WO2013054642A1 - 接着剤層を有する画像表示装置用ユニット及び該ユニットを用いた画像表示装置 - Google Patents
接着剤層を有する画像表示装置用ユニット及び該ユニットを用いた画像表示装置 Download PDFInfo
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- WO2013054642A1 WO2013054642A1 PCT/JP2012/073706 JP2012073706W WO2013054642A1 WO 2013054642 A1 WO2013054642 A1 WO 2013054642A1 JP 2012073706 W JP2012073706 W JP 2012073706W WO 2013054642 A1 WO2013054642 A1 WO 2013054642A1
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- optical film
- polarizer
- layer
- image display
- display device
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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
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G02B1/105—
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Definitions
- the present invention relates to an image display device having an adhesive layer. Specifically, the optical film laminate and the panel for an image display device are laminated via an adhesive layer having a predetermined elastic modulus, so that the optical film is compared with a case where the optical film laminate is measured alone.
- the present invention relates to a unit for an image display device in which a decrease in surface hardness of a laminate is suppressed, and an image display device using the unit.
- a polarizer produced by stretching a polyvinyl alcohol-based resin (hereinafter referred to as “PVA-based resin”) is easily cracked or split in the stretching direction. Therefore, the polarizer is generally not used alone but in the form of an optical film laminate in which a polarizer protective functional layer for protecting the polarizer and improving durability is formed on both sides.
- a transparent protective film such as triacetyl cellulose (TAC) is usually used.
- TAC triacetyl cellulose
- An optical film laminate having a further improved function may be used by laminating a layer having an ultraviolet absorbing function or the like on the protective film.
- a retardation film for optical compensation may be used as a polarizer protective functional layer.
- an image display device unit used in an image display device is obtained by bonding such an optical film laminate to a substrate of an image display device panel through an adhesive layer.
- the pressure-sensitive adhesive used when the image display device panel and the optical film laminate are bonded together can be defined as having the following properties. ⁇ Semi-solid substance with high viscosity and low elastic modulus, which can be bonded to the adherend by applying pressure. ⁇ It can be peeled off from the adherend even after bonding.
- a pressure-sensitive adhesive having such properties that does not change in the process is a kind of adhesive in a broad sense, and expresses adhesive force by applying pressure between two adherends. be called.
- the pressure-sensitive adhesive means such a pressure-sensitive adhesive.
- the surface of the optical film laminate is not damaged.
- Anti-stick function is added. This function is generally realized by laminating a hard coat layer on the polarizer side or the polarizer protective functional layer on the viewing side of the optical film laminate.
- the hard coat layer is formed by, for example, applying a polymerizable composition containing polyfunctional (meth) acrylate as a main component to the viewing side of a polarizer or a polarizer protective functional layer, and irradiating active energy rays such as ultraviolet rays. It is obtained by curing the polymerizable composition. Details of such a hard coat layer are described in Patent Document 1, for example.
- the polarizer protective functional layer itself is not damaged by increasing the hardness of the polarizer protective functional layer, instead of laminating a hard coat layer on the polarizer protective functional layer.
- a sticking prevention function can also be provided. Such a technique is described in Patent Document 2, for example.
- the pressure-sensitive adhesive layer is a semi-solid substance having a high viscosity and a low elastic modulus, and has a weak repulsive force. Therefore, when a force is applied to the surface of the optical film laminate, the stress concentrates on the adhesive layer that is the lowest elastic modulus layer among the optical film laminate, the adhesive layer, and the image display device panel. The pressure-sensitive adhesive layer is deformed. When the pressure-sensitive adhesive layer is deformed, the optical film laminate is deformed accordingly, and plastic deformation (dents) is easily generated on the surface on the viewing side.
- a pencil hardness measurement method based on JIS K5600-5-4 is generally used.
- the pencil hardness of the optical film laminate is the optical film even when the hard coat layer is provided. There exists a problem that it falls significantly compared with the case where it measures only a laminated body.
- the adhesive is used in distinction from the above-mentioned pressure-sensitive adhesive and can be defined as a substance having the following properties.
- ⁇ Initially a fluid, low-viscosity liquid that, when applied to an adherend, sufficiently wets the adherend to increase the contact area and adhere by curing by light irradiation or heating.
- the adhesive having such properties is an energy curable adhesive that develops an adhesive force by being cured by applying energy such as light or heat. Depending on the type of energy applied, for example, an ultraviolet curable adhesive Called thermosetting adhesive.
- Image display devices used for home televisions are required to be larger, thinner and lighter, while the price is being reduced. Therefore, it is expected that the optical film laminate used in such an image display device will be further increased in size, thickness and weight in the future.
- the surface hardness of the optical film laminate may be more significantly reduced.
- the means for increasing the thickness of the hard coat layer is not desirable from the viewpoint of reducing the weight, thickness, and cost of the image display device, and the curling of the optical film laminate is increased, resulting in poor handling. There exists a tendency for the adhesiveness of a hard-coat layer and an optical film laminated body to deteriorate.
- An object of the present invention is to provide an image display device unit and an image display device using the unit.
- the present inventors bonded the optical film laminate and the panel for an image display device through an adhesive layer having an elastic modulus after curing within a predetermined range, not an adhesive, and thus the above-described problem.
- the present invention has been completed based on the knowledge that can be solved.
- the present invention provides an image display device unit in which an optical film laminate and an image display device panel are laminated via an adhesive layer.
- the optical film laminate is laminated on a polarizer, a polarizer protective functional layer laminated on one surface side of the polarizer, and a surface side of the polarizer opposite to the surface in contact with the polarizer protective functional layer. And a thickness of 120 ⁇ m or less.
- the adhesive layer is laminated on the surface of the polarizer protective functional layer opposite to the surface that contacts the polarizer.
- the panel for an image display device is laminated on the surface side opposite to the surface on which the polarizer protective functional layer is in contact with the adhesive layer.
- the elastic modulus at 25 ° C. of the adhesive layer after curing is 1/50 or more of the elastic modulus of the layer having the smallest elastic modulus among the layers included in the optical film laminate.
- the present invention is for an image display device in which an optical film laminate having a configuration different from that of the optical film laminate in the first aspect and an image display device panel are laminated via an adhesive layer.
