WO2011102314A1 - 液晶表示装置の製造方法 - Google Patents
液晶表示装置の製造方法 Download PDFInfo
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- WO2011102314A1 WO2011102314A1 PCT/JP2011/053030 JP2011053030W WO2011102314A1 WO 2011102314 A1 WO2011102314 A1 WO 2011102314A1 JP 2011053030 W JP2011053030 W JP 2011053030W WO 2011102314 A1 WO2011102314 A1 WO 2011102314A1
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- liquid crystal
- resin layer
- resin composition
- crystal panel
- uncured
- Prior art date
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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
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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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
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
Definitions
- the present invention relates to a method for manufacturing a liquid crystal display device in which a liquid crystal panel is protected by a protective plate.
- a liquid crystal panel in which a liquid crystal cell is sandwiched between a pair of polarizing plates and a protective plate for protecting the liquid crystal panel are bonded together via a resin layer.
- a liquid crystal panel is usually obtained by sticking polarizing plates to both surfaces of a liquid crystal cell with an adhesive. At this time, it is necessary to accurately align the polarization axes of the pair of polarizing plates. However, a soft film-like polarizing plate is difficult to handle, and it is difficult to finely adjust the polarization axis when the polarizing plate is attached. If the polarization axes of the pair of polarizing plates after being attached do not match, the polarizing plate cannot be reattached, resulting in a defective product.
- the polarizing plate located on the protective plate side of the two polarizing plates is attached in advance to the protective plate instead of the liquid crystal panel, and the polarizing plate is attached only to the surface opposite to the protective plate side.
- the liquid crystal panel which is a rigid member that is easier to handle than the soft film-like polarizing plate itself, just before bonding the liquid crystal panel and the protective plate with the polarizing plate attached to the surface on the liquid crystal panel side, It has been proposed to finely adjust the polarization axis by relatively moving the protective plate (paragraph [0086], etc. of Patent Document 1).
- the present invention provides a liquid crystal display device in which the preferred angle formed by the polarization axes of the pair of polarizing means can be easily adjusted, and the remaining of bubbles in the resin layer sandwiched between the protective plate and the liquid crystal panel can be sufficiently suppressed.
- a manufacturing method is provided.
- the method for producing a liquid crystal display device of the present invention includes a protective plate in which a first polarizing means is provided on the surface of a transparent surface material, a liquid crystal panel in which a second polarizing means is provided on the surface of a liquid crystal cell, and a protective plate. And a resin layer sandwiched between the liquid crystal panel and a seal portion surrounding the periphery of the resin layer, the first polarizing means is located between the transparent surface material and the resin layer, and the second polarizing means
- A1 A step of forming an uncured seal part by applying a liquid curable resin composition for forming a seal part to the peripheral part of the surface opposite to the second polarizing means side of the liquid crystal panel.
- B1 A step of supplying a liquid curable resin composition for forming a resin layer to a region surrounded by an uncured seal portion.
- C1 In a reduced pressure atmosphere of 100 Pa or less, a protective plate is stacked on the resin layer forming curable resin composition so that the first polarizing means is on the resin layer forming curable resin composition side. The process which obtains the laminated body by which the uncured resin layer which consists of a curable resin composition for resin layer formation with the protective plate, the liquid crystal panel, and the uncured seal part was sealed.
- D1 A step of curing the uncured seal portion and the uncured resin layer in a state where the laminate is placed in a pressure atmosphere of 50 kPa or more.
- A2 A step of forming an uncured seal portion by applying a liquid seal portion forming curable resin composition to the peripheral portion of the surface of the protective plate on the first polarizing means side.
- B2 A step of supplying a liquid curable resin composition for forming a resin layer to a region surrounded by an uncured seal portion.
- C2 In a reduced-pressure atmosphere of 100 Pa or less, the liquid crystal is formed on the curable resin composition for resin layer formation so that the second polarizing means is on the side opposite to the curable resin composition side for resin layer formation.
- (D2) A step of curing the uncured seal portion and the uncured resin layer in a state where the laminate is placed under a pressure atmosphere of 50 kPa or more.
- the positions of the protective plate and the liquid crystal panel are adjusted so that the angle formed by the polarization axes of the first polarizing means and the second polarizing means matches the design of the liquid crystal cell. It is preferable.
- the preferred angle formed by the polarization axes of the pair of polarizing means can be easily adjusted, and bubbles remain in the resin layer sandwiched between the protective plate and the liquid crystal panel. Is sufficiently suppressed.
- FIG. 1 is a cross-sectional view illustrating an example of a liquid crystal display device in which a liquid crystal panel is protected by a protective plate.
- FIG. 2 is a plan view of the liquid crystal display device of FIG.
- FIG. 3 is a plan view showing an example of the state of the step (a1).
- FIG. 4 is a sectional view showing an example of the state of the step (a1).
- FIG. 5 is a plan view showing an example of the state of the step (b1).
- FIG. 6 is a cross-sectional view showing an example of the state of the step (b1).
- FIG. 7 is a cross-sectional view showing an example of the state of the step (c1).
- FIG. 8 is a cross-sectional view showing an example of the state of the step (d1).
- transparent means having light transmittance
- (meth) acrylate means acrylate or methacrylate.
- FIG. 1 is a cross-sectional view showing an example of a liquid crystal display device according to the present invention
- FIG. 2 is a plan view.
- the liquid crystal display device 1 includes a protection plate 10, a liquid crystal panel 20, a resin layer 40 sandwiched between the protection plate 10 and the liquid crystal panel 20, and a seal portion 50 that surrounds the periphery of the resin layer 40.
- the shape of the liquid crystal display device 1 is usually rectangular.
- the size of the liquid crystal display device 1 is suitably 0.5 m ⁇ 0.4 m or more in the case of a television receiver because the manufacturing method of the present invention is particularly suitable for manufacturing a relatively large area liquid crystal display device. Yes, 0.7 m ⁇ 0.4 m or more is particularly preferable.
- the upper limit of the size of the liquid crystal display device is often determined by the size of the display panel. Also, an excessively large liquid crystal display device tends to be difficult to handle during installation.
- the upper limit of the size of the liquid crystal display device 1 is usually about 2.5 m ⁇ 1.5 m due to these restrictions.
- the dimensions of the protection plate 10 and the liquid crystal panel 20 may be substantially equal, but the protection plate 10 is often slightly larger than the liquid crystal panel 20 because of the relationship with the housing that houses the liquid crystal display device 1. Conversely, the protective plate 10 may be slightly smaller than the liquid crystal panel 20 depending on the structure of the casing.
- the protection plate 10 is provided on the image display side of the liquid crystal panel 20 to protect the liquid crystal panel 20.
- the protective plate 10 is provided on the transparent surface material 12, the light shielding printing portion 14 formed on the peripheral edge of the surface of the transparent surface material 12 on the resin layer 40 side, and the surface of the transparent surface material 12 on the resin layer 40 side.
- First polarizing means 16 Unlike the conventional protective plate which consists only of a transparent surface material or the transparent surface material which provided the light-shielding printing part in the peripheral part, the protective plate 10 is provided with the 1st polarizing means 16 on the surface of the protective plate 10.
- FIG. in the present invention, such a protective plate with polarizing means is also simply referred to as a protective plate.
- the transparent surface material 12 examples include a glass plate or a transparent resin plate.
- the transparent surface material 12 has high transparency with respect to light emitted from the liquid crystal panel 20 and reflected light, light resistance, low birefringence, high planar accuracy,
- the glass plate is most preferable from the viewpoint of surface scratch resistance and high mechanical strength.
- a glass plate is also preferred from the viewpoint of sufficiently transmitting light for curing the photocurable resin composition.
- the material of the glass plate examples include glass materials such as soda lime glass, and high transmittance glass (white plate glass) having lower iron content and less bluishness is more preferable. Tempered glass may be used to increase safety. In particular, when a thin transparent surface material is required, tempered glass obtained by a chemical strengthening method can be used. For example, when the thickness of the transparent face material is 1.5 mm or less, it is preferable to use a tempered glass produced by a chemical strengthening method because the mechanical strength can be improved. Examples of the material of the transparent resin plate include highly transparent resin materials (such as polycarbonate and polymethyl methacrylate).
- the surface of the transparent surface material 12 on the first polarizing means 16 side may be subjected to a surface treatment in order to improve the interfacial adhesive force with the first polarizing means 16.
- a surface treatment method include a method of treating the surface of the transparent surface material 12 with a silane coupling agent, a treatment of forming a silicon oxide thin film through an oxidation flame using a frame burner, and the like.
- An antireflection layer may be provided on the surface of the transparent face 12 opposite to the first polarizing means 16 in order to increase the contrast of the image.
- the antireflection layer can be provided by a method of directly forming an inorganic thin film on the surface of the transparent surface material 12 or a method of sticking a transparent resin film provided with an antireflection layer to the transparent surface material 12.
- a part or the whole of the transparent surface material 12 is colored, or a part or the whole of the surface of the transparent surface material 12 is polished to form a glass to scatter light. Further, a minute unevenness or the like may be formed on a part or the whole of the light to refract or reflect the transmitted light. Further, a colored film, a light scattering film, a photorefractive film, a light reflecting film, or the like may be attached to a part or the whole of the surface of the transparent surface material 12.
- the thickness of the transparent surface material 12 is usually 0.5 to 25 mm in the case of a glass plate from the viewpoint of mechanical strength and transparency.
- 1 to 6 mm is preferable from the viewpoint of reducing the weight of the liquid crystal display device, and 3 to 20 mm is preferable for public display applications installed outdoors.
- 2 to 10 mm is preferable.
- the light-shielding printing unit 14 hides the wiring member and the like connected to the liquid crystal panel 20 so that areas other than the image display area of the liquid crystal panel 20 cannot be seen from the protective plate 10 side.
- the light shielding printing part 14 can be provided on the resin layer 40 side of the transparent surface material 12 or on the opposite side, and in terms of reducing the parallax between the light shielding printing part 14 and the image display region, the resin layer 40 of the transparent surface material 12. It is preferable to provide on the side.
- the transparent face material 12 is a glass plate, it is preferable to use ceramic printing containing a black pigment for the light shielding printing portion 14 because of high light shielding properties.
- the light-shielding printing part can also be provided in the resin layer 40 side of the 1st polarizing means 16 installed in the resin layer 40 side of the transparent surface material 12, or the back surface.
- the first polarizing means 16 is provided by a resin film, printing with an organic ink containing a black pigment or a black dye is preferable because the temperature for forming the printing portion can be lowered.
- the first polarizing means 16 is composed of a member including a polarizer having a polarization function.
- the first polarizing means 16 is a method of sticking a polarizing plate to the surface of the transparent surface material 12 with an adhesive, a film-like absorption polarizer is sandwiched between the transparent surface material 12 and a protective film, and these are bonded together. It can be provided by a method or the like.
