placed in a pressure atmosphere of 50 kPa or more.
- the seal portion formed on the peripheral edge portion of the first face material is preferably formed of a seal member made of a photocurable resin composition having a viscosity at 25 ° C. of 200 to 3000 Pa ⁇ s. It is preferable to cure the seal portion before curing the photocurable resin composition by light irradiation through the transparent face material. It is preferable to cure the seal portion by light irradiation from the side surface of the transparent face material.
- the display device of the present invention is sandwiched between the first face material and the second face material, one of which is a display device and the other is a transparent face material, and the first face material and the second face material. And a sealing portion surrounding the resin layer without gaps.
- the display device of the present invention was obtained by the above-described manufacturing method of each display device. Any one is a display device, and the other is a transparent face material.
- the present invention relates to a display device having a seal portion sandwiched between the face material and the second face material and surrounding the resin layer without gaps.
- the display device is not easily damaged, the interface adhesive force between the resin layer and the display device and the interface adhesive force between the resin layer and the transparent surface material can be increased, and the liquid curability is increased. Generation of bubbles due to the resin composition is sufficiently suppressed.
- the display device of the present invention is resistant to breakage of the display device, has high interfacial adhesive force between the resin layer and the display device and high interfacial adhesive force between the resin layer and the transparent surface material, and sufficiently suppresses bubbles remaining in the resin layer. It is done.
- the present invention is excellent in that a transparent surface material can be adhered to a large area display device such as a large liquid crystal device with good flatness.
- a transparent surface material serving as a protective plate of the display device is referred to as a “surface material”, and the display device is referred to as a “back material”.
- the surface material and the back material are collectively referred to as “face material”.
- face material in the production method of the present invention, a face material in which a liquid curable resin composition is supplied to a region where a seal portion is formed at a peripheral portion and surrounded by the seal portion is referred to as “first surface”.
- the face material that is superimposed on the curable resin composition is referred to as a “second face material”.
- a face material having optical transparency is referred to as a “transparent face material”.
- a transparent surface material made of glass is called a “glass plate”.
- FIG. 1 is a cross-sectional view illustrating an example of an embodiment of a display device according to the present invention
- FIG. 2 is a front view.
- the display device 4 includes a transparent surface material 10 that is a surface material, a display device 50 that is a back material, a resin layer 40 sandwiched between the transparent surface material 10 and the display device 50, and a seal portion that surrounds the periphery of the resin layer 40. 42 and a flexible printed wiring board (FPC) 54 on which a driving IC for operating the display device 50 connected to the display device 50 is mounted.
- FPC flexible printed wiring board
- the transparent face material 10 is the first. It becomes a face material, and the display device 50 becomes a second face material.
- the display device 50 becomes the first face material.
- the transparent face material 10 is the second face material.
- the display device 50 is a liquid crystal display in which a transparent surface material 52 provided with a color filter and a transparent surface material 53 provided with a TFT are bonded and sandwiched between a pair of polarizing plates 51.
- a transparent surface material 52 provided with a color filter and a transparent surface material 53 provided with a TFT are bonded and sandwiched between a pair of polarizing plates 51.
- the light shielding printing portion 55 is formed on the outer peripheral portion of the transparent surface material 10.
- the surface material is a protective plate of the display device, and is a transparent surface material that transmits a display image of the display device.
- the transparent face material include a glass plate or a transparent resin plate, and of course high light transparency and reflected light from a display device that forms a display image, light resistance, low birefringence,
- the glass plate is most preferable from the viewpoints of high planar accuracy, surface scratch resistance, and high mechanical strength. From the viewpoint of curing the photocurable resin composition from the surface material with incident light, a transparent surface material is preferable.
- soda lime glass is preferable, but a glass material such as highly transmissive glass (white plate) having a lower iron content and less bluishness is more preferable.
- tempered glass can also be used as a surface material.
- the thickness is 1.5 mm or less, it is preferable to use a chemically strengthened glass plate.
- the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the antireflection layer can also be formed by providing an inorganic thin film directly on the surface of the transparent face material, or bonding a transparent resin film provided with an antireflection layer to the transparent face material.
- the light-shielding printing part can be provided on the joint surface with the resin layer of the transparent surface material or on the back surface thereof, but it is disposed on the joint surface between the light shielding part and the image display part on the joint surface with the resin layer. Is preferred.
- the transparent face material is a glass plate, it is preferable to use printing using a ceramic paint containing a black pigment in the light-shielding printing portion because of high light-shielding properties.
- the light-shielding printing part can also be formed by bonding a transparent film having the light-shielding printing part on the front or back surface to a transparent surface material.
- the transparent surface material is relatively thin, such as 1 mm or less, the parallax between the light shielding portion and the image display portion does not increase so much even if a transparent film provided with a light shielding printing portion is bonded to the back surface of the joint surface with the resin layer. .
- Other functional layers such as a touch panel and a 3D filter can be provided on the joint surface with the resin layer of the transparent surface material. In this case, the resin layer is a state in which the other functional layer on the transparent surface material is joined to the back surface material. It becomes.
- the transparent surface material may be subjected to a surface treatment in order to improve the interfacial adhesive force with the resin layer.
- the surface treatment method include a method of treating the surface of the transparent surface material with a silane coupling agent, a method of forming a silicon oxide thin film on the surface of the transparent surface material, and the like.
- the thickness of the transparent face material is preferably 0.5 to 25 mm in the case of a glass plate.
- thicker glass plates are used for indoor applications such as televisions and other household appliances and PC displays, so the thickness is 0.7 to 6 mm.
- the thickness is 3 to 20 mm. Are preferable, and can be appropriately selected depending on the size and use environment of the display device.
- a thickness of 2 to 10 mm is preferable.
- glass substrates for display devices tend to be further increased in size and thickness, and specifically, glass having a thickness of about 0.5 to 1.5 mm may be used.
- the strength of the glass substrate can be increased by performing chemical strengthening treatment on the glass substrate.
- the back material is a display device.
- a display device a display material whose optical state is changed by an external electric signal is sandwiched between a pair of electrodes that are transparent on at least one side, and a liquid crystal display device, an EL display device, a plasma display device, an electronic ink depending on the type of the display material Type display devices.
- the display device has a structure in which a pair of face materials, at least one of which is transparent, are bonded together, and the display device is disposed so that the transparent face material side is in contact with the resin layer.
- other functional members such as a polarizing plate, a retardation plate, a touch panel, and a 3D filter may be installed on the outermost layer side of the transparent surface material in contact with the resin layer. is there.
- the resin layer is in a state of bonding the other functional member on the display device and the surface material.
- the other functional member may be formed on another transparent surface material by applying the functional layer or attaching a film having the functional layer (referred to as a functional surface material).
- a laminated body can be obtained first by the manufacturing method shown below and a display device and a functional surface material can be used as a back surface material.
- it can also be used as a surface material obtained by laminating the surface material and the functional surface material by a manufacturing method described later. At this time, lamination is performed so that the functional surface material is in contact with the side of the surface material that is in contact with the back surface material.
- a functional surface material having different functional layers on the front and back surfaces such as a touch panel formed on one surface and a 3D filter formed on the other surface, may be used. The bonding surface with the surface material or the bonding surface with the back material is selected.
- the display device including the functional surface material has a structure having three surface materials and two resin layers sandwiched between them, but the front surface material, the resin layer sandwiched between the functional surface materials, and the back surface material
- the resin layers sandwiched between the functional face materials may be the same or different resins.
- a wiring member such as an FPC that transmits an electrical signal for operating the display device may be installed on the outer periphery of the display device.
- the back face material as the first face material as the lower face material during lamination.
- the bonding surface with the resin layer of the display device may be subjected to a surface treatment in order to improve the interfacial adhesive force with the seal portion.
- the surface treatment may be performed only on the peripheral edge or on the entire surface of the face material.
- Examples of the surface treatment method include a treatment method using an adhesion primer capable of low-temperature processing.
- the thickness of the display device is usually 0.4 to 4 mm in the case of a liquid crystal display device operated by TFT, and is usually 0.2 to 3 mm in the case of an EL display device.
- the resin layer is a layer that finally serves to bond the front surface material and the back surface material, and is a layer formed by curing a curable resin composition described later.
- a curable resin composition the resin composition from which the elasticity modulus of resin after hardening becomes low is preferable. This is because when the elastic modulus of the resin layer is large, stress generated by curing shrinkage or the like may have an adverse effect on the display performance of the display device when the resin is cured.
- the thickness of the resin layer is not particularly limited and may be a required thickness depending on the purpose, but is preferably 0.03 to 2 mm, particularly preferably 0.1 to 0.8 mm.
- the thickness is less than 0.03 mm, it may be difficult to protect the display device by the resin layer effectively buffering an impact caused by an external force from the transparent surface material side.
- the thickness of the resin layer may change at that portion, and the light transmission performance may be adversely affected.
- the thickness of the resin layer exceeds 2 mm, there is a possibility that a slight amount of bubbles may remain in the resin layer, or the entire thickness of the display device including the transparent surface material may become unnecessarily thick.
- Examples of a method for adjusting the thickness of the resin layer include a method of adjusting the thickness of a seal portion described later and adjusting the supply amount of the curable resin composition supplied to the first face material.
- the thickness of the resin layer can be determined using a double-sided adhesive tape having a thickness suitable for the purpose.
- spacer particles having a predetermined particle diameter may be arranged in the seal part. .
- the seal portion is made of a seal member (double-sided adhesive tape, curable resin composition, etc.) described later. Since the area where the seal outside the image display area of the display device is installed is relatively narrow, it is preferable to provide a narrow seal portion. Depending on the thickness of the resin layer, the width of the seal part is preferably 0.5 to 2 mm, more preferably 0.8 to 1.6 mm. In order to install a narrow seal portion, it is preferable to use a curable resin material having a high viscosity as the seal member.
- a curable resin material having a room temperature viscosity of 200 to 3000 Pa ⁇ s is preferably used as the seal member, and a curable resin material having a viscosity of 500 to 2000 Pa ⁇ s is more preferably used as the seal member, and the viscosity is 1000 to 2000 Pa. -It is more preferable to use s curable resin material.
- the shape of the display device is usually rectangular.
- a curable resin composition coating device or dropping device used for the supply is used.
- the resin layer can be arranged on a large-area surface material in a short time.
- the manufacturing method of the present invention is particularly suitable for manufacturing a display device having a relatively large area as described above. Therefore, in the case of a PC monitor using a liquid crystal display device, the long side is 0.3 m.
- the long side is 0.5 m or longer and the short side is 0.4 m or longer, and the long side is 0.7 m or longer and the short side is 0.4 m or longer.
- the upper limit of the size of the display device is determined by the size of the display device, but a display device that is too large tends to be difficult to handle in installation or the like.
- the upper limit of the size of the display device is usually about 2.5 m long side ⁇ 1.5 m short side due to these restrictions.
- the long side is preferably 0.14 m or longer and the short side is 0.08 m or longer, but is not limited thereto.
- the size of the transparent surface material that is the surface material and the display device that is the back surface material may be substantially equal.
- the surface material is slightly more than the back surface material. In many cases, it becomes larger.
- the surface material can be made slightly smaller than the back material.