- the optical film laminate includes a polarizer, a polarizer protective functional layer laminated on both sides of the polarizer, and a surface on the opposite side to the surface on which one polarizer of the polarizer protective functional layer is in contact. And a surface protective layer laminated on the side, and the thickness is 120 ⁇ m or less.
- the adhesive layer is laminated on the surface of the polarizer protective functional layer opposite to the surface that is in contact with the other polarizer.
- the panel for an image display device is laminated on the surface side opposite to the surface on which the polarizer protective functional layer is in contact with the adhesive layer.
- the elastic modulus at 25 ° C. of the adhesive layer after curing is 1/50 or more of the elastic modulus of the layer having the smallest elastic modulus among the layers included in the optical film laminate.
- the thickness of the optical film laminate of the unit for an image display device is 120 ⁇ m or less
- the adhesive layer has an elastic modulus at 25 ° C. after curing included in the optical film laminate. It is preferable that it is 1/10 or more of the elastic modulus of the layer with the smallest elastic modulus among each layer.
- the thickness of the optical film laminate of the unit for an image display device is 100 ⁇ m or less
- the adhesive layer has an elastic modulus at 25 ° C. after curing included in the optical film laminate. It is preferable that it is 1/50 or more of the elasticity modulus of the layer where the elasticity modulus is the smallest among each layer.
- the thickness of the optical film laminate of the image display device unit is 100 ⁇ m or less
- the adhesive layer has an elastic modulus at 25 ° C. after curing of the optical film laminate. It is preferable that it is 1/10 or more of the elasticity modulus of the layer with the smallest elasticity among each layer contained.
- the thickness of the optical film laminate of the unit for image display device is 100 ⁇ m or less, and the adhesive layer has an elastic modulus at 25 ° C. after curing of 1 ⁇ 10 8 Pa. It is preferably ⁇ 1 ⁇ 10 10 Pa.
- the pencil hardness on the exposed surface of the surface protective layer of the optical film laminate in the image display unit is the pencil hardness on the exposed surface of the surface protective layer as measured by the optical film laminate alone.
- the decrease is only one rank even if it is lower than the pencil hardness on the exposed surface of the surface protective layer as measured by the optical film laminate alone.
- the present invention provides an image display device using the image display device unit according to any one of claims 1 to 7 in the claims. provide.
- the effect of suppressing the occurrence of plastic deformation on the surface of the optical film laminate is obtained by laminating the optical film laminate and the panel for an image display device via an adhesive layer having a predetermined elastic modulus. It is possible to provide a large-sized image display device that achieves both weight reduction and thickness reduction.
- FIG. 1 is a schematic view showing a cross section of an image display device unit 1 including an optical film laminate 10 according to an embodiment of the present invention.
- the image display device unit 1 is an optical film laminate on one surface of an image display device panel 30 that can be a liquid crystal display panel or an organic EL display panel, for example, via an optically transparent adhesive layer 20. 10 is laminated.
- the optical film laminate 10 is opposite to the polarizer 12, the polarizer protective functional layer 14 laminated on one surface side of the polarizer 12, and the other surface of the polarizer 12, that is, the polarizer protective functional layer 14. And a surface protective layer 16 laminated on the surface side.
- the surface of the polarizer protective functional layer 14 opposite to the surface in contact with the polarizer 12 is laminated on the image display device panel 30 via the adhesive layer 20.
- the thickness of the optical film laminate 10 in the image display device unit 1 according to the present invention is 120 ⁇ m or less, and more preferably 100 ⁇ m or less.
- the image display device can be formed by providing the image display device unit 1 with various constituent members such as an optical film laminate, another optical function film, a protective film, and a backlight unit as necessary. .
- the polarizer 12 As the polarizer 12, a polarizer well known to those skilled in the art can be used.
- the polarizer 12 is generally manufactured by subjecting a PVA resin to a dyeing process using a dichroic substance and a stretching process. As a manufacturing method, a method well known to those skilled in the art can be used.
- the thickness of the polarizer 12 is usually 20 ⁇ m to 30 ⁇ m.
- thermoplastic resins such as triacetyl cellulose (TAC), polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethersulfone, as is well known to those skilled in the art.
- TAC triacetyl cellulose
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polyethersulfone as is well known to those skilled in the art.
- polarizer protective functional layer 14 a film-like glass that can be bent into a roll like a plastic film can be used. Since the film-like glass is difficult to handle if it is too thin, and is difficult to bend if it is too thick, a glass having a thickness of about 30 ⁇ m to about 120 ⁇ m is preferably used. In general, a transparent TAC film having a thickness of about 40 ⁇ m to 80 ⁇ m is often used as the polarizer protection functional layer 14.
- a material known to those skilled in the art for example, a polymer such as an acrylic polymer, a silicone polymer, a polyester, a polyurethane, and a polyamide is used as a base polymer. Can be appropriately selected and used.
- the surface protective layer 16 laminated on the surface of the polarizer 12 opposite to the polarizer protective functional layer 14 a material well known to those skilled in the art, for example, UV curable acrylic such as polyester acrylate, urethane acrylate, epoxy acrylate and the like.
- a composition containing a resin and a composition in which a polyfunctional acrylate having a plurality of acryloyloxy groups is added to these compositions to increase the cross-linking density of the resin component in the cured film is appropriately selected.
- the surface protective layer 16 can be obtained by a method well known to those skilled in the art, for example, by applying these compositions on the polarizer 12 and applying an energy such as ultraviolet rays after drying to form a cured film. .
- the thickness of the surface protective layer 16 is preferably 20 ⁇ m or less, and more preferably 3 ⁇ m to 10 ⁇ m.
- FIG. 2 is a schematic diagram showing a cross section of the image display device unit 2 including the optical film laminate 50 according to an embodiment of the present invention.
- the image display device unit 2 is an optical film laminate on one surface of an image display device panel 80 that can be a liquid crystal display panel or an organic EL display panel, for example, via an optically transparent adhesive layer 70. 50 is laminated.
- the optical film laminate 50 includes a polarizer 52, a polarizer protection functional layer 54 laminated on both surfaces of the polarizer 52, and a polarizer protection function that is not in contact with one of the polarizer protection function layers 54, that is, the adhesive layer 70.