- an absorption polarizing plate in which a pair of protective films are bonded on both sides of a film-like absorption polarizer, a wire grid type polarizer in which a plurality of fine metal wires are arranged in parallel is the surface of a transparent substrate.
- the wire grid type polarizing plate etc. which were formed in 1 are mentioned.
- the film-like absorption polarizer include those obtained by orienting a dichroic dye such as iodine in a resin film such as polyvinyl alcohol (hereinafter referred to as PVA).
- the protective film include triacetyl cellulose (hereinafter referred to as TAC) film.
- the liquid crystal panel 20 is connected to the liquid crystal cell 22, a flexible printed wiring board 24 mounted with a driving IC connected to the liquid crystal cell 22 and operating the liquid crystal cell 22, and a surface of the liquid crystal cell 22 opposite to the resin layer 40 side. And a second polarizing means 26 provided. Unlike the conventional liquid crystal panel in which the liquid crystal panel 20 is provided with polarizing plates on both sides of the liquid crystal cell, the second polarizing means 26 such as a polarizing plate is provided only on the surface opposite to the protective plate 10 side. However, in the present invention, such a liquid crystal panel with polarization means only on one side is also simply referred to as a liquid crystal panel.
- the liquid crystal cell 22 is obtained by bonding a transparent surface material 32 provided with a color filter and a transparent surface material 34 provided with a TFT through a liquid crystal layer 36.
- the surface of the liquid crystal cell 22 on the resin layer 40 side may be subjected to a surface treatment in order to improve the interfacial adhesive force with the resin layer 40 and the seal portion 50.
- the surface treatment may be performed only on the peripheral portion of the surface, or may be performed on the entire surface. Examples of the surface treatment method include a treatment method using an adhesion primer or the like which can be processed at a low temperature.
- the thickness of the liquid crystal cell 22 is usually 0.4 to 4 mm in the case of a liquid crystal cell operated by a TFT.
- the second polarizing means 26 is composed of a member including a polarizer having a polarization function.
- the second polarizing means 26 can be provided by a method of sticking a polarizing plate to the surface of the liquid crystal cell 22 with an adhesive. Examples of the polarizing plate include the above-described absorption polarizing plate and wire grid polarizing plate.
- the resin layer 40 is a layer formed by curing a liquid resin layer forming curable resin composition to be described later.
- a curable resin composition for forming a resin layer in which the elastic modulus of the cured resin is low is preferable.
- the elastic modulus of the resin is large, stress generated due to curing shrinkage or the like when the resin is cured may adversely affect the display performance of the liquid crystal panel 20.
- the thickness of the resin layer 40 is preferably 0.03 to 2 mm, more preferably 0.1 to 0.8 mm. If the thickness of the resin layer is 0.03 mm or more, the resin layer 40 can effectively buffer an impact caused by an external force from the protective plate 10 side, and the liquid crystal panel 20 can be protected. Further, in the manufacturing method of the present invention, even if foreign matter exceeding the thickness of the resin layer 40 is mixed between the protective plate 10 and the liquid crystal panel 20, the thickness of the resin layer 40 does not change greatly, and light transmission is achieved. Little impact on performance. If the thickness of the resin layer 40 is 2 mm or less, bubbles are unlikely to remain in the resin layer 40, and the entire thickness of the liquid crystal display device 1 is not unnecessarily increased.
- the thickness of the resin layer 40 As a method of adjusting the thickness of the resin layer 40, the thickness of an uncured seal portion, which will be described later, is adjusted, and the liquid resin layer forming curability supplied to the region surrounded by the uncured seal portion.
- the method of adjusting the supply amount of a resin composition is mentioned.
- the seal part 50 is formed by applying and curing a liquid seal part forming curable resin composition to be described later. Since the area outside the image display area of the liquid crystal panel 20 is relatively narrow, the width of the seal portion 50 is preferably narrowed. The width of the seal portion 50 is preferably 0.5 to 2 mm, and more preferably 0.8 to 1.6 mm.
- the method for producing a liquid crystal display device of the present invention is a method ( ⁇ ) having the following steps (a1) to (d1) or a method ( ⁇ ) having the following steps (a2) to (d2).
- (A1) A step of forming an uncured seal part by applying a liquid curable resin composition for forming a seal part to the peripheral part of the surface opposite to the second polarizing means side of the liquid crystal panel.
- (B1) A step of supplying a liquid curable resin composition for forming a resin layer to a region surrounded by an uncured seal portion.
- (C1) In a reduced pressure atmosphere of 100 Pa or less, a protective plate is stacked on the resin layer forming curable resin composition so that the first polarizing means is on the resin layer forming curable resin composition side.
- (A2) A step of forming an uncured seal portion by applying a liquid seal portion forming curable resin composition to the peripheral portion of the surface of the protective plate on the first polarizing means side.
- (B2) A step of supplying a liquid curable resin composition for forming a resin layer to a region surrounded by an uncured seal portion.
- (C2) In a reduced-pressure atmosphere of 100 Pa or less, the liquid crystal is formed on the curable resin composition for resin layer formation so that the second polarizing means is on the side opposite to the curable resin composition side for resin layer formation.
- D2 A step of curing the uncured seal portion and the uncured resin layer in a state where the laminate is placed under a pressure atmosphere of 50 kPa or more.
- a liquid curable resin composition for forming a resin layer is contained between the protective plate and the liquid crystal panel in a reduced pressure atmosphere, and is contained in a high pressure atmosphere such as an atmospheric pressure atmosphere.
- a resin layer is formed by curing a curable resin composition for forming a resin layer.
- the containment of the curable resin composition for forming a resin layer under reduced pressure is not a method of injecting the curable resin for forming a resin layer into a narrow and wide space between the protective plate and the liquid crystal panel.
- the curable resin composition for resin layer formation is supplied to almost the entire surface of one of the members, and then the other member is stacked to enclose the curable resin composition for resin layer formation between the protective plate and the liquid crystal panel. Is the method.
- WO 2008/81838 pamphlet and WO 2009/16943 pamphlet describe a method for producing a transparent laminate and a curable resin composition used in the production method, which are incorporated herein. It is done.
- the method ( ⁇ ) is the same as the method ( ⁇ ) except that the liquid crystal panel in the method ( ⁇ ) is replaced with a protective plate and the protective plate in the method ( ⁇ ) is replaced with a liquid crystal panel.
- the description of ⁇ ) is omitted.
- Step (a1) First, an uncured seal portion is formed by applying a liquid seal portion-forming curable resin composition to the peripheral portion of the surface opposite to the second polarizing means side of the liquid crystal panel.
- the application is performed using a printing machine, a dispenser, or the like.
- a liquid resin layer-forming curable resin is formed from the interface between the uncured seal portion and the liquid crystal panel and the interface between the uncured seal portion and the protective plate in the step (c1) described later. It is necessary to have an interface adhesive strength that is higher than the level at which the composition does not leak and a hardness that can maintain the shape. Therefore, it is preferable to use a sealant-forming curable resin composition having a high viscosity for the uncured seal part. Moreover, in order to maintain the space
- the viscosity of the curable resin composition for forming a seal part is preferably 500 to 3000 Pa ⁇ s, more preferably 800 to 2500 Pa ⁇ s, and still more preferably 1000 to 2000 Pa ⁇ s. If the viscosity is 500 Pa ⁇ s or more, the shape of the uncured seal portion can be maintained for a relatively long time, and the height of the uncured seal portion can be sufficiently maintained. If the viscosity is 3000 Pa ⁇ s or less, an uncured seal portion can be formed by coating. The viscosity of the curable resin composition for forming a seal part is measured at 25 ° C. using an E-type viscometer.
- the photocurable resin composition may be sufficient as the curable resin composition for seal part formation, and a thermosetting resin composition may be sufficient as it.
- a photocurable resin composition containing a curable compound and a photopolymerization initiator (C1) is preferable because it can be cured at a low temperature and has a high curing rate. Moreover, since high temperature is not required for hardening, there is also little possibility of damage to the liquid crystal panel by high temperature.
- the photocurable resin composition for forming a seal part is an oligomer (A) having a curable group and a number average molecular weight of 30,000 to 100,000 as the curable compound because the viscosity is easily adjusted within the above range. ) And one or more monomers (B) having a curable group and a molecular weight of 125 to 600, and the proportion of the monomers (B) is such that the oligomer (A) and the monomer (B ) And the total (100% by mass) is preferably 15 to 50% by mass.
- the number average molecular weight of the oligomer (A) is 30,000 to 100,000, preferably 40,000 to 80,000, more preferably 50,000 to 65,000. If the number average molecular weight of an oligomer (A) is this range, it will be easy to adjust the viscosity of the photocurable resin composition for seal part formation to the said range.
- the number average molecular weight of the oligomer (A) is a number average molecular weight in terms of polystyrene obtained by GPC measurement. In addition, in GPC measurement, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated
- Examples of the curable group of the oligomer (A) include addition-polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, etc.
- a group selected from an acryloyloxy group and a methacryloyloxy group is preferable from the viewpoint of obtaining a highly sealable portion.
- the curable group in the relatively high molecular weight oligomer (A) tends to be less reactive than the curable group in the relatively low molecular weight monomer (B)
- the curing of the monomer (B) proceeds first.
- the viscosity of the entire composition suddenly increases and the curing reaction may become inhomogeneous.
- the curable group of the oligomer (A) is changed to a relatively reactive acryloyloxy group and the curable property of the monomer (B). More preferably, the group is a methacryloyloxy group having relatively low reactivity.
- the oligomer (A) preferably has an average of 1.8 to 4 curable groups per molecule from the viewpoint of curability of the photocurable resin composition for forming a seal portion and mechanical properties of the seal portion.
- examples of the oligomer (A) include urethane oligomers having a urethane bond, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like.
- the urethane oligomer (A1) is preferable from the viewpoint that the mechanical properties, the adhesion to the liquid crystal panel or the protective plate and the like can be adjusted widely.
- the urethane oligomer (A1) having a number average molecular weight of 30,000 to 100,000 has a high viscosity, it is difficult to synthesize by a normal method, and even if synthesized, it is difficult to mix with the monomer (B). Therefore, in this invention, after synthesize
- a monomer (B) described later monomer (B1), monomer (B3), etc.
- Method for synthesizing urethane oligomer (A1) As a diluent, a polyol and a polyisocyanate are reacted in the presence of a monomer (B1) that does not have a group that reacts with an isocyanate group, which is one of the monomers (B) described later, to obtain a prepolymer having an isocyanate group. And then reacting the isocyanate group of the prepolymer with the monomer (B2) having a group that reacts with the isocyanate group and a curable group.
- polyol and polyisocyanate examples include known compounds, for example, polyol (i) and diisocyanate (ii) described as raw materials for the urethane oligomer (a) described in International Publication No. 2009/016943. , Incorporated herein.