- the manufacturing method of the display device of the present invention is a method having the following steps (a) to (d).
- (A) A step of forming a seal portion at the peripheral portion of the surface of the first face material (however, when the first face material is a display device, the seal portion is formed at the peripheral portion of the surface on the image display side) To do).
- the first face material described above may be a back surface material or a surface material.
- the second face material is stacked on the curable resin composition supplied on the first face material, and the first face material and the second face Step of obtaining a laminated precursor in which a curable resin composition is sealed with a material and a seal portion (however, when the second face material is a display device (that is, a back face material), the surface on the side where an image is displayed is When the second face material is a transparent face material (that is, a surface material) and an antireflection layer is provided on the surface of the second face material. Then, the back side is overlapped so that the surface on the back side becomes the curable resin composition side).
- D A step of forming a resin layer by curing the curable resin composition in a state where the lamination precursor is placed in a pressure atmosphere of 50 kPa or more.
- the liquid curable resin composition is sealed between the first face material and the second face material in a reduced pressure atmosphere, and then sealed in a high pressure atmosphere such as an atmospheric pressure atmosphere.
- the curable resin composition is cured to form a resin layer.
- the containment of the curable resin composition under reduced pressure is not a method of injecting the curable resin into a narrow and wide space between the first face material and the second face material, but almost the entire first face material.
- the curable resin composition is supplied, and then the second face material is stacked to enclose the curable resin composition between the first face material and the second face material.
- Examples of the method for producing a laminate by containing a liquid curable resin composition under reduced pressure and curing the curable resin composition under atmospheric pressure include, for example, International Publication No. 2008/81838, International Publication No. 2009 / No. 16943 pamphlet (incorporated in the present application) can refer to a method for producing laminated safety glass and a photocurable resin composition used in the production method.
- a seal portion is formed along the peripheral portion of one surface of the first face material.
- the surface forming the seal portion is any one of the two surfaces. If the properties of the two surfaces are different, one of the surfaces is selected. For example, when a surface treatment for improving the interfacial adhesive force with the resin layer is performed on one surface, a seal portion is formed on the surface. Further, when an antireflection layer is provided on one surface, a seal portion is formed on the back surface.
- the surface that forms the seal portion is the surface on the image display side.
- the liquid curable resin composition does not leak into the seal portion from the interface between the seal portion and the first face material and from the interface between the seal portion and the second face material.
- the above-mentioned interfacial adhesive force and the hardness that can maintain the shape are important. Therefore, as the seal portion, a seal member having an adhesive or a pressure-sensitive adhesive on the surface is preferable.
- the sealing member include the following. -A tape-like or rod-like long body (double-sided adhesive tape, etc.) with a pressure-sensitive adhesive layer or adhesive layer provided on the surface in advance. -The adhesive layer or the adhesive layer was formed in the peripheral part of the surface of the 1st face material, and the elongate body was stuck to this.
- a dam-shaped seal precursor is formed on the peripheral edge of the surface of the first face material by printing or dispensing, and the curable resin composition is cured and then adhered to the surface.
- a material layer or adhesive layer is formed.
- the seal portion formed from the curable resin composition for forming the seal portion may be cured simultaneously with the curing of the curable resin composition for forming the resin layer, or the curing of the curable resin composition for forming the resin layer. It may be cured before.
- an amount of the uncured curable resin composition required for the first face material and the second face material is It supplies to the area
- the high viscosity curable resin composition is used as the sealing member without being cured, it is preferably formed slightly thicker than the predetermined thickness of the resin layer.
- the first The seal precursor is preferably cured before the curable resin composition supplied to form a resin layer between the face material and the second face material is cured.
- the seal precursor formed on the peripheral portion of the first face material or the second face material is irradiated with light from the side surface side of the face material, and the seal precursor is cured to form the seal portion.
- light curing is performed by irradiating the curable resin composition sandwiched between the first face material and the second face material from the main surface side of the first face material or the second face material.
- the resin layer is formed between the first face material and the second face material by, for example, a method of curing the functional resin composition or curing by applying heat.
- a liquid curable resin composition is supplied to a region surrounded by the seal portion of the first face material.
- the supply amount of the curable resin composition is set in advance to such an amount that the space formed by the seal portion, the first face material, and the second face material is filled with the curable resin composition.
- the volume of the resin layer after hardening can be defined in consideration of volume reduction by hardening shrinkage of a curable resin composition beforehand. Examples of the supply method include a method in which the first face material is placed flat and supplied in a dot shape, a linear shape, or a planar shape by a supply means such as a dispenser or a die coater.
- a curable resin composition having a high viscosity or a high molecular weight curable compound is used as compared with a conventional method in which a curable resin is injected into the gap between the protective plate and the display panel.
- the curable resin composition containing can be used. Since the high molecular weight curable compound can reduce the number of chemical bonds in the curable resin composition, the curing shrinkage of the resin layer obtained by curing the curable resin composition is reduced, and the mechanical strength is improved. . On the other hand, many high molecular weight curable compounds are highly viscous.
- the viscosity of the photocurable resin composition at 40 ° C. is preferably 50 Pa ⁇ s or less.
- a photocurable resin composition is preferable.
- the photocurable resin composition is cured in a short time with less heat energy than the thermosetting resin. Therefore, the environmental load with respect to a display device becomes small by using a photocurable resin composition in this invention. Moreover, since the photocurable resin composition can be substantially cured in several minutes to several tens of minutes, the production efficiency of the display device is high.
- a photocurable resin composition is a material that is cured by the action of light to form a resin layer.
- a photocurable resin composition the following are mentioned, for example, It can use in the range by which the hardness of a resin layer does not become high too much.
- a composition comprising a compound having an addition polymerizable unsaturated group and a photopolymerization initiator.
- a polyene compound having 1 to 6 unsaturated groups triallyl isocyanurate, etc.
- a polythiol compound having 1 to 6 thiol groups triethylene glycol dimercaptan
- a composition containing a photopolymerization initiator which is contained in a proportion in which the number of moles is substantially equal.
- a composition comprising an epoxy compound having two or more epoxy groups and a photocation generator.
- the photocurable resin composition at least one group selected from an acryloyloxy group and a methacryloyloxy group (hereinafter referred to as a (meth) acryloyloxy group) from the viewpoint that the curing speed is high and the transparency of the resin layer is high. It is more preferable to include at least one compound having a photopolymerization initiator.
- the compound having a (meth) acryloyloxy group (hereinafter also referred to as a (meth) acrylate compound), a compound having 1 to 6 (meth) acryloyloxy groups per molecule is preferable, and the resin layer becomes too hard. In view of this, compounds having 1 to 3 (meth) acryloyloxy groups per molecule are particularly preferred.
- the (meth) acrylate compound is preferably an aliphatic or alicyclic compound that contains as few aromatic rings as possible from the light resistance point of the resin layer.
- a compound having a hydroxyl group is more preferable from the viewpoint of improving the interfacial adhesive force.
- the content of the (meth) acrylate compound having a hydroxyl group is preferably 25% by mass or more, more preferably 40% by mass or more, of all (meth) acrylate compounds.
- a compound having a hydroxyl group tends to have a high elastic modulus after curing, and the cured product may be too hard, particularly when a methacrylate having a hydroxyl group is used.
- the content of the methacrylate having a hydroxyl group is preferably 40% by mass or less and more preferably 30% by mass or less among all (meth) acrylate compounds. .
- the (meth) acrylate compound may be a relatively low molecular compound (hereinafter referred to as an acrylate monomer), and a relatively high molecular weight compound having a repeating unit (hereinafter referred to as a (meth) acrylate oligomer). May be).
- Examples of the (meth) acrylate compound include one or more (meth) acrylate monomers, one or more (meth) acrylate oligomers, one or more (meth) acrylate monomers (meth) )
- One or more acrylate oligomers are mentioned, and one or more acrylate oligomers, or one or more acrylate oligomers and one or more (meth) acrylate monomers Is preferred.
- a urethane oligomer having an average of 1.8 to 4 curable functional groups each consisting of one or both of acryloyloxy group and methacryloyloxy group, and a hydroxyl group Particularly preferred is a curable resin composition containing a hydroxyalkyl methacrylate having a hydroxyalkyl group of 3 to 8 carbon atoms, wherein the number of is one or two.
- a resin layer having a lower elastic modulus is preferable so that the shrinkage of the resin in the curing process does not adversely affect the display performance of the display device.
- An oligomer having an average of 1.8 to 4 curable functional groups each consisting of a (meth) acryloyloxy group, and a hydroxy having a hydroxyalkyl group having 3 to 8 carbon atoms and having 1 or 2 hydroxyl groups A curable resin composition containing alkyl methacrylate and at least one (meth) acrylate monomer having no hydroxyl group is preferable.
- the total content of the (meth) acrylate monomer having no hydroxyl group is larger in weight ratio than the content of the methacrylate monomer having a hydroxyl group.
- a hydroxyalkyl (meth) acrylate hydroxyl group having a hydroxyalkyl group having 12 to 22 carbon atoms and having one hydroxyl group can be used instead of the (meth) acrylate monomer having no hydroxyl group.
- the (meth) acrylate monomer a compound having a vapor pressure that is low enough to sufficiently suppress volatility is preferable considering that the photocurable resin composition is placed in a reduced-pressure atmosphere in a reduced-pressure apparatus.
- the curable resin composition contains a (meth) acrylate monomer having no hydroxyl group, an alkyl (meth) acrylate having 8 to 22 carbon atoms, a polyether such as polyethylene glycol or polypropylene glycol having a relatively low molecular weight
- a diol mono (meth) acrylate or di (meth) acrylate can be used, and an alkyl methacrylate having 8 to 22 carbon atoms is preferred.
- the (meth) acrylate oligomer is a (meth) acrylate polymer having a molecular structure having a chain (polyurethane chain, polyester chain, polyether chain, polycarbonate chain, etc.) having two or more repeating units and a (meth) acryloyloxy group. Oligomers are preferred. Examples of the (meth) acrylate oligomer include a urethane bond (usually further including a polyester chain and a polyether chain) called a urethane acrylate oligomer and two or more (meth) acryloyloxy groups (meth). Examples include acrylate oligomers.
- Urethane acrylate oligomers are more preferred because they can broadly adjust the mechanical performance of the cured resin and the adhesion to the substrate by the molecular design of the urethane chain.
- the number average molecular weight of the (meth) acrylate oligomer is preferably from 1,000 to 100,000, more preferably from 10,000 to 70,000. If the number average molecular weight is less than 1000, the crosslink density of the cured resin layer becomes high, and the flexibility of the resin layer may be impaired. If the number average molecular weight is greater than 100,000, the viscosity of the uncured curable resin composition may be too high.
- the (meth) acrylate oligomer is more preferably an acrylate oligomer that can increase the reactivity in curing.
- Examples of the photopolymerization initiator include acetophenone-based, ketal-based, benzoin or benzoin ether-based, phosphine oxide-based, benzophenone-based, thioxanthone-based, and quinone-based photopolymerization initiators. Photoinitiators are preferred. When curing with visible light having a short wavelength, a phosphine oxide photopolymerization initiator is more preferable from the absorption wavelength region of the photopolymerization initiator. By using two or more kinds of photopolymerization initiators having different absorption wavelength ranges in combination, the curing time can be further accelerated, and the surface curability can be increased in the seal portion, which is more preferable.