- the layer 54 includes a surface protective layer 56 laminated on the side opposite to the polarizer 52.
- the surface of the polarizer protective functional layer 54 opposite to the surface in contact with the polarizer 52 is laminated with the image display device panel 80 via the adhesive layer 70.
- the thickness of the optical film laminate 10 in the image display device unit 2 according to the present invention is 120 ⁇ m or less, and more preferably 100 ⁇ m or less.
- the image display device can be formed by providing the image display device unit 2 with various constituent members such as an optical film laminate, another optical function film, a protective film, and a backlight unit as necessary. .
- a film made of a thermoplastic resin similar to that of the polarizer protection functional layer 14 can be used as the polarizer protection functional layer 54.
- a retardation film having an optical compensation function may be used as the polarizer protection functional layer 54.
- the material used as such a retardation film is well known to those skilled in the art, and a film made of a material such as a cycloolefin resin or a TAC resin can be used.
- the image display device panel 30 or 80 in the image display device unit 1 or 2 may be an image display device panel such as a liquid crystal display panel, an organic EL display panel, or a plasma display panel.
- the surface on which the optical film laminate 1 or 2 is laminated via the adhesive layer is a glass or plastic substrate or front protective plate of the panel for an image display device. These optical film laminates are used for exhibiting functions such as image display, antireflection, and hue adjustment in an image display device.
- the adhesive layer 20 or 70 for bonding the optical film laminate 1 or 2 and the image display device panel 30 or 80 is an acrylic compound or an epoxy compound.
- an energy curable adhesive composition containing a urethane compound is preferably cured by irradiation with energy rays such as visible light, ultraviolet rays, X-rays, or electron beams, or heating. It is not limited to. Any adhesive composition may be used as long as the elastic modulus after curing falls within a predetermined range.
- the adhesive layer 20 or 70 one having an elastic modulus within a predetermined range is used.
- the lower limit of the predetermined range of the elastic modulus is the elasticity of the layer having the lowest elastic modulus among the layers included in the optical film laminate 10 or 50, that is, the polarizer, the polarizer protective functional layer, and the surface protective layer.
- the ratio is preferably 1/50, more preferably 1/20, and most preferably 1/10.
- the upper limit of the predetermined range of the elastic modulus is preferably 1 ⁇ 10 10 Pa, and each of the layers included in the optical film laminate 10 or 50, that is, a polarizer, a polarizer protective functional layer, and a surface protective layer Of these, it is more preferable that the elastic modulus is equal to that of the layer having the highest elastic modulus.
- an optical film laminate and an image display device panel are laminated using an adhesive layer or a pressure-sensitive adhesive layer having a lower elastic modulus than the lower limit as described above, an optical film is formed when an image display device unit is formed.
- an adhesive layer or a pressure-sensitive adhesive layer having a lower elastic modulus than the lower limit As described above, an optical film is formed when an image display device unit is formed.
- the adhesive layer or the pressure-sensitive adhesive layer is deformed, and plastic deformation (dents) is generated on the surface of the optical film laminate.
- an adhesive layer or a pressure-sensitive adhesive layer having an elastic modulus after curing is higher than the above upper limit, an optical display laminate and an image display device panel are laminated to form an image display device unit.
- an impact is applied to the unit, there is a problem that the optical film laminate is easily peeled off from the panel for an image display device.
- the optical film laminate 10 or 50 is laminated. Even when a force is applied to the surface of the film, there is no problem of occurrence of plastic deformation of the film surface when the film is laminated through a low elastic modulus layer such as an adhesive defined in the present specification. This is because the high elastic modulus adhesive layer has a strong repulsive force, so that the force applied to the surface of the optical film laminate is dispersed without concentrating in a narrow range. As a result, the optical film laminate itself and the adhesive layer It can be considered that the deformation can be suppressed by the repulsive force, or the deformation is not recognized as a deformation because the shape is shallow and wide.
- the adhesive layer 20 or 70 used in the image display device unit 1 or 2 according to the present invention has an elastic modulus in a predetermined range.
- the adhesive composition for obtaining such an adhesive layer 20 or 70 will be described.
- the adhesive layer 20 or 70 is formed of an energy ray such as visible light, ultraviolet ray, X-ray, or electron beam on an energy curable adhesive composition containing an acrylic compound, an epoxy compound, or a urethane compound. It is preferable that it is obtained by irradiating and curing, or heating and curing the adhesive composition.
- a polymerizable (meth) acrylic monomer As an acrylic compound contained in the adhesive composition, a polymerizable (meth) acrylic monomer can be used.
- the polymerizable (meth) acrylic monomer has a hydroxyl group, a carboxyl group, an adhesive property with a polarizer, and an adhesive property with a glass or plastic substrate or front protective plate glass of a panel for an image display device. It preferably contains at least one of a cyano group, an amino group, an amide group, a heterocyclic group, a lactone ring group, and an isocyanate ring group.
- the polymerizable (meth) acrylic monomer is preferably mainly composed of a monofunctional acryloyl group-containing monomer containing only one acryloyl group, and a monomer containing a polyfunctional vinyl group or acryloyl group as a subcomponent. May be included.
- acrylic compound contained in the adhesive composition include the following substances.
- examples of the acrylic compound having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like.
- examples of the acrylic compound having a carboxyl group include acrylic acid and methacrylic acid.
- examples of the acrylic compound having a cyano group include acrylonitrile and methacrylonitrile.
- acrylic compound having an amino group examples include dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diisopropylaminoethyl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate (DEAA).
- acrylic compound having an amide group include acrylamide, dimethylacrylamide, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, hydroxyethylacrylamide, acryloylmorpholine, and the like.
- Examples of the acrylic compound having a heterocyclic group include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, glycidyl acrylate, glycidyl methacrylate, pentamethylpiperidinyl methacrylate, and tetramethylpiperidinyl methacrylate.
- Examples of the acrylic compound having a lactone ring group include ⁇ -butyrolactone acrylate monomer and ⁇ -butyrolactone methacrylate monomer.
- Examples of the acrylic compound having an isocyanate group include 2-isocyanatoethyl acrylate monomer and 2-isocyanatoethyl methacrylate monomer.