- Monomers (B1) having no groups that react with isocyanate groups include alkyl (meth) acrylates having an alkyl group having 8 to 22 carbon atoms (n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, n -Behenyl (meth) acrylate and the like) and (meth) acrylate having an alicyclic hydrocarbon group (isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like).
- Examples of the monomer (B2) having a group that reacts with an isocyanate group and a curable group include active hydrogen (hydroxyl group, amino group, etc.) and a monomer having a curable group. Specifically, the monomer has 2 to 6 carbon atoms.
- Hydroxyalkyl (meth) acrylate having a hydroxyalkyl group (2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.))
- a hydroxyalkyl acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferable.
- the molecular weight of the monomer (B) is 125 to 600, preferably 140 to 400, more preferably 150 to 350. If the molecular weight of the monomer (B) is 125 or more, the volatilization of the monomer (B) when the liquid crystal display device is produced by the below-described reduced pressure lamination method can be suppressed. If the molecular weight of the monomer (B) is 600 or less, the solubility of the monomer (B) in the high molecular weight oligomer (A) can be increased, and the viscosity adjustment as a photocurable resin composition for forming a seal part is suitable. Can be done.
- Examples of the curable group of the monomer (B) include addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, etc.
- a group selected from an acryloyloxy group and a methacryloyloxy group is preferable from the viewpoint of obtaining a highly sealable portion.
- the curable group in the relatively low molecular weight monomer (B) tends to be more reactive than the curable group in the relatively high molecular weight oligomer (A)
- the curing of the monomer (B) proceeds first. The viscosity of the entire composition suddenly increases and the curing reaction may become inhomogeneous.
- the curable group of the monomer (B) is a methacryloyloxy group having a relatively low reactivity
- the curable group of the oligomer (A) is a acryloyloxy group having a relatively high reactivity. Is more preferable.
- the monomer (B) those having 1 to 3 curable groups per molecule are preferred from the viewpoint of curability of the photocurable resin composition for forming a seal portion and mechanical properties of the seal portion.
- the photocurable resin composition for forming a seal part may contain a monomer (B1) used as a diluent in the method for synthesizing the urethane oligomer (A1) described above as the monomer (B). Moreover, the unreacted monomer (B2) used for the synthesis
- the monomer (B) preferably contains a monomer (B3) having a hydroxyl group from the viewpoint of the adhesion between the liquid crystal panel or protective plate and the seal part and the solubility of various additives described later.
- a monomer (B3) having a hydroxyl group a hydroxy methacrylate having a hydroxyalkyl group having 1 to 2 hydroxyl groups and 3 to 8 carbon atoms (2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6 -Hydroxyhexyl methacrylate and the like are preferred, and 2-hydroxybutyl methacrylate is particularly preferred.
- the proportion of the monomer (B) is 15 to 50% by mass, preferably 20 to 45% by mass, and preferably 25 to 40% by mass in the total (100% by mass) of the oligomer (A) and the monomer (B). More preferred. When the proportion of the monomer (B) is 15% by mass or more, the curability of the photocurable resin composition for forming a seal part and the adhesion between the liquid crystal panel or the protective plate and the seal part are good. If the ratio of a monomer (B) is 50 mass% or less, it will be easy to adjust the viscosity of the photocurable resin composition for seal part formation to 500 Pa.s or more.
- Examples of the photopolymerization initiator (C1) include acetophenone series, ketal series, benzoin or benzoin ether series, phosphine oxide series, benzophenone series, thioxanthone series, quinone series, and the like. Benzoin ether photopolymerization initiators are preferred. When curing with visible light having a short wavelength, a phosphine oxide-based photopolymerization initiator is more preferable from the viewpoint of the absorption wavelength region. By using two or more kinds of photopolymerization initiators (C1) having different absorption wavelength ranges in combination, the curing time can be further increased and the surface curability at the seal portion can be increased.
- the ratio of the polymerization initiator (C1) to the polymerization initiator (C2) is preferably 20: 1 to 5: 1 from the viewpoint that curing can be efficiently and effectively performed.
- the amount of the photopolymerization initiator (C1) (when the photopolymerization initiator (C2) is included, the total amount of (C1) and (C2)) is a total of 100 parts by mass of the oligomer (A) and the monomer (B). Is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 2.5 parts by mass.
- the photocurable resin composition for forming a seal part of the present invention includes a polymerization inhibitor, a photocuring accelerator, a chain transfer agent, a light stabilizer (such as an ultraviolet absorber and a radical scavenger), and an antioxidant as necessary.
- various additives such as a flame retardant, an adhesion 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.
- a polymerization inhibitor in a smaller amount than the polymerization initiator, the stability of the photocurable resin composition for forming a seal portion can be improved, and the molecular weight of the cured resin layer can also be adjusted.
- 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.
- the antioxidant include phosphorus-based and sulfur-based compounds.
- the total amount of various additives is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the oligomer (A) and the monomer (B).
- Step (b1)) After the step (a1), a liquid curable resin composition for forming a resin layer is supplied to a region surrounded by an uncured seal portion.
- the supply amount of the curable resin composition for resin layer formation is such that the space formed by the uncured seal portion, the liquid crystal panel and the protective plate is filled with the curable resin composition for resin layer formation, and the liquid crystal panel and the protective plate Is set in advance so as to be a predetermined interval (that is, the resin layer has a predetermined thickness).
- the amount is preferably such that the thickness of the curable resin composition for forming a resin layer is slightly larger than the predetermined thickness of the resin layer.
- the supply method include a method in which the liquid crystal panel is placed flat and supplied in a dotted, linear or planar manner by a supply means such as a dispenser or a die coater.
- the viscosity of the curable resin composition for forming a resin layer is preferably 0.05 to 50 Pa ⁇ s, more preferably 1 to 20 Pa ⁇ s. If the viscosity is 0.05 Pa ⁇ s or more, the proportion of the monomer (B ′) described later can be suppressed, and the deterioration of the physical properties of the resin layer can be suppressed. Moreover, since the component having a low boiling point is reduced, it is suitable for the reduced pressure laminating method described later. If the viscosity is 50 Pa ⁇ s or less, bubbles are unlikely to remain in the resin layer.
- the viscosity of the curable resin composition for resin layer formation is measured using an E-type viscometer at 25 ° C.
- the curable resin composition for forming a resin layer may be a photocurable resin composition or a thermosetting resin composition.
- the curable resin composition for forming a resin layer is preferably a photocurable resin composition containing a curable compound and a photopolymerization initiator (C2) because it can be cured at a low temperature and has a high curing rate. Moreover, since high temperature is not required for hardening, there is also little possibility of damage to the liquid crystal panel by high temperature.
- an oligomer (A) having a curable group and a number average molecular weight of 1,000 to 100,000 is used as the curable compound because the viscosity is easily adjusted to the above range.
- the number average molecular weight of the oligomer (A ′) is 1,000 to 100,000, preferably 10,000 to 70,000. When the number average molecular weight of the oligomer (A ′) is within this range, it is easy to adjust the viscosity of the photocurable resin composition for resin layer formation within the above range.
- the number average molecular weight of the oligomer (A ′) is a polystyrene-equivalent number average molecular weight obtained by GPC measurement. In addition, in GPC measurement, when the peak of an unreacted low molecular weight component (monomer etc.) appears, this peak is excluded and a number average molecular weight is calculated
- Examples of the curable group of the oligomer (A ′) include addition-polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, and the like. From the viewpoint of obtaining a highly transparent resin layer, a group selected from an acryloyloxy group and a methacryloyloxy group is preferable. Further, since the curable group in the relatively high molecular weight oligomer (A ′) tends to be less reactive than the curable group in the relatively low molecular weight monomer (B ′), the monomer (B ′) is cured.
- the curable group of the oligomer (A ′) is an acryloyloxy group having a relatively high reactivity
- the curable group of the monomer (B ′) is a methacryloyloxy group having a relatively low reactivity. More preferably.
- oligomer (A ′) those having an average of 1.8 to 4 curable groups per molecule are preferable from the viewpoint of the curability of the photocurable resin composition for resin layer formation and the mechanical properties of the resin layer.
- examples of the oligomer (A ′) include urethane oligomers having urethane bonds, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, etc., and resins after curing by molecular design of urethane chains Of these, urethane oligomers are preferred because they can be widely adjusted in terms of their mechanical properties, adhesion to liquid crystal panels or protective plates, and the like.
- the proportion of the oligomer (A ′) is preferably 20 to 60% by mass and more preferably 30 to 50% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′).
- the proportion of the oligomer (A ′) is 20% by mass or more, the heat resistance of the resin layer is good.
- the proportion of the oligomer (A ′) is 60% by mass or less, the curability of the photocurable resin composition for resin layer formation and the adhesion between the liquid crystal panel or the protective plate and the resin layer are improved.
- the molecular weight of the monomer (B ′) is from 125 to 600, preferably from 140 to 400. If the molecular weight of the monomer (B ′) is 125 or more, volatilization of the monomer during the production of the display device by the reduced pressure lamination method described later can be suppressed. When the molecular weight of the monomer (B ′) is 600 or less, the adhesion between the liquid crystal panel or the protective plate and the resin layer becomes good.
- Examples of the curable group of the monomer (B ′) include addition polymerizable unsaturated groups (acryloyloxy group, methacryloyloxy group, etc.), combinations of unsaturated groups and thiol groups, etc. From the viewpoint of obtaining a highly transparent resin layer, a group selected from an acryloyloxy group and a methacryloyloxy group is preferable. Further, since the curable group in the relatively low molecular weight monomer (B ′) tends to be more reactive than the curable group in the relatively high molecular weight oligomer (A ′), the monomer (B ′) is cured. There is a possibility that the viscosity of the whole composition increases suddenly and the curing reaction becomes inhomogeneous.
- the curable group of the monomer (B ′) is a methacryloyloxy group having a relatively low reactivity
- the curable group of the oligomer (A ′) is a acryloyloxy group having a relatively high reactivity. More preferably.
- the monomer (B ′) is preferably one having 1 to 3 curable groups per molecule from the viewpoint of curability of the photocurable resin composition for forming a resin layer and mechanical properties of the resin layer.
- the monomer (B ′) preferably contains a monomer (B3) having a hydroxyl group from the viewpoint of adhesion between the liquid crystal panel or the protective plate and the resin layer.
- a monomer (B3) having a hydroxyl group examples include those similar to the monomer (B3) in the photocurable resin composition for forming a seal portion, and 2-hydroxybutyl methacrylate is particularly preferable.
- the proportion of the monomer (B3) is preferably 15 to 70% by mass and more preferably 20 to 50% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′).
- the proportion of the monomer (B3) is 15% by mass or more, the curability of the photocurable resin composition for resin layer formation and the adhesion between the liquid crystal panel or the protective plate and the resin layer are improved.