- Examples of the photo cation generator include onium salt compounds.
- the curable resin composition may contain a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (such as an ultraviolet absorber or a radical scavenger), an antioxidant, a flame retardant, and an adhesive as necessary.
- a polymerization inhibitor such as an ultraviolet absorber or a radical scavenger
- a light stabilizer such as an ultraviolet absorber or a radical scavenger
- an antioxidant such as an ultraviolet absorber or a radical scavenger
- a flame retardant such as an adhesive
- Various additives such as an improver (such as a silane coupling agent), a pigment, and a dye may be included, and a polymerization inhibitor and a light stabilizer are preferably included.
- an improver such as a silane coupling agent
- a pigment such as a silane coupling agent
- a dye such as a pigment
- a dye such as a pigment, and a dye
- the addition may cause the transmission of those light beams.
- the ultraviolet absorber may adversely affect the color tone of the display image in the display device.
- the resin layer is required to have light resistance, particularly durability against short-wavelength light such as ultraviolet rays. Therefore, when an ultraviolet absorber or the like is included, it is preferable to appropriately adjust the absorption characteristics, blending amount, and the like.
- a chain transfer agent is preferably included, and a chain transfer agent having a thiol group in the molecule is particularly preferable.
- Polymerization inhibitors include hydroquinone (2,5-di-t-butylhydroquinone, etc.), catechol (pt-butylcatechol, etc.), anthraquinone, phenothiazine, hydroxytoluene and the like. Can be mentioned.
- the light stabilizer include ultraviolet absorbers (benzotriazole series, benzophenone series, salicylate series, etc.), radical scavengers (hindered amine series), and the like.
- Examples of the antioxidant include phosphorus-based and sulfur-based compounds.
- a compound having a relatively large molecular weight and a low vapor pressure under reduced pressure is preferable because the curable resin composition is placed under a reduced pressure atmosphere.
- the first face material supplied with the curable resin composition is put into a decompression device so that the surface of the curable resin composition is on the fixed support board in the decompression device. Place the first face material flat.
- a movement support mechanism that can move in the vertical direction is provided in an upper portion of the decompression device, and a second face material is attached to the movement support mechanism.
- the second face material is a display device, the surface on which the image is displayed is directed downward.
- the antireflection layer is provided on the surface of the second face material, the surface on which the antireflection layer is not formed is directed downward.
- the second face material is placed at a position above the first face material and not in contact with the curable resin composition. That is, the curable resin composition on the first face material and the second face material are opposed to each other without being brought into contact with each other.
- a moving support mechanism that can move in the vertical direction may be provided in the lower part of the decompression device, and the first face material supplied with the curable resin composition may be placed on the moving support mechanism.
- the second face material is attached to a fixed support board provided at the upper part in the decompression device, and the first face material and the second face material are opposed to each other.
- you may support both the 1st face material and the 2nd face material with the movement support mechanism provided in the upper and lower sides in a decompression device.
- the inside of the pressure reducing device is depressurized to form a predetermined reduced pressure atmosphere.
- the first face material and the second face material may be positioned at predetermined positions in the decompression device during the decompression operation or after a predetermined decompressed atmosphere.
- the second face material supported by the moving support mechanism is moved downward, and the second face material is moved onto the curable resin composition on the first face material. Laminate the face materials.
- the surface of the first face material when the first face material is a display device, the surface on the image display side
- the surface of the second face material when the second face material is a display device
- the curable resin composition is sealed in the space surrounded by the seal portion and the surface on the image display side.
- the curable resin composition is spread by the weight of the second face material, the pressure from the moving support mechanism, etc., and the space is filled with the curable resin composition, and then the step (d ), A layer of a curable resin composition with few or no bubbles is formed when exposed to a high pressure atmosphere.
- the reduced pressure atmosphere at the time of superposition is 100 Pa or less, preferably 10 Pa or more. If the reduced-pressure atmosphere is too low, each component (curable compound, photopolymerization initiator, polymerization inhibitor, light stabilizer, etc.) contained in the curable resin composition may be adversely affected. For example, if the reduced-pressure atmosphere is too low, each component may be vaporized, and it may take time to provide the reduced-pressure atmosphere.
- the pressure in the reduced pressure atmosphere is more preferably 15 to 40 Pa.
- the time from when the first face material and the second face material are overlapped to when the reduced pressure atmosphere is released is not particularly limited, and even after the reduced pressure atmosphere is released immediately after sealing the curable resin composition.
- the reduced pressure state may be maintained for a predetermined time.
- the curable resin composition flows in the sealed space, the interval between the first face material and the second face material becomes uniform, and the sealed state is maintained even when the atmospheric pressure is increased. Easy to maintain.
- the time for maintaining the reduced pressure state may be several hours or longer, but is preferably within 1 hour, more preferably within 10 minutes from the viewpoint of production efficiency.
- the lamination precursor After releasing the reduced pressure atmosphere in the step (c), the lamination precursor is placed in a pressure atmosphere having an atmospheric pressure of 50 kPa or more.
- a pressure atmosphere of 50 kPa or more bubbles are present in the sealed space in the layered precursor because it is pressed in the direction in which the first and second face materials are in close contact with each other due to the increased pressure.
- the curable resin composition flows into the bubbles, and the entire sealed space is uniformly filled with the curable resin composition.
- the pressure atmosphere is usually 80 kPa to 120 kPa.
- the pressure atmosphere may be an atmospheric pressure atmosphere or a higher pressure.
- An atmospheric pressure atmosphere is most preferable because operations such as curing of the curable resin composition can be performed without requiring special equipment.
- the time from when the lamination precursor is placed in a pressure atmosphere of 50 kPa or more to the start of curing of the curable resin composition (hereinafter referred to as high pressure holding time) is not particularly limited.
- the time required for the process becomes the high pressure holding time. Therefore, if there are no bubbles in the sealed space of the laminated precursor already when placed in an atmospheric pressure atmosphere, or if bubbles disappear during the process, the curable resin composition should be cured immediately. Can do.
- the lamination precursor is held in an atmosphere at a pressure of 50 kPa or more until the bubbles disappear.
- the high-pressure holding time may be a long time of one day or longer, but is preferably within 6 hours from the viewpoint of production efficiency, more preferably within 1 hour, and particularly within 10 minutes from the viewpoint of further increasing production efficiency. preferable.
- a display device is manufactured by irradiating the photocurable resin composition in the laminated precursor with light in an atmosphere of pressure of 50 kPa or more to cure.
- the photocurable resin composition is cured by irradiating ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, etc.).
- a resin layer for bonding the display device of the display device and the protective plate is formed by curing the photocurable resin composition.
- Light is irradiated from the light-transmitting side of the first face material and the second face material. When both have light transmittance, you may irradiate from both sides.
- light transmission can be obtained by operating a transmissive display device, but since there are many that do not have light transmission in the state where it is not operated, from a transparent surface material serving as a protective plate Irradiate the light to be cured.
- a transmission-scattering type display device that exhibits a transparent state when not operating is used, light from the display device side can also be used.
- the light is preferably ultraviolet light or visible light of 450 nm or less.
- a transparent surface material is provided with an antireflection layer and the antireflection layer or the resin film on which the antireflection layer is formed does not transmit ultraviolet rays, curing with visible light is important.
- a light-shielding printing part is provided in the periphery of the transparent surface material, and a seal part or a resin layer made of a photocurable resin composition is provided in an area sandwiched between the light-shielding printing part and the display device, it is transparent. There is a possibility that the light cannot be sufficiently cured only by light from the opening other than the light-shielding printing portion of the face material.
- the light source for light irradiation from the side surface a light source used for light irradiation from the transparent surface material side can be used, but using an LED that emits ultraviolet light or visible light of 450 nm or less is a surface of the light source arrangement space. More preferred.
- the light irradiation step after the light irradiation from the transparent surface material, the light irradiation may be performed from the side surface of the display device, or vice versa, or the light irradiation may be performed simultaneously. In order to further promote the photocuring of the layer, it is preferable to first irradiate light from the side surface, or to irradiate light from the transparent surface material side simultaneously with the side surface.
- the display device can be manufactured by the following two methods according to the selection of the first face material.
- A-2) A method of using a transparent surface material 10 (front surface material) serving as a protective plate as the first surface material and using a display device (back surface material) as the second surface material.
- the double-sided adhesive tape 12 is adhered along the peripheral edge of the display device 50 (first face material) to form a part of the seal portion.
- the photocurable resin composition 14 is supplied to the rectangular region 13 surrounded by the double-sided adhesive tape 12 of the display device 50.
- the supply amount of the photocurable resin composition 14 is such that the space sealed by the double-sided adhesive tape 12, the display device 50, and the transparent surface material 10 (see FIG. 7) is filled with the photocurable resin composition 14.
- the amount is preset.
- the photocurable resin composition 14 is supplied by placing the display device 50 flat on the lower surface plate 18 and moving the photocurable resin composition 14 to the line by the dispenser 20 that moves in the horizontal direction. It is carried out by supplying in the form of strips, strips or dots.
- the dispenser 20 is horizontally movable over the entire range of the region 13 by a known horizontal movement mechanism including a pair of feed screws 22 and a feed screw 24 orthogonal to the feed screws 22.
- a die coater may be used instead of the dispenser 20.
- the display device 50 and the transparent face material 10 are carried into the decompression device 26.
- An upper surface plate 30 having a plurality of suction pads 32 is disposed in the upper portion of the decompression device 26, and a lower surface plate 31 is disposed in the lower portion.
- the upper surface plate 30 can be moved in the vertical direction by an air cylinder 34.
- the transparent face material 10 is attached to the suction pad 32 with the surface on the side where the light-shielding printing part 55 is formed facing down.
- the display device 50 is fixed on the lower surface plate 31 with the surface to which the photocurable resin composition 14 is supplied facing up.
- the air in the decompression device 26 is sucked by the vacuum pump 28.
- the display device 50 stands by below in a state where the transparent surface material 10 is sucked and held by the suction pad 32 of the upper surface plate 30.
- the air cylinder 34 is operated and moved downward.
- the display device 50 and the transparent surface material 10 are superposed via the double-sided adhesive tape 12 to constitute a laminated precursor, and the laminated precursor is held for a predetermined time in a reduced pressure atmosphere.
- the mounting position of the display device 50 with respect to the lower surface plate 31, the number of suction pads 32, the mounting position of the transparent surface material 10 with respect to the upper surface plate 30, and the like depend on the size, shape, etc. of the display device 50 and the transparent surface material 10. Adjust as appropriate.
- the glass substrate can be stably held in a reduced-pressure atmosphere.
- ultraviolet light or short-wavelength visible light is irradiated from the transparent precursor 10 side of the laminated precursor to cure the photocurable resin composition 14 inside the laminated precursor, and display.
- UV light or visible light having a short wavelength is irradiated from the side surface of the device 50, the photocurable resin composition 36 for forming the seal portion and the photocurable resin composition 14 hidden in the light-shielding print portion 55 are cured, thereby displaying.
- the device 4 is manufactured.