- epoxy compound contained in the adhesive composition known compounds can be used, for example, bisphenol A type, bisphenol F type, bisphenol S type, and bisphenol types such as these water additives; phenol novolac type and cresol.
- Novolak type such as novolak type; nitrogen-containing ring type such as triglycidyl isocyanurate type and hydantoin type; alicyclic type; aliphatic type; naphthalene type; low water absorption type such as glycidyl ether type and biphenyl type; dicyclopentadiene Examples include dicyclo type such as type; ester type; ether ester type; and modified types thereof.
- epoxy compound contained in the adhesive composition include the following substances.
- the bisphenol type epoxy compound include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S.
- the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, and the like. .
- Examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and the like.
- a conventionally used compound such as a compound having active hydrogen or an isocyanate compound can be used.
- the compound having active hydrogen include polyol compounds.
- the polyol compound include polymer polyol compounds such as polyether polyol, polyester polyol, polyacryl polyol, and polycarbonate polyol.
- the urethane prepolymer which made the terminal a hydroxyl group can be used.
- examples of the compound having active hydrogen include compounds having a carboxylic acid and compounds having an amino group.
- Examples of the isocyanate compound include 2,4- / 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and tetraxylylene diisocyanate.
- Examples of the polymer isocyanate compound include polymer compounds having an isocyanate group at the molecular end. Moreover, a short-chain polyol and polyamine can be used as a chain extender as needed. Add additives such as inorganic fillers typified by silica, calcium carbonate, alumina, titanium oxide, and clay, reaction catalysts typified by tin compounds and amine compounds, leveling agents, and plasticizers. You can also.
- the adhesive composition used in the present invention is one in which the adhesive layer has an elastic modulus in the above predetermined range at 25 ° C. when cured to form an adhesive layer among the above-mentioned compounds, or cured.
- the adhesive layer when the adhesive layer is formed, two or more of the above compounds are appropriately mixed so that the adhesive layer has an elastic modulus in a predetermined range at 25 ° C.
- ⁇ Polymerization initiator> When the compound contained in the adhesive composition is an acrylic compound or an epoxy compound, a known polymerization initiator can be used as the polymerization initiator. In the present invention, it is more preferable to use a photopolymerization initiator as the polymerization initiator. Since a polymerization reaction can be caused by light by using a photopolymerization initiator, it is easy to control the adhesive force and state of the adhesive composition used in the present invention, and the optical film laminate to be bonded together In addition, the image display device panel is not deteriorated or destroyed.
- photopolymerization initiator examples include alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, titanocene photopolymerization initiators, and cationic photopolymerization initiators.
- photopolymerization initiators using ultraviolet rays examples include benzoin photopolymerization initiators, benzophenone photopolymerization initiators, anthraquinone photopolymerization initiators, xanthone photopolymerization initiators, thioxanthone photopolymerization initiators, and ketal photopolymerization initiators.
- Various photoinitiators, such as a polymerization initiator can be mentioned.
- the photopolymerization initiator examples include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ ′-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy Acetophenone compounds such as -2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropan-1-one Benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether, ⁇ -ketol compounds such as 2-methyl-2-hydroxypropiophenone, ketal compounds such as benzyldimethyl ketal, 2- Naphthalene Aromatic sulfonyl chloride compounds such as sulfonyl chloride, photoactive oxime compounds such as
- the energy required for the polymerization initiator to generate active species is usually given through one of the optical film laminate and the image display device panel to be bonded together. Therefore, when a photopolymerization initiator is used as a component of the adhesive composition, the available photopolymerization initiator has a light absorption wavelength that is transmitted through the optical film laminate and the image display device panel to be bonded together.
- the wavelength is
- the irradiated light is not absorbed by the light absorber included in the TAC film.
- the compound contained in the adhesive composition is an acrylic compound or an epoxy compound
- ultraviolet rays or electromagnetic waves having a wavelength in the vicinity of the ultraviolet rays as an energy source given to the adhesive composition.
- visible light When visible light is used, the polymerization reaction may proceed due to the influence of ambient light, making it difficult to control the reaction, and absorption of visible light due to the residue of the polymerization initiator remains, and the adhesive composition may be colored. There is a problem of having sex. When infrared rays are used, there is a problem that the polymerization reaction proceeds by heat and the control of the reaction becomes difficult.
- the photopolymerization initiator preferably has no absorption in the visible light region or has a low absorbance in the visible light region after reacting with light.
- the photopolymerization initiator does not absorb light having wavelengths near 440 nm, 530 nm, and 610 nm, which are the peak of the bright line of the backlight, so as not to affect the hue at the time of visual recognition. It is preferable that the absorbance is low.
- the mixing ratio of the acrylic compound or epoxy compound and the polymerization initiator in the adhesive composition is not particularly limited. However, when the ratio of the polymerization initiator is too large, the progress of the polymerization reaction is too fast and it becomes difficult to control the reaction, the adhesive composition may be colored, and the dispersibility of the polymerization initiator may be deteriorated. is there. If the ratio of the polymerization initiator is too small, it takes time for the polymerization reaction, and the productivity of the process of bonding using the adhesive composition is lowered, which is not preferable.
- the adhesive composition becomes 100 parts of HEAA in the adhesive composition.
- the adhesive composition may contain an additive as shown below.
- various Si coupling agents or crosslinking agents can be added to the adhesive composition in order to enhance the adhesion between the substrate of the image display device panel and the optical film laminate.
- a polymerization inhibitor can also be added to an adhesive composition from a viewpoint of preventing a dark reaction or increasing a pot life.
- a polymerization initiator having a light absorption wavelength different from the transmission wavelength of the optical film laminate is used by adding a photosensitizer matched to the transmission wavelength of the optical film laminate to the adhesive composition.
- a conductive material for imparting conductivity, a fine particle having birefringence for imparting a phase difference, or a surface leveling property can be increased.
- a surfactant can also be added.
- various curing agents can be added to the adhesive composition. Examples of the curing agent include phenol resins, various imidazole compounds and derivatives thereof, hydrazide compounds, dicyandiamide, isocyanate compounds, and microencapsulated ones thereof. For example, when a phenol resin is added as a curing agent. Furthermore, phosphorus compounds such as triphenylphosphine can be used in combination as a curing accelerator.