- the monomer (B ′) preferably contains the following monomer (B4) from the viewpoint of the mechanical properties of the resin layer.
- Monomer (B4) alkyl methacrylate having an alkyl group having 8 to 22 carbon atoms.
- Examples of the monomer (B4) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate and the like, and n-dodecyl methacrylate and n-octadecyl methacrylate are preferable.
- the proportion of the monomer (B4) is preferably 5 to 50% by mass and more preferably 15 to 40% by mass in the total (100% by mass) of the oligomer (A ′) and the monomer (B ′).
- the proportion of the monomer (B4) is 5% by mass or more, the flexibility of the resin layer is improved.
- the photopolymerization initiator (C2) has an absorption wavelength region ( ⁇ 2) existing on the longer wavelength side than the absorption wavelength region ( ⁇ 1) of the photopolymerization initiator (C1).
- the photopolymerization initiator (C2) may have only an absorption wavelength region ( ⁇ 2), and has an absorption wavelength region ( ⁇ 1 ′) and an absorption wavelength region ( ⁇ 2) overlapping with the absorption wavelength region ( ⁇ 1). It may be a thing.
- Examples of the photopolymerization initiator (C2) include acetophenone series, ketal series, benzoin or benzoin ether series, phosphine oxide series, benzophenone series, thioxanthone series, quinone series photopolymerization initiators, phosphine oxide series, A thioxanthone photopolymerization initiator is preferable, and a phosphine oxide system is particularly preferable in terms of suppressing coloring after the photopolymerization reaction.
- these photopolymerization initiators (C2) those having an absorption wavelength region ( ⁇ 2) with respect to the photopolymerization initiator (C1) are appropriately selected and used.
- the amount of the photopolymerization initiator (C2) is preferably 0.01 to 10 parts by mass, and preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass in total of the oligomer (A ′) and the monomer (B ′). Part is more preferred.
- the photocurable resin composition for resin layer formation can be prepared by using polymerization inhibitors, photocuring accelerators, chain transfer agents, light stabilizers (ultraviolet absorbers, radical scavengers, etc.), antioxidants, and flame retardants as necessary.
- Various additives such as an agent, an adhesion 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.
- a polymerization inhibitor in a smaller amount than the polymerization initiator, the stability of the photocurable resin composition for resin layer formation can be improved, and the molecular weight of the cured resin layer can also be adjusted.
- Step (c1) After the step (b1), the liquid crystal panel to which the resin layer forming curable resin composition is supplied is put into a decompression device, and the resin layer forming curable resin composition is placed on the fixed support plate in the decompression device.
- the protective plate is held at a position above the liquid crystal panel and not in contact with the curable resin composition for forming a resin layer. That is, the curable resin composition for forming a resin layer on the surface of the liquid crystal panel and the protective plate are opposed to each other without being brought into contact with each other.
- the mounting position of the liquid crystal panel and the mounting position of the protective plate are adjusted so that the angle formed by the polarization axes of the first polarizing means and the second polarizing means matches the design of the liquid crystal cell.
- the angle formed by the polarization axes of the first polarizing means and the second polarizing means is approximately 90. °.
- a moving support mechanism that can move in the vertical direction may be provided in the lower part of the decompression device, and a liquid crystal panel supplied with the curable resin composition for resin layer formation may be placed on the moving support mechanism.
- the protective plate is attached to a fixed support plate provided at the upper part in the decompression device, and the liquid crystal panel and the protective plate are opposed to each other.
- you may support both a liquid crystal panel and a protection board with the movement support mechanism provided in the upper and lower sides in the decompression device.
- the inside of the decompression device is decompressed to obtain a predetermined decompressed atmosphere.
- the liquid crystal panel and the protective plate may be positioned at predetermined positions in the decompression device during the decompression operation or after a predetermined decompression atmosphere.
- the protective plate supported by the moving support mechanism is moved downward, and the second surface is placed on the curable resin composition for forming the resin layer on the surface of the liquid crystal panel. Overlay the materials.
- the curable resin composition for forming a resin layer is sealed in the space surrounded by the surface of the liquid crystal panel, the surface of the protective plate, and the uncured seal portion.
- the curable resin composition for resin layer formation is spread by the weight of the protective plate, the pressure from the moving support mechanism, etc., and the photocurable resin composition for resin layer formation is filled in the space.
- An uncured resin layer is formed. Thereafter, when exposed to a high pressure atmosphere in the step (d), an uncured resin layer with few or no bubbles is obtained.
- 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 for resin layer formation 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 liquid crystal panel and the protective plate are overlapped to the time when the reduced pressure atmosphere is released is not particularly limited, and after the sealing of the resin layer forming curable resin composition, the reduced pressure atmosphere may be released immediately, After sealing the curable resin composition for forming a resin layer, the reduced pressure state may be maintained for a predetermined time.
- the curable resin composition for resin layer formation flows in the sealed space, the distance between the liquid crystal panel and the protective plate becomes uniform, and the sealed state is maintained even when the atmospheric pressure is increased. It becomes easy.
- 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.
- an uncured resin layer in the laminate obtained in the step (c) when an uncured seal portion is formed by applying a curable resin composition for forming a seal portion having a high viscosity can be made relatively thick, from 30 ⁇ m to 3 mm.
- Step (d1) After releasing the reduced pressure atmosphere in the step (c1), the laminate is placed in a pressure atmosphere having an atmospheric pressure of 50 kPa or more.
- the liquid crystal panel and the protective plate are pressed in the direction in which they are brought into close contact with each other due to the increased pressure. If bubbles exist in the sealed space in the laminate, the bubbles are uncured. The resin layer flows, and the entire sealed space is uniformly filled with the uncured resin layer.
- the pressure atmosphere is usually 80 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 uncured resin layer can be performed without requiring special equipment.
- the time from when the laminate is placed under a pressure atmosphere of 50 kPa or more to the start of curing of the uncured resin layer (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 laminate already when placed in an atmospheric pressure atmosphere, or if bubbles disappear during the process, the uncured resin layer can be cured immediately. it can.
- the laminate is held in an atmosphere of 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.
- the uncured seal portion may be cured simultaneously with the curing of the uncured resin layer, or may be cured in advance before the curing of the uncured resin layer.
- the uncured resin layer and the uncured seal portion are made of a photocurable composition, they are cured by irradiation with light.
- 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, UV-LED, etc.).
- a light source ultraviolet light or short wavelength visible light from a light source (ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.).
- a light source ultraviolet lamp, high pressure mercury lamp, UV-LED, etc.
- liquid crystal panels do not have optical transparency when not operated, and therefore light is irradiated from the protective plate side through a light transmitting portion surrounded by the light-shielding printing portion.
- the light shielding printing portion is provided at the peripheral portion of the protection plate, and there is an uncured seal portion and an uncured resin layer in the region sandwiched between the light shielding printing portion and the liquid crystal panel, the light transmission of the protection plate It cannot be cured sufficiently by only the light from the part. Therefore, light is irradiated from the side of the laminate.
- the light is preferably ultraviolet light or visible light of 450 nm or less.
- the protective plate is provided with an antireflection layer and the antireflection layer or the transparent resin film on which the antireflection layer is formed or the adhesive layer provided between the antireflection film and the transparent surface material does not transmit ultraviolet rays. Curing with visible light is required.
- a light source for light irradiation from the side of the laminate a light source used for light irradiation from the side of the protective plate may be used, but an LED that emits ultraviolet light or visible light of 450 nm or less is used. It is preferable because it is suitable for efficient light irradiation to a space and a specific place.
- the light may be irradiated from the side of the laminate after irradiation from the side of the protective plate, may be irradiated from the side of the protective plate after irradiation from the side of the laminate, and the side of the protective plate and You may irradiate simultaneously from the side of a layered product.
- the photopolymerization initiator (C2) contained in the resin layer forming photocurable resin composition is used as the photopolymerization initiator contained in the seal portion forming photocurable resin composition.
- a photopolymerization initiator having an absorption wavelength region ( ⁇ 2) existing on the longer wavelength side than the absorption wavelength region ( ⁇ 1) of the initiator (C1), and absorbing light as light irradiated from the side of the laminate It is preferable to use light including light having a wavelength in the wavelength range ( ⁇ 1) and light having a wavelength in the absorption wavelength range ( ⁇ 2).
- the width of the uncured seal part sandwiched between the light-shielding printed part and the liquid crystal panel is 0.5 to 2 mm, and the width of the uncured resin layer sandwiched between the light-shielded printed part and the liquid crystal panel is 1 to 10 mm. That is, the thickness of the uncured resin layer is often larger than 0.03 to 2 mm. Therefore, the light irradiated from the side is difficult to reach the uncured resin layer at the boundary portion between the light-shielding printed portion and the translucent portion.
- the photopolymerization initiator of the uncured seal portion and the photopolymerization initiator of the uncured resin layer are used having exactly the same absorption wavelength region, the light irradiated from the side is Since most of the light is absorbed by the photopolymerization initiator in the uncured seal portion, light necessary for curing does not sufficiently reach the uncured resin layer, and curing cannot be performed sufficiently. If the uncured resin layer is not sufficiently cured in the light-shielding printed part, the resin layer-forming photocurable resin composition or the uncured resin layer is not sufficiently cured at the boundary between the light-shielded printed part and the light transmitting part.
- the photo-curable resin composition for formation may diffuse over time, and the light-shielding printed part and the transparent part are transparent due to a slight difference in refractive index between the sufficiently cured resin layer of the light-transmitting part and the part that is not sufficiently cured. Optical distortion may occur in the transmitted light at the boundary with the optical part, which may reduce the image quality.
- the absorption wavelength region ( ⁇ 2) existing on the longer wavelength side than the absorption wavelength region ( ⁇ 1) of the photopolymerization initiator (C1) of the uncured seal portion As the photopolymerization initiator (C2) of the uncured resin layer, the absorption wavelength region ( ⁇ 2) existing on the longer wavelength side than the absorption wavelength region ( ⁇ 1) of the photopolymerization initiator (C1) of the uncured seal portion. And a light having a wavelength within the absorption wavelength region ( ⁇ 1) and a light having a wavelength within the absorption wavelength region ( ⁇ 2) as light irradiated from the side of the laminate. Both are used. As a result, light having a wavelength within the absorption wavelength region ( ⁇ 2) that has not been absorbed by the photopolymerization initiator (C1) of the uncured seal portion is applied to the uncured resin layer sandwiched between the light-shielding print portion and the liquid crystal panel.
- the uncured resin layer can be sufficiently cured by the photopolymerization initiator (C2) having a sufficient wavelength and an absorption wavelength region ( ⁇ 2).
- the photopolymerization initiator (C2) having a sufficient wavelength and an absorption wavelength region ( ⁇ 2).