- the method for manufacturing the display device of the present invention has been specifically described above by taking the case of the method (A-1) as an example, but the display device can be manufactured in the same manner in the case of the other method (A-2).
- a seal portion is formed on the peripheral portion of the surface on the side where the light-shielding print portion 55 of the transparent surface material is formed, and the photocurable resin composition is applied to the region surrounded by the seal portion. Supply.
- the transparent surface material is put into a decompression device, and after the inside of the decompression device has a predetermined reduced pressure atmosphere, the display device is stacked on the transparent surface material to seal the photocurable resin composition, and the obtained laminated precursor is obtained.
- a display device is obtained by placing the photocurable resin composition in an atmosphere having a pressure of 50 kPa or more and photocuring the photocurable resin composition.
- the seal part and the light shielding printing part are irradiated by light irradiation from the side of the display device. It is preferable to cure the resin layer.
- the electrostatic chuck holding method since static electricity may adversely affect the display performance of the display device, the method (A-1), that is, the first face material is used as the display device, and the second The face material is preferably held by an electrostatic chuck as a transparent face material.
- the end of the second face material can be mechanically supported without using the electrostatic chuck.
- a display device having a relatively large area can be manufactured without generating bubbles in the resin layer. Even if bubbles remain in the curable resin composition sealed under reduced pressure, the pressure is also applied to the sealed curable resin composition in a high pressure atmosphere before curing, and the volume of the bubbles decreases. The bubbles disappear easily.
- the volume of gas in the bubbles in the curable resin composition sealed under 100 Pa is considered to be 1/1000 under 100 kPa. Since the gas may be dissolved in the curable resin composition, the gas in the minute volume of bubbles quickly dissolves in the photocurable resin composition and disappears.
- the liquid curable resin composition is a fluid composition, so that the pressure is uniformly distributed on the surface of the display device.
- no further stress is applied to a part of the surface of the display device in contact with the curable resin composition, and there is little risk of damage to the display device.
- the curable resin composition is a photocurable composition, a high temperature is not required for curing, so that there is little risk of damage to the display device due to high temperatures.
- the interfacial adhesive force between the resin layer by curing of the curable resin composition and the display device or the transparent face material is higher than the interfacial adhesive force by fusion of the heat-fusible resin.
- the fluid curable resin composition is pressurized and adhered to the surface of the display device or the transparent surface material and cured in that state, higher interfacial adhesive force can be obtained, and the display device or the transparent surface material Uniform adhesion to the surface is obtained, and the interfacial adhesive force is unlikely to be partially reduced. Therefore, there is a low possibility that peeling will occur on the surface of the resin layer, and there is little possibility that moisture or corrosive gas will enter from a portion where the interfacial adhesive force is insufficient.
- the generation of bubbles is small and the curable property is shortened in a short time.
- the resin composition can be filled.
- there are few restrictions on the viscosity of the curable resin composition and the curable resin composition having a high viscosity can be easily filled. Therefore, a high viscosity curable resin composition containing a relatively high molecular weight curable compound capable of increasing the strength of the resin layer can be used.
- Examples 1 and 3 are examples, and example 2 is a comparative example.
- the liquid crystal display device was taken out from a commercially available 32-inch liquid crystal television receiver (HDV-32WX2D-V manufactured by PC DEPOT CORPORATION).
- the liquid crystal display device had a long side of 712 mm, a short side of 412 mm, and a thickness of about 2 mm.
- Polarizing plates were bonded to both surfaces of the liquid crystal display device, and six driving FPCs were bonded to one side of the long side, and a printed wiring board was bonded to the end of the FPC.
- the image display unit had a long side of 696 mm and a short side of 390 mm. This liquid crystal display device was designated as display device G.
- a light-shielding printing part was formed in a frame shape.
- an antireflective film (Realoc X4001 manufactured by Nippon Oil & Fats Co., Ltd.) was attached to the entire back surface of the light-shielding printed part with a protective film attached thereto, thereby producing a glass plate H serving as a protective plate.
- the number of functional groups of UA-2 was 2, the measured value of the number average molecular weight was about 24,000, and the measured value of the viscosity at 25 ° C. was about 830 Pa ⁇ s (measured with an E-type viscometer, Toki Sangyo). (RE-85U).
- composition I 100 parts by weight of UA-2, 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (photopolymerization initiator, product name “IRGACURE 184” manufactured by Ciba Specialty Chemicals), and bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide (photopolymerization initiator, product name “IRGACURE 819”, manufactured by Ciba Specialty Chemicals) is uniformly mixed with 0.1 part by mass to form a photocurable resin for forming a seal part.
- Composition I was obtained.
- the photocurable resin composition I was applied to the entire circumference with a dispenser at a position of about 5 mm outside the image display area of the display device G so that the width was about 1 mm and the coating thickness was about 0.6 mm.
- Defoaming treatment was performed by placing the photocurable resin composition J in a vacuum chamber in an open state while being placed in a container, and reducing the pressure in the vacuum chamber to about 20 Pa ⁇ s and holding it for 10 minutes.
- the viscosity of the photocurable resin composition J was measured, it was 1.7 Pa ⁇ s (measured with an E-type viscometer, manufactured by Toki Sangyo Co., Ltd., RE-85U).
- the photocurable resin composition J was supplied to a plurality of locations in a region inside the seal portion applied to the outer periphery of the image display region of the display device G using a dispenser so that the total mass became 125 g.
- the display device G was placed flat on the upper surface of the lower surface plate in the vacuum chamber in which a pair of surface plate lifting devices were installed so that the surface of the curable resin composition was on the upper surface.
- a pair of surface plate lifting devices were installed so that the surface of the curable resin composition was on the upper surface.
- the glass plate H is viewed from the upper surface using an electrostatic chuck on the lower surface of the upper surface plate of the lifting device in the vacuum chamber so that the surface on the side where the light-shielding printing portion is formed faces the display device G
- the opening without the light-shielding printing portion of the glass plate H and the image display area of the display device G are held at the same position with a margin of about 1 mm so that the distance from the display device G is 30 mm in the vertical direction. I let you.
- the vacuum chamber was sealed and evacuated until the pressure in the chamber reached about 15 Pa.
- the upper and lower surface plates were brought close to each other by an elevating device in the vacuum chamber, and the display device G and the glass plate H were pressure-bonded with a pressure of 2 kPa through the photocurable resin composition J and held for 1 minute.
- the static electricity is removed from the electrostatic chuck to separate the glass plate H from the upper platen, and the vacuum chamber is returned to atmospheric pressure in about 15 seconds.
- the photocurable resin composition J is formed in the display device G, the glass plate H, and the seal portion.
- a sealed laminated precursor K was obtained.
- an ultraviolet LED having a main emission wavelength of about 390 nm is linearly arranged on the photocurable resin composition I forming the seal portion provided on the peripheral edge of the display device G of the laminated precursor K.
- the ultraviolet light source light was irradiated for about 10 minutes over the entire circumference of the seal portion to cure the photocurable resin composition I, and the laminated precursor K was kept horizontal and allowed to stand for about 10 minutes.
- the display device L was obtained by irradiating UV light and visible light of 450 nm or less from the chemical lamp uniformly from the surface of the glass plate H surface of the laminated precursor K to cure the photocurable resin composition J.
- the display device L defects such as bubbles remaining in the resin layer were not confirmed although the bubble removing step required for manufacturing by the conventional injection method was unnecessary. Also, the flatness was good.
- a joined body was prepared in the same manner using a transparent glass plate of substantially the same size in place of the display device G, and the haze value in a portion without the light-shielding printed portion was measured. Met.
- the haze value is a value obtained by measurement according to ASTM D1003 using a haze guard II manufactured by Toyo Seiki Seisakusho.
- Example 2 A double-sided adhesive tape having a thickness of 0.5 mm and a width of 2 mm was attached to the peripheral edge of the display device G, and the release film on the surface was peeled off leaving only the release film of the double-sided adhesive tape on one side.
- the display device G was overlaid on the glass plate H and bonded together with a double-sided adhesive tape on three sides. Between the double-sided adhesive tape on one side leaving the release film and the display device G, about 2 mm was peeled open with a screwdriver, and 155 g of the photocurable resin composition J was poured from that portion.
- Example 3 40 parts by weight of UA-2 used in Example 1, 30 parts by weight of 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester HOB), and 30 parts by weight of n-dodecyl methacrylate were uniformly mixed.
- n-dodecyl mercaptan 0.5 part by mass of a chain transfer agent, manufactured by Kao Corporation, thiocalcol 20
- Defoaming treatment was performed by placing the photocurable resin composition K in an open state in a container while being kept in a container, and reducing the pressure in the vacuum chamber to about 20 Pa ⁇ s and holding it for 10 minutes.
- the photocurable resin composition K was supplied to a plurality of locations in a region inside the seal portion applied to the outer periphery of the image display region of the display device G using a dispenser so that the total mass became 125 g. Thereafter, a display device M was obtained in the same manner as in Steps (c) and (d) of Example 1. Defects such as bubbles remaining in the resin layer of the display device M were not confirmed.
- a joined body was prepared in the same manner using a transparent glass plate of substantially the same size in place of the display device G, and the haze value in a portion without the light-shielding printed portion was measured. Met. Also, the flatness was good.
- a display device in which a display device is protected by a transparent surface material and a display device in which the display device is protected by a transparent surface material using a low-viscosity curable resin composition.
- a display device in which the display device is not easily damaged has a high interface adhesive force between the resin layer and the display device, and an interface adhesive force between the resin layer and the transparent surface material, and air bubbles remaining in the resin layer are sufficiently suppressed. It can be easily obtained and is useful for a large-area display device such as a large liquid crystal device.