- the thickness of the adhesive layer 20 or 70 is preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the thickness of the adhesive layer is greater than 20 ⁇ m, the shrinkage force due to the curing of the adhesive layer increases, and in particular, in the case of a large-sized image display device unit, a warping force is applied to the panel. There is a possibility.
- the manufacturing method of the unit for image display apparatuses which concerns on this invention shall include the following processes. First, a polarizer 12 or 52 made of PVA-based resin and a polarizer protective functional layer 14 or 54 are laminated, and an optical film laminate in which a polarizer protective functional layer is laminated on one or both sides of the polarizer is prepared. . In the optical film laminate in which the polarizer protective functional layer 14 is laminated only on one side, it is preferable that a temporary protective film is laminated on the surface opposite to the polarizer protective functional layer 14.
- the temporary protective film on the surface opposite to the polarizer protective functional layer 14 can be peeled to form a hard coat layer on the surface of the polarizer 12.
- the surface protective layer 16 can be formed by coating and drying a layer containing the composition and irradiating the layer with energy rays to cure.
- a temporary protective film is not laminated, a layer containing a composition capable of forming a hard coat layer is applied to the surface of the polarizer 12 and dried, and this layer is irradiated with energy rays and cured.
- the surface protective layer 16 can be formed.
- a layer containing a composition capable of forming a hard coat layer is coated on a peelable film and dried, and this layer is bonded to the surface of the polarizer 12 and irradiated with energy rays.
- the surface protective layer 16 can be formed by curing the layer and finally peeling the peelable film.
- This peelable film may be used as a surface protective film for preventing scratches during the production process without peeling.
- a film-like glass that can be bent like a plastic film may be used as the surface protective layer 16. Glass has a very high surface hardness and good transparency as compared to plastic films and hard-coated plastic films.
- the film-like glass used as the surface protective layer 16 is preferably about 30 ⁇ m to about 120 ⁇ m in thickness because it is difficult to handle if it is too thin, and difficult to bend if it is too thick. Thus, the optical film laminate 10 is obtained.
- a composition capable of forming a hard coat layer on the other surface of the two polarizer protective functional layers 54 on the side opposite to the surface on which the polarizer 52 is laminated The surface protective layer 56 can be formed by coating and drying a layer containing, and irradiating the layer with energy rays and curing. As another method, a layer containing a composition capable of forming a hard coat layer is applied onto a peelable film and dried, and the other of the two polarizer protective functional layers 54, the polarizer 52 is laminated.
- the surface protective layer 56 can be formed by bonding the surface opposite to the formed surface, irradiating energy rays, curing the layer, and finally peeling the peelable film. This peelable film may be used as a surface protective film for preventing scratches during the production process without peeling.
- the optical film laminate 50 is obtained.
- a layer of the adhesive composition is formed on the surface of the polarizer protective functional layer 14 opposite to the surface on which the polarizer 12 is laminated. Or after forming the layer of adhesive composition on a release liner and making it dry, the layer of adhesive composition is the surface on the opposite side to the surface where the polarizer 12 of the polarizer protective functional layer 14 was laminated
- a layer of the adhesive composition is formed on the surface of the polarizer protective functional layer 54 opposite to the surface on which the one polarizer 52 is laminated.
- the adhesive composition layer is opposite to the surface of the polarizer protective functional layer 54 on which one polarizer 52 is laminated. It may be transferred to the surface.
- the layer of the adhesive composition any method known to those skilled in the art can be appropriately used.
- the release liner any one known to those skilled in the art, which is obtained by subjecting a base film such as polyethylene terephthalate or triacetyl cellulose to a release treatment, can be used as appropriate.
- the surface of the adhesive composition layer opposite to the surface on which the optical film laminate is laminated is laminated on the image display device panel 30 or 80.
- the image display device panel 30 the adhesive composition layer, the polarizer protective functional layer 14, the polarizer 12, and the surface protective layer 16 are laminated in this order.
- a laminated body is formed.
- the image display device panel 80, the adhesive composition layer, the polarizer protective functional layer 54, the polarizer 52, the polarizer protective functional layer 54, and the surface protective layer 56 is formed.
- a method of forming these laminates a method of forming an adhesive composition layer on an optical film laminate as described above, and then laminating an image display device panel on the adhesive composition layer.
- a method of laminating the optical film laminate on the layer of the adhesive composition after forming the layer of the adhesive composition on the panel for an image display device may be adopted.
- the layer of the adhesive composition is cured by irradiating these laminates with energy rays such as visible light, ultraviolet rays, X-rays, or electron beams, or by heating these laminates.
- the adhesive layer 20 or 70 is formed.
- the layer of the adhesive composition is completely cured, and the optical film laminate 10 or 50 and the image display device panel 30 or 80 are completely bonded.
- optical film laminate In order to specifically explain the present invention, the following six types of optical film laminates having different thicknesses were prepared.
- Optical film laminate 1 (Nitto Denko, product number NPF-SEG5224DUHC)
- the optical film laminate 1 is obtained by laminating a triacetyl cellulose film (TAC film) as a polarizer protective functional layer, a polarizer, a TAC film, and a hard coat layer (HC layer) as a surface protective layer in this order. It is.
- the total thickness is 188 ⁇ m
- the polarizer is 22 ⁇ m
- the TAC film 80 ⁇ m
- the HC layer is 3 ⁇ m.
- the hardness of the optical film laminate on the surface of the HC layer was 3H in pencil hardness.
- Optical film laminate 2 (Nitto Denko, product number NPF-CIG5484DUARC9)
- the optical film laminate 2 is obtained by laminating an acrylic film, a polarizer, a TAC film, and an HC layer in this order.
- the total thickness is 137 ⁇ m
- the acrylic film is 40 ⁇ m
- the polarizer is 25 ⁇ m
- the TAC film is 60 ⁇ m
- the HC layer is 12 ⁇ m.
- the hardness of the optical film laminate on the surface of the HC layer was 2H in pencil hardness.
- Optical film laminate 3 (Nitto Denko, product number NPF-CVS5774HC)
- the optical film laminate 3 is obtained by laminating an acrylic film, a polarizer, a TAC film, and an HC layer in this order.