- light from a light source having an emission wavelength region at least partially overlapping with the absorption wavelength region ( ⁇ 1) and light from a light source having an emission wavelength region at least partially overlapping with the absorption wavelength region ( ⁇ 2) Irradiation may be performed simultaneously or separately. Further, light from a light source having a light emission wavelength region that overlaps at least part of both the absorption wavelength region ( ⁇ 1) and the absorption wavelength region ( ⁇ 2) may be irradiated.
- Step (a1) As shown in FIG. 3 and FIG. 4, a photocurable resin composition for forming a seal portion by a dispenser (not shown) or the like along the peripheral edge of the surface of the liquid crystal panel 20 opposite to the second polarizing means 26 side. Is applied to form an uncured seal portion.
- a wiring member such as a flexible printed wiring board 24 that transmits an electrical signal for operating the liquid crystal panel 20 may be provided on the outer periphery of the liquid crystal panel 20.
- the liquid crystal panel 20 is preferably disposed on the lower side in terms of facilitating the arrangement of the wiring members.
- Step (b1)) Next, as shown in FIGS. 5 and 6, a resin layer forming photocurable resin composition 44 is supplied to a rectangular region 42 surrounded by an uncured seal portion 52 of the liquid crystal panel 20.
- the supply amount of the photocurable resin composition 44 for resin layer formation is such that the space sealed by the uncured seal portion 52, the liquid crystal panel 20 and the protective plate 10 (see FIG. 7) is a photocurable resin for resin layer formation. The amount is enough to be filled with the composition 44.
- the resin layer forming photocurable resin composition 44 is supplied by placing the liquid crystal panel 20 flat on the lower surface plate 66 and moving the resin layer forming light horizontally by a dispenser 60. It is carried out by supplying the curable resin composition 44 in the form of a line, a band or a dot.
- the dispenser 60 is horizontally movable in the entire range of the region 42 by a known horizontal movement mechanism including a pair of feed screws 62 and a feed screw 64 orthogonal to the feed screw 62.
- a die coater may be used instead of the dispenser 60.
- Step (c1) Next, as shown in FIG. 7, the liquid crystal panel 20 and the protection plate 10 are carried into the decompression device 70.
- An upper surface plate 74 having a plurality of suction pads 72 is disposed in the upper part of the decompression device 70, and a lower surface plate 76 is provided in the lower part.
- the upper surface plate 74 can be moved in the vertical direction by an air cylinder 78.
- the protective plate 10 is attached to the suction pad 72 with the first polarizing means 16 facing down.
- the liquid crystal panel 20 is fixed on the lower surface plate 76 with the photocurable resin composition 44 for resin layer formation facing upward.
- the air in the decompression device 70 is sucked by the vacuum pump 80.
- the atmospheric pressure in the pressure reducing device 70 reaches a reduced pressure atmosphere of, for example, 15 to 40 Pa
- the liquid crystal panel 20 waiting below is placed in a state where the protective plate 10 is sucked and held by the suction pad 72 of the upper surface plate 74.
- the air cylinder 78 is operated and lowered.
- the liquid crystal panel 20 and the protective plate 10 are overlapped via an uncured seal portion 52, and the photocurable resin composition for forming a resin layer is formed by the protective plate 10, the liquid crystal panel 20, and the uncured seal portion 52.
- a laminate is formed by sealing an uncured resin layer made of 44, and the laminate is held for a predetermined time in a reduced-pressure atmosphere.
- the mounting position of the liquid crystal panel 20 with respect to the lower surface plate 76, the number of suction pads 72, the mounting position of the protective plate 10 with respect to the upper surface plate 74, and the like are appropriately adjusted according to the size, shape, etc. of the liquid crystal panel 20 and the protective plate 10. To do.
- the mounting position of the liquid crystal panel 20 and the mounting position of the protection plate 10 are adjusted so that the angle formed by the polarization axes of the first polarizing means 16 and the second polarizing means 26 matches the design of the liquid crystal cell.
- the angle formed by the polarization axes of the first polarizing means and the second polarizing means is approximately 90. °.
- an electrostatic chuck is used as the suction pad, and the glass substrate is mounted by adopting the electrostatic chuck holding method described in the specification (incorporated herein) attached to Japanese Patent Application No. 2008-206124. It can be stably maintained in a reduced-pressure atmosphere.
- Step (d1)) Next, after the inside of the decompression device 70 is set to atmospheric pressure, for example, the laminate is taken out from the decompression device 70.
- the laminate When the laminate is placed under an atmospheric pressure atmosphere, the surface of the laminate on the liquid crystal panel 20 side and the surface of the protective plate 10 are pressed by the atmospheric pressure, and the photocurable resin composition for resin layer formation in the sealed space The object 44 is pressed by the liquid crystal panel 20 and the protective plate 10.
- the uncured resin layer in the sealed space flows, and the entire sealed space is uniformly filled with the uncured resin layer.
- the first polarizing means 16 can be obtained by moving the position of the protective plate 10 relative to the liquid crystal panel 20 if the position is slightly adjusted.
- the angle formed by the polarization axis of the second polarizing means 26 can also be adjusted.
- light (ultraviolet rays) is applied to the uncured seal portion 52 and the uncured resin layer 46 sandwiched between the light-shielding print portion 14 and the liquid crystal panel 20 from the side of the laminate. Irradiate to the periphery and irradiate light (ultraviolet rays) to the uncured resin layer 46 from the side of the protective plate 10 through the light transmitting portion 18, thereby uncured seal portion 52 and uncured resin layer 46 inside the laminate.
- the liquid crystal display device 1 is manufactured by curing.
- the method for manufacturing the liquid crystal display device of the present invention has been specifically described by taking the case of the method ( ⁇ ) as an example.
- the polarizing means located on the protective plate side of the two polarizing means is attached in advance to the protective plate instead of the liquid crystal panel. Just before the protective plate and the protective plate are overlapped, the liquid crystal panel and the protective plate can be relatively moved to finely adjust the polarization axes of the two polarizing means. Therefore, the preferred angle formed by the polarization axes of the two polarizing means can be easily adjusted.
- a liquid crystal display device having a relatively large area can be manufactured without generating bubbles in the resin layer. Even if bubbles remain in the uncured resin layer sealed under reduced pressure, the pressure is also applied to the sealed uncured resin layer 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 uncured resin layer sealed under 100 Pa is considered to be 1/1000 under 100 kPa. Since the gas may be dissolved in the uncured resin layer, the gas in the minute volume of bubbles quickly dissolves in the uncured resin layer and disappears.
- liquid curable resin composition for forming a resin layer is a fluid composition
- the pressure is applied to the surface of the liquid crystal panel. Is uniformly distributed, and no further stress is applied to a part of the surface of the liquid crystal panel in contact with the uncured resin layer, and there is little risk of damage to the liquid crystal panel.
- the interfacial adhesive force between the resin layer, the liquid crystal panel and the protective plate due to the curing of the curable resin composition for forming the resin layer is higher than the interfacial adhesive force due to the fusion of the heat-fusible resin.
- the curable resin composition for forming a fluid resin layer is pressurized to adhere to the surfaces of the liquid crystal panel and the protective plate and cured in that state, higher interfacial adhesion can be obtained, and the liquid crystal panel and the protection can be obtained. Uniform adhesion to the surface of the plate 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 reduced and the resin layer is formed in a short time.
- the forming curable resin composition can be filled.
- there are few restrictions on the viscosity of the curable resin composition for forming a resin layer and the curable resin composition for forming a resin layer having a high viscosity can be easily filled. Therefore, it is possible to use a curable resin composition for forming a high-viscosity resin layer containing a relatively high molecular weight curable compound capable of increasing the strength of the resin layer.
- the photopolymerization initiator (C2) of the uncured resin layer the absorption wavelength region ( ⁇ 2) existing on the longer wavelength side than the absorption wavelength region ( ⁇ 1) of the photopolymerization initiator (C1) of the uncured seal portion. And a light having a wavelength within the absorption wavelength region ( ⁇ 1) and a light having a wavelength within the absorption wavelength region ( ⁇ 2) as light irradiated from the side of the laminate. Therefore, light having a wavelength within the absorption wavelength region ( ⁇ 2) that was not absorbed by the photopolymerization initiator (C1) of the uncured seal portion was sandwiched between the light-shielding print portion and the liquid crystal panel.
- the uncured resin layer can be sufficiently cured by the photopolymerization initiator (C2) that sufficiently reaches the uncured resin layer and has the absorption wavelength region ( ⁇ 2).
- Example 1 is an example and Example 2 is a comparative example.
- the number average molecular weight of the oligomer was determined using a GPC apparatus (manufactured by TOSOH, HLC-8020).
- the viscosity of the photocurable resin composition was measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U).
- the haze value was determined by measurement according to ASTM D1003 using a haze guard II manufactured by Toyo Seiki Seisakusho.
- Example 1 (LCD panel) When the liquid crystal is not energized, the liquid crystal is oriented in a direction substantially perpendicular to the transparent surface material of the liquid crystal cell.
- the polarization axis is short of the liquid crystal cell only on one side of the liquid crystal cell having a length of 712 mm, a width of 412 mm, and a thickness of about 2 mm.
- a liquid crystal panel A on which an absorptive polarizing plate was stuck so as to be parallel to the side was prepared.
- the image display area was 696 mm long and 390 mm wide.
- a soda-lime glass plate with a length of 794 mm, a width of 479 mm, and a thickness of 3 mm is shielded in a frame shape by ceramic printing including a black pigment so that the translucent portion has a length of 698 mm and a width of 392 mm. A printing part was formed.
- the surface of the side of the soda-lime glass plate on which the light-shielding printing portion is formed is set so that the polarization axis of the film-like absorption polarizer in which iodine is oriented in the PVA film is parallel to the long side of the protective plate.
- the absorptive polarizer was sandwiched between a soda lime glass plate and a TAC film so as to be in contact with each other, and these were bonded together.
- an antireflection film manufactured by Nippon Oil & Fats Co., Ltd., Realak X4001
- the protective plate B is attached.
- UC-1 urethane acrylate oligomer
- Defoaming treatment was performed by placing the photocurable resin composition C for forming a seal part in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding for 10 minutes. .
- the viscosity at 25 ° C. of the photocurable resin composition C for forming a seal part was measured and found to be about 1400 Pa ⁇ s.
- a bifunctional polypropylene glycol having a molecular end modified with ethylene oxide (number average molecular weight calculated from hydroxyl value: 4000) and isophorone diisocyanate were mixed at a molar ratio of 4 to 5, and 70 in the presence of a tin compound catalyst.
- a urethane acrylate oligomer (hereinafter referred to as UA-2) is obtained by adding 2-hydroxyethyl acrylate in a molar ratio of about 1: 2 to the prepolymer obtained by reacting at a temperature of 70 ° C. and reacting at 70 ° C. Got.