- Display device when the display device is a transmissive TFT liquid crystal display device
- Photocurable resin composition 36
- Photocurable resin composition 40
- Resin layer 42 Sealing part 50
- Display device 51 Polarizing plate 52
- Transparent surface material provided with color filter 53
- Transparent surface provided with TFT Material 54
- FPC 55 Shading printing part
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Abstract
Description
表示デバイスとしては、下記のものがよく知られている。
TFTのような面状の能動素子により液晶を動作させるもの、ドットマトリクス状の電極に挟持された液晶を線順次に駆動するもの、セグメント状の電極に挟持された液晶をスタティックに駆動するもの、液晶へ電圧を印加しない時に1つの液晶配向を示すもの、電圧を印加しない時に少なくとも2つの液晶配向を示すメモリー型のもの等。なお、液晶デバイスは自発光型ではないので、透過型の液晶デバイスでは裏面に設けた照明(バックライト)を利用して表示を視認することができ、反射型の液晶デバイスでは表示面に入射する外光や照明(フロントライト)を利用して表示を視認することができる。偏光板を併用して表示コントラストを得るものや、液晶配向による光反射機能(選択反射)、透過-光散乱の入射光変調機能により偏光板を併用しないで表示コントラストが得られるものもある。
ドットマトリクス状またはセグメント状に形成された電極に挟持された、薄膜状の有機物(OLED)または無機物による発光層に電圧を印加することで自発光が得られ、それにより表示を形成するもの。
主にドットマトリクス状に配置された電極に挟持された空間に充填されるXeなどの希ガスの放電により、表示面側基板内面に設けられた蛍光体を発光させて表示を形成するもの。
エレクトロフォレティックデバイスのような電圧印加により表示インクの配列を変化させて発色を得るものや、静電力によるトナーの移動や電気泳動を利用した色素の移動により発色を得るものなどが知られている。
(1)樹脂製の保護板上に液体原料を注入して硬化させて接合樹脂を形成後、またはロールシート状の接合樹脂を樹脂製の保護板上に脱気状態にて貼設後、液晶セルを一端から押圧しながら脱気状態で密着させて表示装置を製造する方法(特許文献1)。
(2)ガラス製の保護板の所定位置に固着部材にて表示パネルを位置決めして仮固定した後、保護板と表示パネルとの間に形成される空間に減圧状態にて液体樹脂材料を注入して硬化させることで表示装置を製造する方法(特許文献2、3)。
・保護板への接合樹脂の形成と、形成された接合樹脂への液晶セルの貼設を個別の工程で行うため、製造が煩雑になりやすい。
・周辺に側壁部を有する皿状の保護板を使用する必要があるため、保護板の加工が別途必要になり、更に保護板が液晶セルの大きさ以下に限定されることから保護板の設置方法の制約が大きい。
・保護板上への接合樹脂の形成において注入時に液体原料中に気泡が発生するおそれがある。
・保護板への液晶パネルの位置決め仮固定と、保護板と液晶パネルとの空間への液体樹脂材料の注入を個別の工程で行う必要があり、製造が煩雑になりやすい。
・大型の表示装置の製造においては、液体樹脂材料の注入に時間を要するおそれがあると共に、注入時の減圧度が1.33×104~6.67×104Paであり注入時に液体樹脂材料に気泡が残留するおそれがある。
・表示装置の表示デバイスと保護板との間の樹脂層に気泡が存在すると、表示デバイスからの出射光または反射光が気泡により乱れ、表示画像の品位を大きく損なうおそれがある。
・表示装置の表示デバイスが画像を表示していない時には、保護板を通して樹脂層に残存する気泡は容易に視認されるため製品品位を大きく損なうおそれがある。
下記の工程(a)~(d)を有する、透明面材により表示デバイスが保護された表示装置の製造方法である。
(a)第1の面材の表面の周縁部にシール部を形成する工程(ただし、第1の面材が表示デバイスである場合は、画像が表示される側の表面の周縁部にシール部を形成する)。
(b)第1の面材のシール部で囲まれた領域に液状の硬化性樹脂組成物を供給する工程。
(c)100Pa以下の減圧雰囲気下にて、第1の面材の上に供給された硬化性樹脂組成物の上に第2の面材を重ねて、第1の面材、第2の面材およびシール部で硬化性樹脂組成物が密封された積層前駆体を得る工程(ただし、第2の面材が表示デバイスである場合は、画像が表示される側の表面が硬化性樹脂組成物側となるように重ねる)。
(d)50kPa以上の圧力雰囲気下に積層前駆体を置いた状態にて、硬化性樹脂組成物を硬化させて樹脂層を形成する工程。
透明面材の外周部に遮光印刷部が設けられていてもよい。
透明面材は、ガラス板であることが好ましい。
透明面材の片面に反射防止層が形成されていてもよい。
50kPa以上の圧力雰囲気は、大気圧雰囲気であることが好ましい。
光硬化性樹脂組成物は、アクリロイルオキシ基およびメタクリロイルオキシ基から選ばれる少なくとも1種の基を1分子あたり1~3個有する化合物の少なくとも1種と、光重合開始剤とを含むことが好ましい。
光硬化性樹脂組成物は、アクリロイルオキシ基とメタクリロイルオキシ基の一方または両方からなる硬化性官能基を1分子あたり平均1.8~4個有する分子量1000以上のオリゴマーと、水酸基の数が1個または2個である炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレートを含むことが好ましい。
光硬化性樹脂組成物は、さらに、炭素数8~22のアルキル基を有するアルキルメタクリレートを含むことが好ましい。
光硬化性樹脂組成物は、水酸基の数が1個または2個である炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレートの含有量より多い、炭素数8~22のアルキル基を有するアルキルメタクリレートを含むことが好ましい。
上記積層前駆体の光硬化性樹脂組成物は、50kPa以上の圧力雰囲気下に置いた状態にて光を照射して硬化することが好ましい。
透明面材を介した光照射により光硬化樹脂組成物を硬化する前にシール部を硬化させることが好ましい。
透明面材の側面からの光照射によりシール部を硬化させることが好ましい。
また、本発明の表示装置は、上記したそれぞれの表示装置の製造方法により得られた、
いずれか一方が表示デバイスであり、他方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、第1の面材および第2の面材に挟まれ、かつ前記樹脂層の周囲をすきまなく囲むシール部とを有する表示装置に関する。
本発明の表示装置は、表示デバイスが破損しにくく、樹脂層と表示デバイスとの界面接着力および樹脂層と透明面材との界面接着力を高く、かつ樹脂層に残存する気泡が充分に抑えられる。特に、本発明は、大型の液晶デバイスのような大面積の表示デバイスに、透明面材を平坦性良く接着できる点ですぐれている。
表示装置においては、表示デバイスの保護板となる透明面材を「表面材」、表示デバイスを「裏面材」という。
表面材および裏面材を総称して「面材」という。
該面材のうち、本発明の製造方法において、周縁部にシール部が形成され、かつシール部で囲まれた領域に液状の硬化性樹脂組成物が供給される面材を「第1の面材」といい、該硬化性樹脂組成物の上に重ねられる面材を「第2の面材」という。
光透過性を有する面材を「透明面材」という。
ガラスからなる透明面材を「ガラス板」という。
上記した本発明の表示装置の製造方法の工程(c)により得られた第1の面材、第2の面材およびシール部で硬化性樹脂組成物が密封された積層物であって、上記した工程(c)を施す前のものを「積層前駆体」という。
本発明における表示装置としては、下記のものが挙げられる。
表示デバイスの保護板となる透明面材が表面材であり、表示デバイスが裏面材である、透明面材により表示デバイスが保護された表示装置。
表示装置4は、表面材である透明面材10と、裏面材である表示デバイス50と、透明面材10および表示デバイス50に挟まれた樹脂層40と、樹脂層40の周囲を囲むシール部42と、表示デバイス50に接続された表示デバイス50を動作させる駆動ICを搭載したフレキシブルプリント配線板(FPC)54とを有する。ここにおいて、上記透明面材10の周辺部にシール部が形成され、かつシール部で囲まれた領域に液状の硬化性樹脂組成物が供給される場合には、透明面材10が第1の面材となり、表示デバイス50が第2の面材となる。一方、上記表示デバイス50の周辺部にシール部が形成され、かつシール部で囲まれた領域に液状の硬化性樹脂組成物が供給される場合には、表示デバイス50が第1の面材となり、透明面材10が第2の面材となる。
また、図1、図2においては、透明面材10の外周部に遮光印刷部55を形成した構成となっている。
表面材は、表示デバイスの保護板であって、表示デバイスの表示画像を透過する透明面材である。
透明面材としては、ガラス板、または透明樹脂板が挙げられ、表示画像を形成する表示デバイスからの出射光や反射光に対して透明性が高い点はもちろん、耐光性、低複屈折性、高い平面精度、耐表面傷付性、高い機械的強度を有する点からも、ガラス板が最も好ましい。光硬化性樹脂組成物を表面材から入射光で硬化させる観点でも透明面材が好ましい。
ガラス板の材料としては、ソーダライムガラスが好ましいが、より鉄分が低く青みの小さい高透過ガラス(白板)等のガラス材料がより好ましい。安全性を高めるために表面材として強化ガラスを用いることもでき、厚さが1.5mm以下の場合には化学強化を施したガラス板を用いることが好ましい。
透明樹脂板の材料としては、透明性の高い樹脂材料(ポリカーボネート、ポリメチルメタクリレート等)が挙げられる。
透明面材の樹脂層との接合面にタッチパネルや3Dフィルタ等の他の機能層を設けることもでき、この場合、樹脂層は透明面材上の他の機能層と裏面材とを接合する様態となる。
透明面材の厚さは、機械的強度、透明性の点から、ガラス板の場合は通常厚さ0.5~25mmのものが好ましく使用できる。しかし、屋内で使用するテレビなどの家電製品やPC用ディスプレイなどの用途ではガラス板が厚いと重くなるため、厚さ0.7~6mmが、屋外に設置する公衆表示用途では厚さ3~20mmがそれぞれ好ましく、表示デバイスの大きさや使用環境に応じて適宜選択できる。透明樹脂板の場合は、厚さ2~10mmが好ましい。
特に、表示デバイス用のガラス基板は、より一層大型化、薄型化が進む傾向にあり、具体的には、0.5~1.5mm程度の厚さのガラスを用いる場合もある。そのような場合は、ガラス基板に化学強化処理を実施することで、ガラス基板の強度を増すことができ好ましい。
裏面材は、表示デバイスである。表示デバイスは、少なくとも片側が透明な一対の電極に外部の電気信号により光学様態が変化する表示材を挟持しており、表示材の種類により液晶表示デバイス、EL表示デバイス、プラズマ表示デバイス、電子インク型表示デバイスなどがある。また、表示デバイスは少なくとも一方が透明な一対の面材を張り合わせた構造を有しており、透明面材側を樹脂層と接するように配置する。このとき、一部の表示デバイスにおいては、樹脂層と接する側の透明面材の最外層側に、偏光板、位相差板、タッチパネル、3Dフィルタ等の他の機能部材が設置されていることがある。この場合、樹脂層は表示デバイス上の他の機能部材と表面材とを接合する様態となる。