- the total thickness is 88 ⁇ m
- the acrylic film is 20 ⁇ m
- the polarizer is 22 ⁇ m
- the TAC film is 40 ⁇ m
- the HC layer is 6 ⁇ m.
- the hardness of the optical film laminate on the surface of the HC layer was 3H in pencil hardness.
- Optical film laminate 4 ⁇ Creating a polarizer>
- a polyvinyl alcohol film having a polymerization degree of 2400, a saponification degree of 99.9% and a thickness of 75 ⁇ m manufactured by Kuraray, VF-PS-N # 7500
- VF-PS-N # 7500 a polyvinyl alcohol film having a polymerization degree of 2400, a saponification degree of 99.9% and a thickness of 75 ⁇ m
- Kuraray VF-PS-N # 7500
- a triacetyl cellulose (TAC) film (manufactured by Fuji Film, TD80UL) serving as a polarizer protective functional layer was bonded to one surface of the obtained polarizer to obtain an optical film laminate.
- a PET film was laminated as a peelable temporary protective film on the other surface of the polarizer.
- a polyvinyl alcohol resin having an acetoacetyl group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) 100 A solution prepared by dissolving 20 parts of methylol melanin in pure water under a condition of 30 ° C. and adjusting the solid content concentration to 3.2% was used. The polarizer and the TAC film were bonded by using this adhesive and using a roll machine under a temperature condition of 30 ° C., and then dried at 60 ° C. for 5 minutes. The adhesive was used only between the polarizer and the TAC.
- the temporary protective PET film was peeled from the optical film laminate, and a commercially available hard coat agent was applied to the peeled surface so as to have a thickness of 8 ⁇ m, and cured by UV irradiation.
- the obtained optical film laminate 4 is obtained by laminating a TAC film, a polarizer, and an HC layer in this order.
- the total thickness is 113 ⁇ m
- the polarizer is 25 ⁇ m
- the TAC film is 80 ⁇ m
- the HC layer is 8 ⁇ m.
- the hardness of the optical film laminate on the surface of the HC layer was 3H in pencil hardness.
- optical film laminate 5 The optical film laminate 5 is obtained by laminating a TAC film, a polarizer, and an HC layer in this order. The total thickness is 50 ⁇ m, the polarizer is 5 ⁇ m, the TAC film is 40 ⁇ m, and the HC layer is 5 ⁇ m.
- the polarizer of the optical film laminate 5 was prepared using the method described in Japanese Patent No. 4691205.
- the hardness of the optical film laminate on the surface of the HC layer was 3H in pencil hardness.
- Optical film laminate 6 A film glass having a thickness of 50 ⁇ m serving as a polarizer protective functional layer was bonded to one surface of the polarizer produced by the same method as the polarizer of the optical film laminate 4 to obtain an optical film laminate. At this time, a PET film was laminated as a peelable temporary protective film on the other surface of the polarizer.
- the said adhesive agent was dripped at the film-form glass with the dropper, and the polarizer and the film-form glass were bonded together between rolls using the laminator.
- a temporary protective PET film was stacked without using an adhesive.
- This laminate was irradiated with ultraviolet rays from the glass side by an ultraviolet irradiation device (UBX0801-01 output 8 kW (high pressure mercury lamp) manufactured by IGraphics) to cure the adhesive composition.
- the irradiation conditions were a wavelength of 365 nm, an irradiation intensity of 30 mW / cm 2 , and an irradiation time of 30 seconds.
- the adhesive was used only between the polarizer and the film glass.
- the total thickness of the obtained optical film laminate 6 is 75 ⁇ m, the thickness of the polarizer is 25 ⁇ m, and the thickness of the film-like glass is 50 ⁇ m.
- the hardness of the optical film laminate 6 on the film-like glass surface was 9H or higher in pencil hardness.
- Adhesive composition containing acrylic compound As a monomer of the energy curable adhesive composition containing an acrylic compound, a mixed monomer in which the following materials were mixed at a ratio (weight ratio) shown in Table 1 was used. Each mixing ratio was determined so that the elastic modulus at 25 ° C. after curing was different.
- HEAA 2-hydroxyethylacrylamide (manufactured by Kojin) 4-HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry)
- ACMO acryloylmorpholine (manufactured by Kojin)
- THFA tetrahydrofurfuryl acrylate (manufactured by Tokyo Chemical Industry)
- Adhesive composition 1 to adhesive composition 8 were applied to each of the optical film laminates 1 to 5 described above, and the optical film laminates 1 to 6 and glass were bonded together.
- the layer of the adhesive composition was adjusted so that the thickness after curing was various.
- This laminate is irradiated with ultraviolet rays from the optical film laminate side by an ultraviolet irradiation device (UBX0801-01 output 8 kW (high pressure mercury lamp) manufactured by iGraphics) in an environment of 80 ° C. to cure the adhesive composition. It was.
- the irradiation conditions were a wavelength of 365 nm, an irradiation intensity of 30 mW / cm 2 , and an irradiation time of 3 minutes.
- the elastic modulus at 25 ° C. after curing of the adhesive compositions 1 to 8 was as shown in Table 1.
- the elastic modulus was measured using a TA Instruments solid viscoelastic device RSAIII. Samples for measurement are sandwiched between PET films that have been easily peeled off from adhesive compositions 1 to 8, and UV rays are emitted by an ultraviolet ray irradiation device (UBX0801-01 output 8 kW (high pressure mercury lamp) manufactured by iGraphics) in an environment of 80 ° C. Irradiation was performed to cure the adhesive composition into a film shape, which was cut into a strip shape.
- UX0801-01 output 8 kW high pressure mercury lamp
- the irradiation conditions were a wavelength of 365 nm, an irradiation intensity of 30 mW / cm 2 , and an irradiation time of 3 minutes.