- the number of curable groups of UA-2 was 2, the number average molecular weight was about 24,000, and the viscosity at 25 ° C. was about 830 Pa ⁇ s.
- IRGACURE 819 has an absorption wavelength region (about 440 nm or less) on the longer wavelength side than the absorption wavelength region (about 380 nm or less) of IRGACURE 184.
- Defoaming treatment was performed by placing the photocurable resin composition D for resin layer formation in a decompression device in an open state while being placed in a container, and reducing the pressure in the decompression device to about 20 Pa and holding for 10 minutes. . It was 1.7 Pa.s when the viscosity at 25 degrees C of the photocurable resin composition D for resin layer formation was measured.
- Step (a1) The surface of the liquid crystal panel A opposite to the polarizing plate side (that is, the surface on which the polarizing plate is not formed) and the entire circumference at a position of about 5 mm outside the image display region are about 1 mm wide and the coating thickness is about
- the photocurable resin composition C for forming a seal part was applied with a dispenser so as to be 0.6 mm, thereby forming an uncured seal part.
- Step (b1) A plurality of photocurable resin compositions D for resin layer formation are applied to the inner region of the uncured seal portion applied to the outer periphery of the image display region of the liquid crystal panel A using a dispenser so that the total mass becomes 125 g. Supply to the place. While the photocurable resin composition D for resin layer formation was supplied, the shape of the uncured seal portion was maintained.
- Step (c1) The liquid crystal panel A was placed flat on the upper surface of the lower surface plate in the decompression device in which a pair of surface plate lifting devices are installed so that the photocurable resin composition D for resin layer formation faces upward.
- the protective plate B When the protective plate B is viewed from above using an electrostatic chuck on the lower surface of the upper plate of the lifting device in the decompression device so that the surface on the absorption polarizer side faces the liquid crystal panel A, the protective plate The translucent part without the B light-shielding printing part and the image display area of the liquid crystal panel A are held at the same position with a margin of about 1 mm so that the distance from the liquid crystal panel A is 30 mm in the vertical direction. .
- the polarizing axes of the polarizing plate of the liquid crystal panel A and the absorbing polarizer of the protective plate B were arranged so as to be orthogonal to each other.
- the decompression device was sealed and evacuated until the pressure in the decompression device reached about 10 Pa.
- the upper and lower surface plates are brought close to each other by the lifting device in the decompression device, and the liquid crystal panel A and the protective plate B are pressure-bonded with a pressure of 2 kPa through the photocurable resin composition D for resin layer formation and held for 1 minute. It was. Static electricity is removed from the electrostatic chuck, the protective plate B is separated from the upper platen, and the pressure reducing device is returned to atmospheric pressure in about 15 seconds.
- the liquid crystal panel A, the protective plate B, and the uncured seal portion are used to form a resin layer.
- a laminate E in which an uncured resin layer made of the curable resin composition D was sealed was obtained. In the laminate E, the shape of the uncured seal portion was maintained in an almost initial state.
- Step (d1) An ultraviolet LED is linearly arranged from the side of the laminate E to an uncured seal portion (photocurable resin composition C for forming a seal portion) provided on the peripheral edge of the liquid crystal panel A of the laminate E.
- an ultraviolet light source (LL146-395 manufactured by Spectrum Illumination)
- light was irradiated for about 10 minutes over the entire circumference of the uncured seal portion to cure the uncured seal portion.
- the intensity of the irradiated light was measured with an illuminometer (manufactured by Oak Manufacturing Co., Ltd., UV-M02, photoreceiver UV-42) and found to be about 5 mW / cm 2 .
- the laminate E was kept horizontal and allowed to stand for about 10 minutes.
- the uncured resin layer (photocurable resin composition D for resin layer formation).
- a resin layer was formed, and a liquid crystal display device F was obtained.
- defects such as bubbles remaining in the resin layer were not confirmed, although a bubble removing step required at the time of manufacturing by the conventional injection method was unnecessary.
- defects such as leakage of the photocurable resin composition for resin layer formation from the seal portion were not confirmed.
- the thickness of the resin layer was a target thickness (about 0.4 mm).
- a transparent laminate was prepared in the same manner using a glass plate of almost the same size in place of the liquid crystal panel A, and the haze value was measured at a portion without the printing light-shielding portion. Met.
- the liquid crystal display device F was put in the housing of a liquid crystal television receiver, the wiring was reconnected, and the power was turned on, an image with high display contrast was obtained. Even when the image display surface was strongly pressed with a finger, the image was not disturbed, and the protective plate B effectively protected the liquid crystal panel A.
- 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 liquid crystal panel A, 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 liquid crystal panel A was overlaid on the protective plate B and bonded with a double-sided adhesive tape on three sides. Between the double-sided adhesive tape on one side leaving the release film and the protective plate B, about 2 mm is opened by a screwdriver, and 155 g of the photocurable resin composition D for resin layer formation is poured from that portion. However, bubbles remained in the lower part of the space between the liquid crystal panel A and the protective plate B, and the photocurable resin composition D for resin layer formation could not be poured into the space densely.
Abstract
Description
(b1)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c1)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第1の偏光手段が樹脂層形成用硬化性樹脂組成物側となるように保護板を重ねて、保護板、液晶パネルおよび未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d1)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。
(b2)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c2)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第2の偏光手段が樹脂層形成用硬化性樹脂組成物側とは反対側となるように液晶パネルを重ねて、保護板、液晶パネルおよび未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d2)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。
前記工程(c1)および工程(c2)にて、第1の偏光手段および第2の偏光手段の偏光軸の成す角度が液晶セルの設計に合うように、保護板および液晶パネルの位置を調整することが好ましい。
図1は、本発明における液晶表示装置の一例を示す断面図であり、図2は、平面図である。