上記他の機能部材が、該機能層の塗布や該機能層を有するフィルムの貼設などにより他の透明面材上に形成されている場合がある(機能面材という)。この場合、表示デバイスと機能面材とを下記に示す製造方法により先に積層体を得て裏面材とすることができる。また、前記表面材と機能面材とを後述する製造方法にて積層させたのもの表面材として用いることもできる。このとき、表面材の裏面材の接する側に機能面材が接するように積層する。一方の面にタッチパネルが形成され、他方の面に3Dフィルタが形成されているなど、機能面材がその表裏面に異なる機能層を有するものを用いてもよく、その場合、各々の機能に適切に表面材との接合面、あるいは裏面材との接合面が選ばれる。
機能面材を含む表示装置は、3つの面材とその其々の間に挟持される2つの樹脂層を有する構造となるが、表面材と機能面材に挟持される樹脂層と、裏面材と機能面材に挟持される樹脂層は同一のものであってもよいし、異なる樹脂であってもよい。
表示デバイスの厚さは、TFTにより動作させる液晶表示デバイスの場合は通常0.4~4mmであり、EL表示デバイスの場合は通常0.2~3mmである。
樹脂層は、最終的には表面材と裏面材とを接着する役目をする層であり、後述の硬化性樹脂組成物を硬化してなる層である。硬化性樹脂組成物としては、硬化後の樹脂の弾性率が低くなる樹脂組成物が好ましい。樹脂層の弾性率が大きいと樹脂の硬化に際して、硬化収縮などで発生する応力が表示デバイスの表示性能への悪影響を与えるおそれがあるからである。
樹脂層の厚さは特に限定されず、目的に応じて必要な厚さとすることができるが、0.03~2mmが好ましく、0.1~0.8mmが特に好ましい。厚さが0.03mmより薄くなると透明面材側からの外力による衝撃などを樹脂層が効果的に緩衝して表示デバイスを保護することが難しくなるおそれがある。また、透明面材と表示デバイスの積層工程において樹脂層の厚さを超える異物が介在すると、樹脂層の厚みがその部分で変化して光透過性能に悪影響がでるおそれもある。一方、樹脂層の厚さが2mmを超えると樹脂層に僅かな気泡が残留する可能性が高まるおそれがあったり、透明面材を含む表示装置全体の厚さが不要に厚くなるおそれもある。
シール部は、後述のシール部材(両面接着テープ、硬化性樹脂組成物等)からなるものである。表示デバイスの画像表示領域の外側のシールを設置する領域が比較的狭いため、幅の狭いシール部を設けることが好ましい。樹脂層の厚みにもよるが、シール部の幅は0.5~2mmが好ましく、0.8~1.6mmがより好ましい。幅の狭いシール部を設置するためには、粘度の高い硬化性樹脂材料をシール部材として用いることが好ましい。室温の粘度が200~3000Pa・sの硬化性樹脂材料をシール部材として用いるのが好ましく、粘度が500~2000Pa・sの硬化性樹脂材料をシール部材として用いるのがより好ましく、粘度が1000~2000Pa・s硬化性樹脂材料を用いるのがさらに好ましい。
表示装置の形状は、通常矩形である。
本発明の製造方法においては、第1の面材への樹脂層を形成する硬化性樹脂組成物の供給が極めて容易であり、特に供給に使用する硬化性樹脂組成物の塗布装置や滴下装置を複数台同時に用いることで短時間で大面積の面材に樹脂層を配することができる。
表示装置の大きさは、本発明の製造方法が上記のように比較的大面積の表示装置の製造に特に適していることから、液晶表示デバイスを用いたPCモニタの場合、長辺0.3m以上×短辺0.18m以上、テレビ受像機の場合、長辺0.5m以上×短辺0.4m以上が適当であり、長辺0.7m以上×短辺0.4m以上が特に好ましい。表示装置の大きさの上限は、表示デバイスの大きさで決まるが、あまりに大きい表示装置は、設置等における取り扱いが困難となりやすい。表示装置の大きさの上限は、これらの制約から、通常長辺2.5m×短辺1.5m程度である。小型ディスプレイの場合、長辺0.14m以上×短辺0.08m以上が好ましいが、これに限定されるものではない。
表示装置の場合、表面材である透明面材と裏面材である表示デバイスの寸法はほぼ等しくても良いが、表示装置を収納する他の筺体との関係から、表面材が裏面材より一回り大きくなる場合も多い。また逆に他の筺体の構造によっては、表面材を裏面材より若干小さくすることもできる。
本発明の表示装置の製造方法は、下記の工程(a)~(d)を有する方法である。
(a)第1の面材の表面の周縁部にシール部を形成する工程(ただし、第1の面材が表示デバイスである場合は画像表示される側の表面の周縁部にシール部を形成する)。なお、上記した第1の面材は、裏面材がなる場合と、また表面材がなる場合とがある。
(b)第1の面材のシール部で囲まれた領域に液状の硬化性樹脂組成物を供給する工程。
(c)100Pa以下の減圧雰囲気下にて、第1の面材の上に供給された硬化性樹脂組成物の上に第2の面材を重ねて、第1の面材、第2の面材およびシール部で硬化性樹脂組成物が密封された積層前駆体を得る工程(ただし、第2の面材が表示デバイス(すなわち裏面材)である場合は、画像が表示される側の表面が硬化性樹脂組成物側となるように重ねる。また、第2の面材が透明面材(すなわち表面材)であり、かつ第2の面材の表面に反射防止層が設けられている場合は、その裏面側の表面が硬化性樹脂組成物側となるように重ねる)。
(d)50kPa以上の圧力雰囲気下に積層前駆体を置いた状態にて、硬化性樹脂組成物を硬化させて樹脂層を形成する工程。
まず、第1の面材の一方の表面の周辺部に沿ってシール部を形成する。第1の面材として裏面材を用いるか表面材を用いるかは任意である。
第1の面材が、表示デバイスの保護板となる透明面材である場合、シール部を形成する面は、2つ表面のいずれか任意である。2つの表面の性状が異なる場合等ではどちらか一方の表面を選択する。たとえば、一方の表面に樹脂層との界面接着力を向上させる表面処理を施した場合、該表面にシール部を形成する。また、一方の表面に反射防止層が設けられている場合、その裏面にシール部を形成する。
第1の面材が表示デバイスである場合、シール部を形成する面は、画像表示される側の表面である。
・あらかじめ表面に粘着剤層または接着剤層が設けられたテープ状または棒状の長尺体(両面接着テープ等)。
・第1の面材の表面の周縁部に接着剤層または粘着剤層を形成し、これに長尺体を貼着したもの。
・硬化性樹脂組成物を用いて第1の面材の表面の周縁部にダム状のシール前駆体を印刷やディスペンス等で形成し、硬化性樹脂組成物を硬化させた後、該表面に接着剤層または粘着剤層を形成したもの。
第1の面材と第2の面材との間を所定の間隔とする、すなわち樹脂層を所定の厚さとするために、必要となる分量の未硬化の硬化性樹脂組成物を第1の面材上のシール部に囲まれた領域に供給する。シール部材として、高粘度の硬化性樹脂組成物を硬化させずに用いる場合は、前記樹脂層の所定厚さよりも若干厚く形成することが好ましい。
第1の面材あるいは第2の面材の周縁部に形成するシール前駆体として光硬化性樹脂組成物を使用し、光を照射して硬化させてシール部を形成する場合には、第1の面材と第2の面材の間に樹脂層を形成するために供給された硬化性樹脂組成物を硬化させる前に、前記シール前駆体を硬化させるのが好ましい。例えば、第1の面材あるいは第2の面材の周縁部に形成されたシール前駆体に対し、その面材の側面側から光を照射し、シール前駆体を硬化させてシール部を形成する。次いで、第1の面材と第2の面材の間に挟まれた硬化性樹脂組成物に対し、第1の面材あるいは第2の面材の主表面側から光を照射して光硬化性樹脂組成物を硬化させるか、あるいは熱を加えて硬化させる方法等によって第1の面材および第2の面材の間に樹脂層を形成する。
工程(a)の後、第1の面材のシール部で囲まれた領域に液状の硬化性樹脂組成物を供給する。
硬化性樹脂組成物の供給量は、シール部、第1の面材および第2の面材によって形成される空間が硬化性樹脂組成物によって充填されるだけの量にあらかじめ設定する。この際、硬化性樹脂組成物の硬化収縮による体積減少をあらかじめ考慮して、硬化後の樹脂層の体積を定めることができる。
供給方法としては、第1の面材を平置きにし、ディスペンサ、ダイコータ等の供給手段によって、点状、線状または面状に供給する方法が挙げられる。
高分子量の硬化性化合物は、硬化性樹脂組成物中の化学結合の数を少なくできることから、硬化性樹脂組成物を硬化させた樹脂層の硬化収縮が小さくなり、また、機械的強度が向上する。一方で、高分子量の硬化性化合物の多くは、粘性が高い。そのため、樹脂層の機械的強度を確保しつつ気泡の残存を抑制する点からは、高分子量の硬化性化合物に、より分子量の小さい硬化性モノマーを溶解させて粘度を調整することが好ましい。ただし、分子量の小さい硬化性モノマーを用いることによって、硬化性樹脂組成物の粘度は下がるが、樹脂層の硬化収縮が大きく、また、機械的強度が低下しやすい。
本発明においては、比較的高粘度の硬化性樹脂組成物を用いることができることから、硬化収縮の低減および機械的強度の向上を図ることができる。光硬化性樹脂組成物の40℃での粘度は、50Pa・s以下が好ましい。
・付加重合性の不飽和基を有する化合物と光重合開始剤とを含む組成物。
・1~6個の不飽和基を有するポリエン化合物(トリアリルイソシアヌレート等)と、1~6個のチオール基を有するポリチオール化合物(トリエチレングリコールジメルカプタン)とを、不飽和基とチオール基のモル数がおおむね等しくなる割合で含み、かつ光重合開始剤を含む組成物。
・エポキシ基を2個以上有するエポキシ化合物と光カチオン発生剤とを含む組成物。
(メタ)アクリレート系化合物としては、樹脂層の耐光性の点からは、芳香環をできるだけ含まない脂肪族または脂環式の化合物が好ましい。
(メタ)アクリレート系化合物としては、界面接着力の向上の点からは、水酸基を有する化合物がより好ましい。水酸基を有する(メタ)アクリレート系化合物の含有量は、全(メタ)アクリレート系化合物のうち、25質量%以上が好ましく、40質量%以上がより好ましい。一方、水酸基を有する化合物は、硬化後の弾性率が高くなりやすく、特に水酸基を有するメタクリレートを用いる場合には硬化物が硬くなり過ぎるおそれがある。表示装置に使用する場合は、低弾性率の樹脂層が好ましいため、水酸基を有するメタクリレートの含有量は、全(メタ)アクリレート系化合物のうち40質量%以下が好ましく、30質量%以下がより好ましい。
(メタ)アクリレート系化合物としては、(メタ)アクリレート系モノマーの1種以上からなるもの、(メタ)アクリレート系オリゴマーの1種以上からなるもの、(メタ)アクリレート系モノマーの1種以上と(メタ)アクリレート系オリゴマーの1種以上とからなるものが挙げられ、アクリレート系オリゴマーの1種以上からなるもの、またはアクリレート系オリゴマーの1種以上と(メタ)アクリレート系モノマーの1種以上とからなるものが好ましい。表示デバイスと樹脂層との密着性を高める目的では、アクリロイルオキシ基とメタクロイルオキシ基の一方または両方からなる硬化性官能基を1分子あたり平均1.8~4個有するウレタン系オリゴマーと、水酸基の数が1個または2個である炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレートを含有する硬化性樹脂組成物が特に好ましい。
(メタ)アクリレート系オリゴマーとしては、繰り返し単位を2個以上有する鎖(ポリウレタン鎖、ポリエステル鎖、ポリエーテル鎖、ポリカーボネート鎖等)と(メタ)アクリロイルオキシ基とを有する分子構造の(メタ)アクリレート系オリゴマーが好ましい。該(メタ)アクリレート系オリゴマーとしては、たとえば、ウレタンアクリレートオリゴマーと呼ばれる、ウレタン結合(通常さらにポリエステル鎖やポリエーテル鎖を含む。)と2個以上の(メタ)アクリロイルオキシ基とを有する(メタ)アクリレート系オリゴマーが挙げられる。ウレタンアクリレートオリゴマーは、ウレタン鎖の分子設計により硬化後の樹脂の機械的性能や基材との密着性などを幅広く調整できるためより好ましい。