- the measurement conditions are as follows. Deformation mode Pull frequency 1Hz Initial strain 0.1% Temperature -40 °C ⁇ 200 °C Temperature increase rate 10 ° C / min
- Adhesive composition containing epoxy compound The following materials were used as the main component of the energy curable adhesive composition containing an epoxy compound. Epolite 80MF (manufactured by Kyoeisha Chemical) Epolite 100MF (manufactured by Kyoeisha Chemical) Epolite 40E (manufactured by Kyoeisha Chemical) To 90 parts of each of these materials, 10 parts of an oxetane compound was added to obtain three types of mixtures. As the oxetane compound, OXT221 manufactured by Toagosei Co., Ltd. was used. Further, 100 parts of these mixtures were mixed with 3 parts of the following photoacid generator and 0.5 parts of sensitizer to prepare Adhesive Composition 9 to Adhesive Composition 11.
- Adhesive composition 9 to adhesive composition 11 were applied to each of the optical film laminates 1 to 6 so as to have various thicknesses, and an ultraviolet irradiation device (UBX0801 made by Eye Graphics Co., Ltd.) at 25 ° C. --01 Output was 8 kW (high pressure mercury lamp)).
- the irradiation conditions were a wavelength of 365 nm, an irradiation intensity of 30 mW / cm 2 , and an irradiation time of 2 seconds.
- these optical film laminates were bonded to glass, and ultraviolet rays were irradiated from the optical film laminate side with an ultraviolet irradiation device to cure the adhesive composition.
- the irradiation conditions were a wavelength of 365 nm, an irradiation intensity of 30 mW / cm 2 , and an irradiation time of 3 minutes.
- the elastic modulus at 25 ° C. after curing of the adhesive composition 9 to the adhesive composition 11 is as shown in Table 2. The elastic modulus was measured in the same manner as for the adhesive composition 1 to the adhesive composition 8.
- Adhesive composition containing urethane compound As the energy curable adhesive composition containing a urethane compound, the following were used, and adhesive compositions 12 to 14 were used.
- Adhesive composition 12 to adhesive composition 14 were applied to each of the optical film laminates 1 to 6 so as to have various thicknesses, and heated at 110 ° C. for 1 hour. Next, these optical film laminates were bonded to glass.
- the elastic modulus at 25 ° C. after curing of the adhesive composition 12 to the adhesive composition 14 is as shown in Table 3. The elastic modulus was measured in the same manner as for the adhesive composition 1 to the adhesive composition 8.
- the acrylic adhesive was prepared as follows. First, 95 parts by weight of butyl acrylate, 3.0 parts by weight of acrylic acid, 0.10 parts by weight of 2-hydroxyethyl acrylate, 0.050 part by weight of 2,2-azobisisobutyronitrile, and 200 parts by weight of ethyl acetate were added. , Put into a four-necked flask equipped with a nitrogen introduction tube and a cooling tube, sufficiently purged with nitrogen, and then subjected to a polymerization reaction at 55 ° C. for 20 hours with stirring under a nitrogen stream to obtain a high molecular weight having a weight average molecular weight of 1,570,000. A solution of acrylic polymer A was obtained.
- the pressure-sensitive adhesive composition was applied to a 38 ⁇ m-thick polyethylene terephthalate film (MRF38 (addition reaction type silicone) manufactured by Mitsubishi Polyester Co., Ltd.) subjected to silicone release treatment, dried at 150 ° C. for 2 minutes and subjected to peroxide decomposition treatment. It was.
- the elastic modulus was measured using a solid viscoelastic device RSAIII manufactured by TA Instruments, and was 3.41 ⁇ 10 5 Pa. Note that the adhesive has a low elastic modulus, and the elastic modulus cannot be measured by applying a tensile stress to the strip-shaped sample. Therefore, the elastic modulus was measured by applying a torsional shear stress.
- the elastic modulus of optical film laminate was measured with Tensilon. The elastic modulus was obtained from the maximum elasticity (primary expression of the tangent of the maximum slope of the SS curve) immediately before the sample was deformed.
- the TAC film which is a polarizer protection functional layer is TD80UL made by Fuji Film.
- the polarizer Since the polarizer is in a state where the PVA is stretched, the MD elastic modulus (elastic modulus in the absorption axis direction) could be measured, but the TD elastic modulus (elastic modulus in the direction crossing the absorption axis) Therefore, it could not be measured.
- Table 4 shows the measurement results of the elastic modulus of each layer. From the results in Table 4, in the optical film laminate, the elastic modulus of the TAC film is the smallest. For this reason, the elastic modulus of the adhesive layer in the present application is defined based on the average value of the elastic modulus of the TAC film.
- the elastic modulus of the film-like glass is at 5 ⁇ 10 10 Pa or more, the digit is different from the modulus of the other polarizer protection layer.
- 3 to 7 show the measurement results of the laminate units using the optical film laminates 1 to 5, respectively.
- the horizontal axis indicates the elastic modulus of the adhesive layer
- the vertical axis indicates the thickness of the adhesive layer.
- Each point in each figure is a measurement point for a laminate unit having a different type and thickness of the adhesive layer.
- Legends F, H, 2H, and 3H in the figure indicate pencil hardness.
- an optical film laminate 1 having a thickness of 137 ⁇ m or more surface hardness of the optical film laminate alone is 3H
- an optical film laminate 2 surface hardness of the optical film laminate alone is 2H
- the surface hardness of the laminate unit using the optical film laminates 3 to 5 is that the elastic modulus is low or the thickness of the adhesive layer As the film thickness increased, a decrease from the surface hardness when measured with the optical film laminate alone was observed.
- the surface hardness of the laminate unit using the optical film laminates 3 to 5 is such that the elastic modulus of the adhesive layer at 25 ° C. is the elastic modulus of the layer having the lowest elastic modulus among the layers constituting the optical film laminate. If it was 1/50 Pa or more, the hardness was at a level that would not cause any problems in actual use regardless of the thickness of the adhesive layer.
- the surface hardness of the laminate unit using the optical film laminates 3 to 5 having a thickness of 113 ⁇ m or less has the lowest elastic modulus among the layers constituting the optical film laminate in which the elastic modulus of the adhesive layer at 25 ° C.
- the elastic modulus of the layer was 1/10 Pa or more, no reduction from the surface hardness when measured with the optical film laminate alone was observed regardless of the thickness of the adhesive layer.
- the surface hardness is 9H or more in all combinations. There was no decline. However, in the laminate unit created by bonding with an adhesive, the glass broke when the surface was pressed with a pointed core of a mechanical pencil. On the other hand, in the case of the laminate unit prepared by bonding with the adhesive compositions 1 to 14, no glass breakage occurred.