液晶表示装置1は、保護板10と、液晶パネル20と、保護板10と液晶パネル20とに挟まれた樹脂層40と、樹脂層40の周囲を囲むシール部50とを有する。
液晶表示装置1の大きさは、本発明の製造方法が比較的大面積の液晶表示装置の製造に特に適していることから、テレビ受像機の場合、0.5m×0.4m以上が適当であり、0.7m×0.4m以上が特に好ましい。液晶表示装置の大きさの上限は、表示パネルの大きさで決まることが多い。また、あまりに大きい液晶表示装置は、設置等における取り扱いが困難となりやすい。液晶表示装置1の大きさの上限は、これらの制約から、通常2.5m×1.5m程度である。
保護板10および液晶パネル20の寸法は、ほぼ等しくてもよいが、液晶表示装置1を収納する筺体との関係から、保護板10が液晶パネル20より一回り大きくなる場合も多い。また逆に、筺体の構造によっては、保護板10を液晶パネル20より若干小さくしてもよい。
保護板10は、液晶パネル20の画像表示側に設けられて液晶パネル20を保護するものである。
保護板10は、透明面材12と、透明面材12の樹脂層40側の表面の周縁部に形成された遮光印刷部14と、透明面材12の樹脂層40側の表面に設けられた第1の偏光手段16とを有する。
保護板10は、透明面材のみ、または周縁部に遮光印刷部を設けた透明面材からなる従来の保護板とは異なり、保護板10の表面に第1の偏光手段16が設けられているが、本発明においては、このような偏光手段付きの保護板も単に保護板と称する。
透明面材12としては、ガラス板または透明樹脂板が挙げられ、液晶パネル20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の硬化のための光を充分に透過させる点でも、ガラス板が好ましい。
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。
遮光印刷部14は、液晶パネル20の画像表示領域以外が保護板10側から視認できないようにして、液晶パネル20に接続されている配線部材等を隠蔽するものである。遮光印刷部14は、透明面材12の樹脂層40側またはその反対側に設けることができ、遮光印刷部14と画像表示領域との視差を低減する点では、透明面材12の樹脂層40側に設けるのが好ましい。透明面材12がガラス板の場合、遮光印刷部14に黒色顔料を含むセラミック印刷を用いると遮光性が高く好ましい。また、透明面材12の樹脂層40側に設置する第1の偏光手段16の樹脂層40側、またはその裏面に遮光印刷部を設けることもできる。第1の偏光手段16が樹脂フィルムにより提供される場合は、黒色顔料や黒色染料を含む有機系インクによる印刷が、印刷部形成の温度を低くでき好ましい。
第1の偏光手段16は、偏光機能を有する偏光子を含む部材から構成される。
第1の偏光手段16は、偏光板を透明面材12の表面に粘着剤で貼着する方法、フィルム状の吸収型偏光子を透明面材12と保護フィルムとで挟み、これらを貼合する方法等によって設けることができる。
フィルム状の吸収型偏光子としては、ヨウ素等の二色性色素をポリビニルアルコール(以下、PVAと記す。)等の樹脂フィルム中に配向させたものが挙げられる。
保護フィルムとしては、トリアセチルセルロース(以下、TACと記す。)フィルム等が挙げられる。
液晶パネル20は、液晶セル22と、液晶セル22に接続され、液晶セル22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24と、液晶セル22の樹脂層40側とは反対側の表面に設けられた第2の偏光手段26とを有する。
液晶パネル20は、液晶セルの両面に偏光板が設けられた従来の液晶パネルとは異なり、保護板10側とは反対側の表面のみに偏光板等の第2の偏光手段26が設けられているが、本発明においては、このような片面のみ偏光手段付きの液晶パネルも単に液晶パネルと称する。
液晶セル22は、カラーフィルタが設けられた透明面材32とTFTが設けられた透明面材34とを液晶層36を介して貼合したものである。
第2の偏光手段26は、偏光機能を有する偏光子を含む部材から構成される。
第2の偏光手段26は、偏光板を液晶セル22の表面に粘着剤で貼着する方法等によって設けることができる。
偏光板としては、上述した吸収型偏光板、ワイヤグリッド型偏光板等が挙げられる。
樹脂層40は、後述する液状の樹脂層形成用硬化性樹脂組成物を硬化してなる層である。液晶表示装置1においては、硬化後の樹脂の弾性率が低くなる樹脂層形成用硬化性樹脂組成物が好ましい。樹脂の弾性率が大きいと、樹脂の硬化に際して硬化収縮等で発生する応力が、液晶パネル20の表示性能に悪影響を与えるおそれがある。
シール部50は、後述する液状のシール部形成用硬化性樹脂組成物を塗布し、硬化してなるものである。液晶パネル20の画像表示領域の外側の領域が比較的狭いため、シール部50の幅は狭くすることが好ましい。シール部50の幅は、0.5~2mmが好ましく、0.8~1.6mmがより好ましい。
本発明の液晶表示装置の製造方法は、下記工程(a1)~(d1)を有する方法(α)、または下記工程(a2)~(d2)を有する方法(β)である。
(a1)液晶パネルの第2の偏光手段側とは反対側の表面の周縁部に、液状のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程。
(b1)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c1)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第1の偏光手段が樹脂層形成用硬化性樹脂組成物側となるように保護板を重ねて、保護板、液晶パネルおよび未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d1)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。
(a2)保護板の第1の偏光手段側の表面の周縁部に、液状のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程。
(b2)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c2)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第2の偏光手段が樹脂層形成用硬化性樹脂組成物側とは反対側となるように液晶パネルを重ねて、保護板、液晶パネルおよび未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d2)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。
まず、液晶パネルの第2の偏光手段側とは反対側の表面の周縁部に、液状のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する。
塗布は、印刷機、ディスペンサ等を用いて行われる。
シール部形成用硬化性樹脂組成物の粘度は、25℃においてE型粘度計を用いて測定する。
オリゴマー(A)の数平均分子量は、GPC測定によって得られた、ポリスチレン換算の数平均分子量である。なお、GPC測定において、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
オリゴマー(A)としては、ウレタン結合を有するウレタンオリゴマー、ポリオキシアルキレンポリオールのポリ(メタ)アクリレート、ポリエステルポリオールのポリ(メタ)アクリレート等が挙げられ、ウレタン鎖の分子設計等によって硬化後の樹脂の機械的特性、液晶パネルまたは保護板との密着性等を幅広く調整できる点から、ウレタンオリゴマー(A1)が好ましい。
希釈剤として、後述するモノマー(B)の1種であるイソシアネート基と反応する基を有さないモノマー(B1)の存在下、ポリオールとポリイソシアネートとを反応させてイソシアネート基を有するプレポリマーを得た後、該プレポリマーのイソシアネート基に、イソシアネート基と反応する基および硬化性基を有するモノマー(B2)を反応させる方法。
モノマー(B)としては、シール部形成用光硬化性樹脂組成物の硬化性、シール部の機械的特性の点から、硬化性基を1分子あたり1~3個有するものが好ましい。
水酸基を有するモノマー(B3)としては、水酸基数1~2、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メタアクリレート(2-ヒドロキシプロピルメタクリレート、2-ヒドロキシブチルメタクリレート、4-ヒドロキシブチルメタクリレート、6-ヒドロキシヘキシルメタクリレート等)が好ましく、2-ヒドロキシブチルメタクリレートが特に好ましい。
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。
工程(a1)の後、未硬化のシール部で囲まれた領域に液状の樹脂層形成用硬化性樹脂組成物を供給する。
樹脂層形成用硬化性樹脂組成物の供給量は、未硬化のシール部、液晶パネルおよび保護板によって形成される空間が樹脂層形成用硬化性樹脂組成物によって充填され、かつ液晶パネルと保護板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)だけの分量にあらかじめ設定する。この際、樹脂層形成用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することが好ましい。よって、該分量は、樹脂層の所定厚さよりも樹脂層形成用硬化性樹脂組成物の厚さが若干厚くなる量が好ましい。
供給方法としては、液晶パネルを平置きにし、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。
樹脂層形成用硬化性樹脂組成物の粘度は、25℃においてE型粘度計を用いて測定する。
オリゴマー(A’)の数平均分子量は、GPC測定によって得られた、ポリスチレン換算の数平均分子量である。なお、GPC測定において、未反応の低分子量成分(モノマー等)のピークが現れる場合は、該ピークを除外して数平均分子量を求める。
オリゴマー(A’)としては、ウレタン結合を有するウレタンオリゴマー、ポリオキシアルキレンポリオールのポリ(メタ)アクリレート、ポリエステルポリオールのポリ(メタ)アクリレート等が挙げられ、ウレタン鎖の分子設計等によって硬化後の樹脂の機械的特性、液晶パネルまたは保護板との密着性等を幅広く調整できる点から、ウレタンオリゴマーが好ましい。
モノマー(B’)としては、樹脂層形成用光硬化性樹脂組成物の硬化性、樹脂層の機械的特性の点から、硬化性基を1分子あたり1~3個有するものが好ましい。
水酸基を有するモノマー(B3)としては、シール部形成用光硬化性樹脂組成物におけるモノマー(B3)と同様のものが挙げられ、2-ヒドロキシブチルメタクリレートが特に好ましい。
モノマー(B4):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。
モノマー(B4)としては、n-ドデシルメタクリレート、n-オクタデシルメタクリレート、n-ベヘニルメタクリレート等が挙げられ、n-ドデシルメタクリレート、n-オクタデシルメタクリレートが好ましい。
光重合開始剤(C2)としては、これらの光重合開始剤のうち、光重合開始剤(C1)に対して吸収波長域(λ2)を有するものを適宜選択して用いる。
工程(b1)の後、樹脂層形成用硬化性樹脂組成物が供給された液晶パネルを減圧装置に入れ、減圧装置内の固定支持盤の上に、樹脂層形成用硬化性樹脂組成物が上を向くように液晶パネルを平置きする。
減圧装置内の上部に設けられた、上下方向に移動可能な移動支持機構に、第1の偏光手段が下を向くように保護板を取り付ける。
保護板は、液晶パネルの上方かつ樹脂層形成用硬化性樹脂組成物と接しない位置に保持される。すなわち、液晶パネルの表面の樹脂層形成用硬化性樹脂組成物と保護板とを接触させることなく対向させる。
また、液晶パネルの取り付け位置および保護板の取り付け位置は、第1の偏光手段および第2の偏光手段の偏光軸の成す角度が液晶セルの設計に合うように調整する。たとえば、非通電時に液晶セル中の液晶が概ね液晶セルの透明面材に対して垂直方向となる液晶セルにおいては、第1の偏光手段および第2の偏光手段の偏光軸の成す角度はほぼ90°とする。
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保護板を下方に移動し、液晶パネルの表面の樹脂層形成用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、保護板の自重、移動支持機構からの押圧等によって、樹脂層形成用硬化性樹脂組成物が押し広げられ、前記空間内に樹脂層形成用光硬化性樹脂組成物が充満し、未硬化の樹脂層が形成される。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未硬化の樹脂層となる。
工程(c1)において減圧雰囲気を解除した後、積層物を雰囲気圧力が50kPa以上の圧力雰囲気下に置く。
積層物を50kPa以上の圧力雰囲気下に置くと、上昇した圧力によって液晶パネルと保護板とが密着する方向に押圧されるため、積層物内の密閉空間に気泡が存在すると、気泡に未硬化の樹脂層が流動していき、密閉空間全体が未硬化の樹脂層によって均一に充填される。
この際、積層物の液晶パネルおよび保護板のうち、光透過性を有する保護板の側から未硬化の樹脂層に光を照射し、また、積層物の側方から遮光印刷部および液晶パネルに挟まれた未硬化のシール部および未硬化の樹脂層に光を照射する。
また、保護板の周縁部に遮光印刷部が設けられていて、遮光印刷部と液晶パネルに挟持される領域に、未硬化のシール部および未硬化の樹脂層が存在すると、保護板の透光部からの光だけでは充分に硬化できない。よって、積層物の側方から光を照射する。
積層物の側方からの光照射の光源としては、保護板の側からの光照射に用いる光源を用いてもよいが、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および特定個所への効率的な光照射に適している点から好ましい。
遮光印刷部および液晶パネルに挟まれた未硬化のシール部の幅は0.5~2mmであり、遮光印刷部および液晶パネルに挟まれた未硬化の樹脂層の幅は1~10mmである、すなわち未硬化の樹脂層の厚さの0.03~2mmよりも大きい場合が多い。そのため、側方から照射された光は、遮光印刷部と透光部との境界の部分の未硬化の樹脂層まで届きにくい。
該状況において、もし、未硬化のシール部の光重合開始剤と、未硬化の樹脂層の光重合開始剤として、まったく同じ吸収波長域を有するものを用いると、側方から照射された光が未硬化のシール部の光重合開始剤にほとんどが吸収されるため、硬化に必要な光が未硬化の樹脂層に充分に到達せず、硬化を充分に行うことができない。遮光印刷部における未硬化の樹脂層の硬化が充分でないと、遮光印刷部と透光部との境界の部分に、硬化が充分でない樹脂層形成用光硬化性樹脂組成物または未硬化の樹脂層形成用光硬化性樹脂組成物が経時的に拡散することがあり、透光部の充分に硬化した樹脂層と、硬化が充分でない部分とのわずかな屈折率の違いにより、遮光印刷部と透光部との境界の部分において、透過光に光学的な歪が発生することがあり、画質が低下するおそれがある。
この際、吸収波長域(λ1)と少なくとも一部が重複する発光波長域を有する光源からの光と、吸収波長域(λ2)と少なくとも一部が重複する発光波長域を有する光源からの光を、同時に照射してもよく、別々に照射してもよい。また、吸収波長域(λ1)および吸収波長域(λ2)の両方と少なくとも一部が重複する発光波長域を有する光源からの光を照射してもよい。
以下、方法(α)の場合を例にして、図1の液晶表示装置の製造方法を、図面を用いて具体的に説明する。
図3および図4に示すように、液晶パネル20の第2の偏光手段26側とは反対側の表面の周縁部に沿ってディスペンサ(図示略)等によってシール部形成用光硬化性樹脂組成物を塗布して未硬化のシール部を形成する。