(メタ)アクリレート系オリゴマーの数平均分子量は、1000~100000が好ましく、10000~70000がより好ましい。数平均分子量が1000より小さいと硬化後の樹脂層の架橋密度が高くなり樹脂層の柔軟性が損なわれるおそれがある。また数平均分子量が100000より大きいと未硬化の硬化性樹脂組成物の粘度が大きくなりすぎるおそれがある。(メタ)アクリレート系オリゴマーの粘度が高すぎる場合、(メタ)アクリレート系モノマーと併用して、(メタ)アクリレート系化合物全体としての粘度を低下させることが好ましい。(メタ)アクリレート系オリゴマーは、硬化において反応性が高めることができるアクリレート系オリゴマーがより好ましい。
光カチオン発生剤としては、オニウム塩系の化合物等が挙げられる。
ただし、表示装置の場合、硬化性樹脂組成物を硬化させてなる樹脂層を表示画像を形成する表示デバイスからの出射光や反射光が透過するため、それらの光線の透過を妨げるおそれのある添加剤を含むことは好ましくない。たとえば、紫外線吸収剤は、表示装置においては表示画像の色調に悪影響を与えるおそれがある。しかし一方で、樹脂層には、耐光性、特に紫外線等の短波長の光に対する耐久性が要求される。よって、紫外線吸収剤等を含ませる場合は、その吸収特性、配合量等を適宜調整することが好ましい。
表示デバイスと樹脂層との密着性を高めたり、樹脂層の弾性率を調整するためには、連鎖移動剤を含むことが好ましく、分子内にチオール基を有する連鎖移動剤が特に好ましい。
光安定剤としては、紫外線吸収剤(ベンゾトリアゾール系、ベンゾフェノン系、サリチレート系等)、ラジカル捕獲剤(ヒンダードアミン系)等が挙げられる。
酸化防止剤としては、リン系、イオウ系の化合物が挙げられる。
光重合開始剤および各種添加剤としては、硬化性樹脂組成物が減圧雰囲気下に置かれることから、比較的分子量の大きい、減圧下での蒸気圧の小さい化合物が好ましい。
工程(b)の後、硬化性樹脂組成物が供給された第1の面材を減圧装置に入れ、減圧装置内の固定支持盤の上に硬化性樹脂組成物の面が上になるように第1の面材を平置きする。
減圧装置内の上部には、上下方向に移動可能な移動支持機構が設けられ、移動支持機構に第2の面材が取り付けられる。第2の面材が表示デバイスの場合、画像を表示する側の表面を下に向ける。第2の面材の表面に反射防止層が設けられている場合、反射防止層が形成されていない側の表面を下に向ける。
第2の面材は、第1の面材の上方かつ硬化性樹脂組成物と接しない位置に置く。すなわち、第1の面材の上の硬化性樹脂組成物と第2の面材とを接触させることなく対向させる。
また、第1の面材および第2の面材の両方を、減圧装置内の上下に設けた移動支持機構で支持してもよい。
減圧装置の内部が所定の減圧雰囲気となった後、移動支持機構で支持された第2の面材を下方に移動し、第1の面材の上の硬化性樹脂組成物の上に第2の面材を重ね合わせる。
重ね合わせの際、第2の面材の自重、移動支持機構からの押圧等によって、硬化性樹脂組成物が押し広げられ、前記空間内に硬化性樹脂組成物が充満し、その後、工程(d)において高い圧力雰囲気に曝した際に、気泡の少ないまたは気泡のない硬化性樹脂組成物の層が形成される。
工程(c)において減圧雰囲気を解除した後、積層前駆体を雰囲気圧力が50kPa以上の圧力雰囲気下に置く。
積層前駆体を50kPa以上の圧力雰囲気下に置くと、上昇した圧力によって第1の面材と第2の面材とが密着する方向に押圧されるため、積層前駆体内の密閉空間に気泡が存在すると、気泡に硬化性樹脂組成物が流動していき、密閉空間全体が硬化性樹脂組成物によって均一に充填される。
表示装置の場合は、透過型の表示デバイスを動作させることで光透過性を得ることはできるが、動作させない状態では光透過性を有さないものが多いため、保護板となる透明面材から硬化させる光を照射する。非動作時に透明状態を呈する透過-散乱型の表示デバイスを用いる場合は、表示デバイス側からの光を利用することもできる。
透明面材の周辺部に遮光印刷部が設けられていて、該遮光印刷部と表示デバイスに挟持される領域に、光硬化性樹脂組成物によるシール部や樹脂層が設けられる場合には、透明面材の遮光印刷部以外の開口部からの光だけでは充分に硬化できないおそれがある。この場合、表示デバイスの側面より紫外線または450nm以下の可視光を照射して、シール部および遮光印刷部の樹脂層を硬化させることが好ましい。側面からの光照射の光源としては、透明面材側からの光照射に用いる光源を使用することもできるが、紫外線または450nm以下の可視光を発光するLEDを用いることが光源の配置スペースの面より好ましい。光照射のステップとしては、透明面材からの光照射の後に表示デバイスの側面から光照射してもよいし、その逆、あるいは同時に光照射してもよいが、遮光印刷部のシール部や樹脂層の光硬化をより促進するためには、先に側面から光を照射するか、側面と同時に透明面材側から光照射することが好ましい。
本発明の製造方法において、第1の面材として裏面材を用いるか表面材を用いるかは任意である。よって、表示装置は、第1の面材の選択に応じて以下の2種類の方法により製造できる。
(A-2)第1の面材として保護板となる透明面材10(表面材)を用い、第2の面材として表示デバイス(裏面材)を用いる方法。
図3および図4に示すように、表示デバイス50(第1の面材)の周縁部に沿って両面接着テープ12を貼着し、シール部の一部を形成する。
ついで、図5、図6に示すように、表示デバイス50の両面接着テープ12に囲まれた矩形状の領域13に光硬化性樹脂組成物14を供給する。光硬化性樹脂組成物14の供給量は、両面接着テープ12と表示デバイス50と透明面材10(図7参照)とによって密閉される空間が光硬化性樹脂組成物14によって充填されるだけの量にあらかじめ設定されている。
ディスペンサ20は、一対の送りねじ22と、送りねじ22に直交する送りねじ24とからなる公知の水平移動機構によって、領域13の全範囲において水平移動可能となっている。なお、ディスペンサ20の代わりに、ダイコータを用いてもよい。
また、図6に示すように、両面接着テープ12の表面に、シール部形成用の光硬化性樹脂組成物36を塗布しておくことが好ましい。
ついで、図7に示すように、表示デバイス50と透明面材10(第2の面材)とを減圧装置26内に搬入する。減圧装置26内の上部には、複数の吸着パッド32を有する上定盤30が配置され、下部には、下定盤31が設けられている。上定盤30は、エアシリンダ34によって上下方向に移動可能とされている。
透明面材10は、遮光印刷部55が形成された側の表面を下にして吸着パッド32に取り付けられる。表示デバイス50は、光硬化性樹脂組成物14が供給された面を上にして下定盤31の上に固定される。
ついで、減圧装置26の内部をたとえば大気圧にした後、積層前駆体を減圧装置26から取り出す。積層前駆体を大気圧雰囲気下に置くと、積層前駆体の表示デバイス50側の表面と透明面材10側の表面とが大気圧によって押圧され、密閉空間内の光硬化性樹脂組成物14が表示デバイス50と透明面材10とで加圧される。この圧力によって、密閉空間内の光硬化性樹脂組成物14が流動して、密閉空間全体が光硬化性樹脂組成物14によって均一に充填される。この後、図8に示すように、積層前駆体の透明面材10側から紫外線、または短波長の可視光を照射し、積層前駆体内部の光硬化性樹脂組成物14を硬化させ、かつ表示デバイス50側面から紫外線、または短波長の可視光を照射し、シール部形成用の光硬化性樹脂組成物36および遮光印刷部55に隠れた光硬化性樹脂組成物14を硬化させることにより、表示装置4が製造される。
方法(A-2)の場合、透明面材の遮光印刷部55が形成された側の表面の周縁部にシール部を形成し、そのシール部に囲まれた領域に光硬化性樹脂組成物を供給する。ついで、透明面材を減圧装置に入れ、減圧装置内を所定の減圧雰囲気にした後、透明面材上に表示デバイスを重ねて光硬化性樹脂組成物を密封し、得られた積層前駆体を50kPa以上の圧力の雰囲気下に置いて、光硬化性樹脂組成物を光硬化させて表示装置を得る。
以上説明した本発明の製造方法によれば、比較的大面積の表示装置を樹脂層中に気泡を発生させることなく製造できる。仮に、減圧下で密封した硬化性樹脂組成物中に気泡が残存しても、硬化前の高い圧力雰囲気下では密封した硬化性樹脂組成物にもその圧力がかかり、その気泡の体積は減少し、気泡は容易に消失する。たとえば、100Pa下で密封した硬化性樹脂組成物中の気泡中の気体の体積は100kPa下では1/1000になると考えられる。気体は硬化性樹脂組成物に溶解することもあるので、微小体積の気泡中の気体は光硬化性樹脂組成物に速やかに溶解して消失する。
市販の32型液晶テレビ受像機(株式会社ピーシーデポ・コーポレーション社製HDV-32WX2D-V)から液晶表示デバイスを取り出した。液晶表示デバイスは、長辺712mm、短辺412mm、厚さ約2mmであった。液晶表示デバイスの両面には偏光板が貼合されており、長辺の片側に駆動用のFPCが6枚接合されていてFPCの端部にはプリント配線板が接合されていた。画像表示部は、長辺696mm、短辺390mmであった。この液晶表示デバイスを表示デバイスGとした。
長辺794mm、短辺479mm、厚さ3mmのソーダライムガラスの一方の面の外周部に、開口部が長辺698mm、短辺392mmとなるように黒色顔料を含むセラミック塗料を用いた印刷にて額縁状に遮光印刷部を形成した。次に遮光印刷部の裏面の全面に反射防止フィルム(日本油脂社製リアルックX4001)を保護フィルムをつけた状態で貼合して、保護板となるガラス板Hを作製した。
水酸基価より算出した数平均分子量が約4000の分子末端をエチレングリコールで一部置換したポリプロピレングリコールとイソホロンジイソシアネートとを、ほぼ4対5となるモル比で混合し、錫化合物の触媒存在下で反応させて得られたプレポリマーに、2-ヒドロキシエチルアクリレートをほぼ1対2となるモル比で加えて反応させることによって、ウレタンアクリレートオリゴマー(以下、UA-2と記す。)を得た。UA-2の官能基数は2であり、数平均分子量の測定値は約24000であり、25℃における粘度の測定値は約830Pa・sであった(E型粘度計にて測定、東機産業社製、RE-85U)。
UA-2の100質量部と1-ヒドロキシ-シクロヘキシル-フェニル-ケトン(光重合開始剤、製品名「IRGACURE 184」チバ・スペシャルティ・ケミカルズ社製)1質量部、およびビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(光重合開始剤、製品名「IRGACURE 819」、チバ・スペシャルティ・ケミカルズ社製)0.1質量部とを均一に混合し、シール部形成用の光硬化性樹脂組成物Iを得た。
表示デバイスGの画像表示領域の外側の約5mmの位置に幅約1mm、塗布厚み約0.6mmとなるように光硬化性樹脂組成物Iをディスペンサにて全周に塗布した。
UA-2の40質量部、2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステル HOB)の24質量部、n-ドデシルメタクリレートの36質量部を均一に混合し、該混合物の100質量部に、光重合開始剤として、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(チバ・スペシャルティ・ケミカルズ社製、IRGACURE 819)の0.2質量部、重合禁止剤として、2,5-ジ-t-ブチルハイドロキノンの0.04質量部、連鎖移動剤として、1,4-ビス(3-メルカプトブチリルオキシ)ブタン(昭和電工社製、カレンズMT BD-1)の1質量部、紫外線吸収剤(チバ・スペシャリティ・ケミカルズ社製、TINUVIN 109)の0.3質量部を均一に溶解させて、光硬化性樹脂組成物Jとした。
表示デバイスGの画像表示領域の外周に塗布されたシール部の内側の領域に、光硬化性樹脂組成物Jを、ディスペンサを用いて総質量が125gとなるように複数個所に供給した。
表示デバイスGを、一対の定盤の昇降装置が設置されている真空チャンバ内の下定盤の上面に、硬化性樹脂組成物の面が上になるように平置した。
ガラス板Hを、遮光印刷部が形成された側の表面が表示デバイスGに対向するように、真空チャンバ内の昇降装置の上定盤の下面に静電チャックを用いて、上面から見た場合にガラス板Hの遮光印刷部のない開口部と表示デバイスGの画像表示領域とが約1mmのマージンをもって同位置となるように、垂直方向では表示デバイスGとの距離が30mmとなるように保持させた。
積層前駆体Kの表示デバイスG周縁部に設けられたシール部を形成する光硬化性樹脂組成物Iに、表示デバイスGの側方から、発光主波長が約390nmの紫外線LEDを線状に配した紫外線光源を用いて、シール部全周に渡って約10分間光を照射し、光硬化性樹脂組成物Iを硬化させ、積層前駆体Kを水平に保って約10分静置した。
積層前駆体Kのガラス板H面の面より均一にケミカルランプから紫外線および450nm以下の可視光を照射して、光硬化性樹脂組成物Jを硬化させることにより、表示装置Lを得た。表示装置Lは、従来の注入法による製造時に要する気泡除去の工程が不要であるにもかかわらず、樹脂層中に残留する気泡等の欠陥が確認されなかった。また、平坦性も良好であった。
表示デバイスGに代えてほぼ同じサイズの透明ガラス板を用いて同様に接合体を作製し、遮光印刷部のない部分でのヘイズ値を測定したところ1%以下であり、透明度が高い良好なものであった。なお、ヘイズ値は、東洋精機製作所社製のヘイズガードIIを用い、ASTM D1003に準じた測定により得られた値である。
表示装置Lを液晶表示デバイスを取り出した液晶テレビ受像機の筺体に戻し、配線を再接合して電源を入れたところ、当初より表示コントラストの高い画像が得られた。画像表示面を指で強く押しても画像が乱れることはなく、ガラス板Hが表示デバイスGを効果的に保護していた。
表示デバイスGの周縁部に、厚さ0.5mm、幅2mmの両面接着テープを貼着し、1辺の両面接着テープの離型フィルムのみを残して、表面の離型フィルムを剥がした。ガラス板Hの上に表示デバイスGを重ね、3辺の両面接着テープで貼り合わせた。
離型フィルムを残した1辺の両面接着テープと表示デバイスGとの間を、ドライバによって2mm程度抉じ開け、その部分から、光硬化性樹脂組成物Jを155g注ぎ入れようとしたが、表示デバイスGとガラス板Hと間の空間の下部に気泡が残り、光硬化性樹脂組成物Jを該空間中に密実に注入できなかった。
〔例3〕
例1で用いたUA-2の40質量部、2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステル HOB)の30質量部、n-ドデシルメタクリレートの30質量部を均一に混合し、該混合物の100質量部に、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド(光重合開始剤、チバ・スペシャルティ・ケミカルズ社製、IRGACURE 819)の0.5質量部、n-ドデシルメルカプタン(連鎖移動剤、花王社製、チオカルコール20)の0.5質量部を均一に溶解させて、樹脂層形成用光硬化性樹脂組成物Kを得た。
光硬化性樹脂組成物Kを容器に入れたまま開放状態で減圧チャンバ内に設置して、減圧チャンバ内を約20Pa・sに減圧して10分保持することで脱泡処理を行った。光硬化性樹脂組成物Kの粘度を測定したところ、2.2Pa・sであった。
表示デバイスGの画像表示領域の外周に塗布されたシール部の内側の領域に、光硬化性樹脂組成物Kを、ディスペンサを用いて総質量が125gとなるように複数個所に供給した。
以下、例1の工程(c)、工程(d)と同様にして表示装置Mを得た。表示装置Mの樹脂層中に残留する気泡等の欠陥が確認されなかった。表示デバイスGに代えてほぼ同じサイズの透明ガラス板を用いて同様に接合体を作製し、遮光印刷部のない部分でのヘイズ値を測定したところ1%以下であり、透明度が高い良好なものであった。また、平坦性も良好であった。
表示装置Mを液晶表示デバイスを取り出した液晶テレビ受像機の筺体に戻し、配線を再接合して電源を入れたところ、当初より表示コントラストの高い画像が得られた。画像表示面を指で強く押しても画像が乱れることはなく、ガラス板Hが表示デバイスGを効果的に保護していた。
なお、2009年9月25日に出願された日本特許出願2009-220584号および2010年8月10日に出願された日本特許出願2010-179503号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
10 透明面材
12 両面接着テープ
14 光硬化性樹脂組成物
36 光硬化性樹脂組成物
40 樹脂層
42 シール部
50 表示デバイス
51 偏光板
52 カラーフィルターを設けた透明面材
53 TFTを設けた透明面材
54 FPC
55 遮光印刷部
Claims (17)
- いずれか一方が表示デバイスであり、他方が透明面材である第1の面材および第2の面材と、第1の面材および第2の面材に挟まれた樹脂層と、樹脂層の周囲を囲むシール部とを有する表示装置を製造する方法であって、
下記の工程(a)~(d)を有する、透明面材により表示デバイスが保護された表示装置の製造方法。
(a)第1の面材の表面の周縁部にシール部を形成する工程(ただし、第1の面材が表示デバイスである場合は、画像が表示される側の表面の周縁部にシール部を形成する)。
(b)第1の面材のシール部で囲まれた領域に液状の硬化性樹脂組成物を供給する工程。
(c)100Pa以下の減圧雰囲気下にて、第1の面材の上に供給された硬化性樹脂組成物の上に第2の面材を重ねて、第1の面材、第2の面材およびシール部で硬化性樹脂組成物が密封された積層前駆体を得る工程(ただし、第2の面材が表示デバイスである場合は、画像が表示される側の表面が硬化性樹脂組成物側となるように重ねる)。
(d)50kPa以上の圧力雰囲気下に積層前駆体を置いた状態にて、硬化性樹脂組成物を硬化させて樹脂層を形成する工程。 - 表示デバイスが液晶表示デバイスである請求項1に記載の製造方法。
- 透明面材の外周部に遮光印刷部が設けられている請求項1または2に記載の製造方法。
- 透明面材が、ガラス板である、請求項1~3のいずれか1項に記載の製造方法。
- 透明面材の片面に反射防止層が形成されている請求項1~4のいずれか1項に記載の製造方法。
- 50kPa以上の圧力雰囲気が、大気圧雰囲気である、請求項1~5のいずれか1項に記載の製造方法。
- 硬化性樹脂組成物が、光硬化性樹脂組成物である、請求項1~6のいずれか1項に記載の製造方法。
- 光硬化性樹脂組成物が、アクリロイルオキシ基およびメタクリロイルオキシ基から選ばれる少なくとも1種の基を、1分子あたり1~3個有する化合物の少なくとも1種と、光重合開始剤とを含む、請求項7に記載の製造方法。
- 光硬化性樹脂組成物が、アクリロイルオキシ基とメタクリロイルオキシ基の一方または両方からなる硬化性官能基を1分子あたり平均1.8~4個有する分子量1000以上のオリゴマーと、水酸基の数が1個または2個である炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレートと、光重合開始剤とを含む、請求項7に記載の製造方法。
- 光硬化性樹脂組成物が、さらに、炭素数8~22のアルキル基を有するアルキルメタクリレートを含む、請求項9に記載の製造方法。
- 光硬化性樹脂組成物が、水酸基の数が1個または2個である炭素数3~8のヒドロキシアルキル基を有するヒドロキシアルキルメタクリレートの含有量より多い、炭素数8~22のアルキル基を有するアルキルメタクリレートを含む、請求項10に記載の製造方法。
- 請求項6~11のいずれか1項に記載の光硬化性樹脂組成物を用いて得られた積層前駆体を、50kPa以上の圧力雰囲気下に置いた状態にて光を照射して前記光硬化性樹脂組成物を硬化させる工程を有する請求項1~5のいずれか1項に記載の製造方法。
- 第1の面材の周縁部に形成されるシール部が、25℃での粘度が200~3000Pa・sである光硬化性樹脂組成物よりなるシール部材で形成される、請求項1~12のいずれか1項に記載の製造方法。
- 透明面材を介した光照射により光硬化樹脂組成物を硬化する前にシール部を硬化させる、請求項13に記載の製造方法。
- 透明面材の側面からの光照射によりシール部を硬化させる、請求項13または14に記載の製造方法。
- いずれか一方が表示デバイスであり、他方が透明面材である第1の面材および第2の面材と、
第1の面材および第2の面材に挟まれた樹脂層と、
第1の面材および第2の面材に挟まれ、かつ前記樹脂層の周囲をすきまなく囲むシール部とを有する、表示装置。 - 請求項1~16のいずれか1項に記載の製造方法により得られた、
いずれか一方が表示デバイスであり、他方が透明面材である第1の面材および第2の面材と、
第1の面材および第2の面材に挟まれた樹脂層と、
第1の面材および第2の面材に挟まれ、かつ前記樹脂層の周囲をすきまなく囲むシール部とを有する、表示装置。
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- 2010-09-13 CN CN201080043264.5A patent/CN102549481B/zh not_active Expired - Fee Related
- 2010-09-13 EP EP10818710A patent/EP2482122A1/en not_active Withdrawn
- 2010-09-13 WO PCT/JP2010/065762 patent/WO2011037035A1/ja active Application Filing
- 2010-09-21 TW TW099132029A patent/TWI457879B/zh not_active IP Right Cessation
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- 2012-03-23 US US13/428,388 patent/US8310649B2/en not_active Expired - Fee Related
- 2012-09-13 US US13/613,686 patent/US20130011597A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
TW201124963A (en) | 2011-07-16 |
US8310649B2 (en) | 2012-11-13 |
KR101708525B1 (ko) | 2017-02-20 |
KR20120087889A (ko) | 2012-08-07 |
TWI457879B (zh) | 2014-10-21 |
CN102549481A (zh) | 2012-07-04 |
US20120183721A1 (en) | 2012-07-19 |
US20130011597A1 (en) | 2013-01-10 |
JP5440608B2 (ja) | 2014-03-12 |
CN102549481B (zh) | 2015-07-22 |
JPWO2011037035A1 (ja) | 2013-02-21 |
EP2482122A1 (en) | 2012-08-01 |
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