液晶パネル20の外周部には、液晶パネル20を動作させるための電気信号を伝達するフレキシブルプリント配線板24等の配線部材が設置されていることがある。本発明の製造方法において液晶パネル20および保護板10を保持する際に、配線部材の配置を容易にする点では、液晶パネル20を下側に配置することが好ましい。
ついで、図5および図6に示すように、液晶パネル20の未硬化のシール部52に囲まれた矩形状の領域42に樹脂層形成用光硬化性樹脂組成物44を供給する。樹脂層形成用光硬化性樹脂組成物44の供給量は、未硬化のシール部52と液晶パネル20と保護板10(図7参照)とによって密閉される空間が樹脂層形成用光硬化性樹脂組成物44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60は、一対の送りねじ62と、送りねじ62に直交する送りねじ64とからなる公知の水平移動機構によって、領域42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60の代わりに、ダイコータを用いてもよい。
ついで、図7に示すように、液晶パネル20と保護板10とを減圧装置70内に搬入する。減圧装置70内の上部には、複数の吸着パッド72を有する上定盤74が配置され、下部には、下定盤76が設けられている。上定盤74は、エアシリンダ78によって上下方向に移動可能とされている。
保護板10は、第1の偏光手段16を下に向けて吸着パッド72に取り付けられる。液晶パネル20は、樹脂層形成用光硬化性樹脂組成物44を上に向けて下定盤76の上に固定される。
ついで、減圧装置70の内部をたとえば大気圧にした後、積層物を減圧装置70から取り出す。積層物を大気圧雰囲気下に置くと、積層物の液晶パネル20の側の表面と保護板10の側の表面とが大気圧によって押圧され、密閉空間内の樹脂層形成用光硬化性樹脂組成物44が液晶パネル20と保護板10とで加圧される。この圧力によって、密閉空間内の未硬化の樹脂層が流動して、密閉空間全体が未硬化の樹脂層によって均一に充填される。上記密閉空間全体が未硬化の樹脂層によって充填された後であっても、僅かな位置調整であれば保護板10の位置を液晶パネル20に対して移動させることにより、第1の偏光手段16および第2の偏光手段26の偏光軸の成す角度を調整することもできる。
以上説明した本発明の液晶表示装置の製造方法にあっては、2つの偏光手段のうち保護板側に位置する偏光手段を、液晶パネルではなく、保護板にあらかじめ貼り付けているため、液晶パネルと保護板とを重ねる直前に、液晶パネルと保護板とを相対的に移動させ、2つの偏光手段の偏光軸の微調整を行うことができる。そのため、2つの偏光手段の偏光軸の成す好ましい角度を容易に合わせることができる。
オリゴマーの数平均分子量は、GPC装置(TOSOH社製、HLC-8020)を用いて求めた。
光硬化性樹脂組成物の粘度は、E型粘度計(東機産業社製、RE-85U)にて測定した。
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に準じた測定によって求めた。
(液晶パネル)
非通電時に液晶が液晶セルの透明面材に対して概ね垂直な方向に配向している、長さ712mm、幅412mm、厚さ約2mmの液晶セルの片面だけに、偏光軸が液晶セルの短辺と平行となるように吸収型偏光板が貼着された液晶パネルAを用意した。画像表示領域は、長さ696mm、幅390mmであった。
長さ794mm、幅479mm、厚さ3mmのソーダライムガラス板の一方の表面の周縁部に、透光部が長さ698mm、幅392mmとなるように黒色顔料を含むセラミック印刷にて額縁状に遮光印刷部を形成した。
ついで、ヨウ素をPVAフィルム中に配向させたフィルム状の吸収型偏光子の偏光軸が保護板の長辺と平行となるようにして、ソーダライムガラス板の遮光印刷部を形成した側の表面と接するように、吸収型偏光子をソーダライムガラス板とTACフィルムとで挟み、これらを貼合した。
ついで、ソーダライムガラス板の吸収型偏光子側とは反対側の表面全体に、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着して、保護板Bを作製した。
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、ヘキサメチレンジイソシアネートとを、6対7となるモル比で混合し、ついでイソボルニルアクリレート(大阪有機化学工業社製、IBXA)で希釈した後、錫化合物の触媒存在下で70℃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70℃で反応させることによって、30質量%のイソボルニルアクリレートで希釈されたウレタンアクリレートオリゴマー(以下、UC-1と記す。)溶液を得た。UC-1の硬化性基数は2であり、数平均分子量は約55000であった。UC-1溶液の60℃における粘度は約580Pa・sであった。
分子末端をエチレンオキシドで変性した2官能のポリプロピレングリコール(水酸基価より算出した数平均分子量:4000)と、イソホロンジイソシアネートとを、4対5となるモル比で混合し、錫化合物の触媒存在下で70℃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70℃で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の硬化性基数は2であり、数平均分子量は約24000であり、25℃における粘度は約830Pa・sであった。
IRGACURE 819は、IRGACURE 184の吸収波長域(約380nm以下)よりも長波長側にも吸収波長域(約440nm以下)を有する。
液晶パネルAの偏光板側とは反対側の表面(つまり、偏光板が形成されていない面)、かつ画像表示領域の外側の約5mmの位置の全周にわたって、幅約1mm、塗布厚さ約0.6mmとなるようにシール部形成用光硬化性樹脂組成物Cをディスペンサにて塗布し、未硬化のシール部を形成した。
液晶パネルAの画像表示領域の外周に塗布された未硬化のシール部の内側の領域に、樹脂層形成用光硬化性樹脂組成物D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。
樹脂層形成用光硬化性樹脂組成物Dを供給する間、未硬化のシール部の形状は維持されていた。
液晶パネルAを、一対の定盤の昇降装置が設置されている減圧装置内の下定盤の上面に、樹脂層形成用光硬化性樹脂組成物Dが上を向くように平置した。
保護板Bを、吸収型偏光子側の表面が液晶パネルAに対向するように、減圧装置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保護板Bの遮光印刷部のない透光部と液晶パネルA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、垂直方向では液晶パネルAとの距離が30mmとなるように保持させた。このとき、液晶パネルAの偏光板および保護板Bの吸収型偏光子の偏光軸はお互いに直交するように配置されていた。
積層物Eにおいて未硬化のシール部の形状は、ほぼ初期の状態のまま維持されていた。
積層物Eの液晶パネルAの周縁部に設けられた未硬化のシール部(シール部形成用光硬化性樹脂組成物C)に、積層物Eの側方から、紫外線LEDを線状に配した紫外線光源(Spectrum Illumination社製 LL146-395)を用いて、未硬化のシール部の全周にわたって約10分間光を照射し、未硬化のシール部を硬化させた。照射光の強度を、照度計(オーク製作所社製、UV-M02、受光器UV-42)で測定したところ、約5mW/cm2であった。未硬化のシール部を硬化させた後、積層物Eを水平に保って約10分静置した。
液晶表示装置Fを、液晶テレビ受像機の筺体に入れ、配線を再接続して電源を入れたところ、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、保護板Bが液晶パネルAを効果的に保護していた。
液晶パネルA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。保護板Bの上に液晶パネルA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保護板Bとの間を、ドライバによって2mm程度抉じ開け、その部分から樹脂層形成用光硬化性樹脂組成物Dを155g注ぎ入れようとしたが、液晶パネルAと保護板Bと間の空間の下部に気泡が残り、樹脂層形成用光硬化性樹脂組成物Dを該空間中に密実に注入できなかった。
本出願は、2010年2月18日出願の日本特許出願2010-033702に基づくものであり、その内容はここに参照として取り込まれる。
10 保護板
12 透明面材
16 第1の偏光手段
20 液晶パネル
22 液晶セル
26 第2の偏光手段
40 樹脂層
42 シール部に囲まれた領域
44 樹脂層形成用光硬化性樹脂組成物
46 未硬化の樹脂層
50 シール部
52 未硬化のシール部
Claims (4)
- 透明面材の表面に第1の偏光手段が設けられた保護板と、液晶セルの表面に第2の偏光手段が設けられた液晶パネルと、保護板と液晶パネルと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し、第1の偏光手段が透明面材と樹脂層との間に位置し、第2の偏光手段が樹脂層側とは反対側の液晶セルの表面に位置する液晶表示装置を製造する方法であって、
下記工程(a1)~(d1)を有する、液晶表示装置の製造方法。
(a1)液晶パネルの第2の偏光手段側とは反対側の表面の周縁部に、液状のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程。
(b1)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c1)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第1の偏光手段が樹脂層形成用硬化性樹脂組成物側となるように保護板を重ねて、液晶パネル、保護板および未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d1)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。 - 前記工程(c1)にて、第1の偏光手段および第2の偏光手段の偏光軸の成す角度が液晶セルの設計に合うように、保護板および液晶パネルの位置を調整する、請求項1に記載の液晶表示装置の製造方法。
- 透明面材の表面に第1の偏光手段が設けられた保護板と、液晶セルの表面に第2の偏光手段が設けられた液晶パネルと、保護板と液晶パネルと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し、第1の偏光手段が透明面材と樹脂層との間に位置し、第2の偏光手段が樹脂層側とは反対側の液晶セルの表面に位置する液晶表示装置を製造する方法であって、
下記工程(a2)~(d2)を有する、液晶表示装置の製造方法。
(a2)保護板の第1の偏光手段側の表面の周縁部に、液状のシール部形成用硬化性樹脂組成物を塗布して未硬化のシール部を形成する工程。
(b2)未硬化のシール部で囲まれた領域に、液状の樹脂層形成用硬化性樹脂組成物を供給する工程。
(c2)100Pa以下の減圧雰囲気下にて、樹脂層形成用硬化性樹脂組成物の上に、第2の偏光手段が樹脂層形成用硬化性樹脂組成物側とは反対側となるように液晶パネルを重ねて、液晶パネル、保護板および未硬化のシール部で樹脂層形成用硬化性樹脂組成物からなる未硬化の樹脂層が密封された積層物を得る工程。
(d2)50kPa以上の圧力雰囲気下に積層物を置いた状態にて、未硬化のシール部および未硬化の樹脂層を硬化させる工程。 - 前記工程(c2)にて、第1の偏光手段および第2の偏光手段の偏光軸の成す角度が液晶セルの設計に合うように、保護板および液晶パネルの位置を調整する、請求項3に記載の液晶表示装置の製造方法。
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JP2012500584A JPWO2011102314A1 (ja) | 2010-02-18 | 2011-02-14 | 液晶表示装置の製造方法 |
CN2011800100697A CN102770799A (zh) | 2010-02-18 | 2011-02-14 | 液晶显示装置的制造方法 |
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JP2014010219A (ja) * | 2012-06-28 | 2014-01-20 | Asahi Kasei E-Materials Corp | ワイヤグリッド偏光子シート及びワイヤグリッド偏光子の製造方法 |
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JP5961366B2 (ja) * | 2011-11-28 | 2016-08-02 | 東芝機械株式会社 | ワーク設置装置およびワーク設置方法 |
JP5798020B2 (ja) | 2011-12-01 | 2015-10-21 | 東芝機械株式会社 | ワーク設置装置およびワーク設置方法 |
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JPH0365542A (ja) * | 1989-08-01 | 1991-03-20 | Nippon Zeon Co Ltd | 合せガラスの製造方法 |
WO2008081838A1 (ja) * | 2006-12-28 | 2008-07-10 | Asahi Glass Company, Limited | 透明積層体及びその製造方法 |
JP2009075217A (ja) * | 2007-09-19 | 2009-04-09 | Hitachi Chem Co Ltd | 液晶表示装置 |
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JP3471555B2 (ja) * | 1997-03-14 | 2003-12-02 | シャープ株式会社 | 表示装置の製造方法 |
JPWO2007026659A1 (ja) * | 2005-08-30 | 2009-03-05 | 日東電工株式会社 | 偏光子保護フィルム、偏光板、および画像表示装置 |
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JPH0365542A (ja) * | 1989-08-01 | 1991-03-20 | Nippon Zeon Co Ltd | 合せガラスの製造方法 |
WO2008081838A1 (ja) * | 2006-12-28 | 2008-07-10 | Asahi Glass Company, Limited | 透明積層体及びその製造方法 |
JP2009075217A (ja) * | 2007-09-19 | 2009-04-09 | Hitachi Chem Co Ltd | 液晶表示装置 |
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JP2014010219A (ja) * | 2012-06-28 | 2014-01-20 | Asahi Kasei E-Materials Corp | ワイヤグリッド偏光子シート及びワイヤグリッド偏光子の製造方法 |
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CN102770799A (zh) | 2012-11-07 |
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