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Abstract
Description
・高粘度で低弾性率の半固体状物質であり、圧力を加えることによって被着体と結合する
・結合後においても被着体から剥離することが可能である
・粘着剤の状態は結合の過程で変化しない
こうした性質を有する粘着剤は、広義の接着剤の一種であり、2つの被着体の間に介在して圧力を加えられることによって接着力を発現するため、感圧型接着剤とも呼ばれる。本明細書において粘着剤というときは、こうした感圧型接着剤を意味する。
・当初は流動性のある低粘度の液体であり、被着体に塗布されたときに被着体に十分に濡れることによって接触面積を大きくし、光の照射や加熱によって硬化することにより被着体と結合する
・光の照射量や加熱量の増加によって粘着状態を経て硬化に至る
・結合後においては被着体や接着剤層の凝集破壊を生じることなく両者を剥離することが不可能である
・接着剤の状態は結合の過程で不可逆的に変化する(液体から固体に変化する)
こうした性質を有する接着剤は、光や熱などのエネルギーを与えることによって硬化することにより接着力を発現するエネルギー硬化型接着剤であり、与えられるエネルギーの種類に応じて、例えば紫外線硬化型接着剤、熱硬化型接着剤などと呼ばれる。
[光学フィルム積層体]
図1は、本発明の一実施形態に係る、光学フィルム積層体10を含む画像表示装置用ユニット1の断面を示す模式図である。画像表示装置用ユニット1は、例えば液晶表示パネル又は有機EL表示パネルとすることができる画像表示装置用パネル30の一方の面に、光学的に透明な接着剤層20を介して光学フィルム積層体10が積層されたものである。光学フィルム積層体10は、偏光子12と、偏光子12の一方の面側に積層された偏光子保護機能層14と、偏光子12の他方の面すなわち偏光子保護機能層14とは反対の面側に積層された表面保護層16とを含む。光学フィルム積層体10は、偏光子保護機能層14の偏光子12が接する面とは反対側の面が、接着剤層20を介して画像表示装置用パネル30に積層されている。本発明に係る画像表示装置用ユニット1における光学フィルム積層体10の厚みは、120μm以下であり、100μm以下であることがより好ましい。画像表示装置は、この画像表示装置用ユニット1に、必要に応じてさらに光学フィルム積層体、他の光学機能フィルム、保護用フィルム、バックライトユニットなどの各種構成部材を設けて形成することができる。
画像表示装置用ユニット1又は2における画像表示装置用パネル30又は80は、液晶表示パネル、有機EL表示パネル、又はプラズマ表示パネルなどの画像表示装置用パネルとすることができる。接着剤層を介して光学フィルム積層体1又は2が積層される面は、画像表示装置用パネルのガラス若しくはプラスチックの基板又は前面保護板である。これらの光学フィルム積層体は、画像表示装置において画像表示、反射防止、色相調整などの機能を発揮させるために用いられる。
本発明に係る画像表示装置ユニット1又は2において、光学フィルム積層体1又は2と画像表示装置用パネル30又は80とを貼り合わせるための接着剤層20又は70は、アクリル系化合物、エポキシ系化合物、又はウレタン系化合物を含むエネルギー硬化型接着剤組成物を、可視光線、紫外線、X線、若しくは電子線などのエネルギー線の照射、又は加熱などによって硬化させたものであることが好ましいが、これらに限定されるものではない。硬化後の弾性率が所定の範囲内に入るものであれば、いずれの接着剤組成物を用いてもよい。
接着剤層20又は70は、弾性率が所定の範囲内にあるものが用いられる。弾性率の所定の範囲の下限は、光学フィルム積層体10又は50に含まれる層の各々、すなわち、偏光子、偏光子保護機能層、及び表面保護層のうち、弾性率が最も低い層の弾性率の1/50であることが好ましく、1/20であることがより好ましく、1/10であることが最も好ましい。弾性率の所定の範囲の上限は、1×1010Paであることが好ましく、光学フィルム積層体10又は50に含まれる層の各々、すなわち、偏光子、偏光子保護機能層、及び表面保護層のうち、弾性率が最も高い層の弾性率と同等であることがより好ましい。
以上のように、本発明に係る画像表示装置用ユニット1又は2に用いられる接着剤層20又は70は、弾性率が所定の範囲にあるものである。以下に、こうした接着剤層20又は70を得るための接着剤組成物について説明する。本発明においては、接着剤層20又は70は、アクリル系化合物、エポキシ系化合物、又はウレタン系化合物を含むエネルギー硬化型接着剤組成物に可視光線、紫外線、X線、若しくは電子線などのエネルギー線を照射して硬化させるか、又は接着剤組成物を加熱して硬化させることによって、得られるものであることが好ましい。
接着剤組成物に含まれるアクリル系化合物として、重合性(メタ)アクリル系モノマーを用いることができる。重合性(メタ)アクリル系モノマーは、偏光子との接着性、及び、画像表示装置用パネルのガラス若しくはプラスチックの基板又は前面保護板ガラスとの接着性を付与するために、ヒドロキシル基、カルボキシル基、シアノ基、アミノ基、アミド基、複素環基、ラクトン環基、イソシアネート環基のうちの少なくとも1つを含んでいることが好ましい。重合性(メタ)アクリル系モノマーは、1つのアクリロイル基のみを含む単官能アクリロイル基含有モノマーを主成分とするものであることが好ましく、多官能のビニル基又はアクリロイル基を含むモノマーを副成分として含んでもよい。
接着剤組成物に含まれるエポキシ系化合物として、公知の化合物を用いることができ、例えば、ビスフェノールA型、ビスフェノールF型、ビスフェノールS型及びこれらの水添加物等のビスフェノール型;フェノールノボラック型やクレゾールノボラック型等のノボラック型;トリグリシジルイソシアヌレート型やヒダントイン型等の含窒素環型;脂環式型;脂肪族型;ナフタレン型;グリシジルエーテル型やビフェニル型等の低吸水率型;ジシクロペンタジエン型等のジシクロ型;エステル型;エーテルエステル型;及びこれらの変性型等が挙げられる。さらに、これらにオキセタン系化合物を添加してもよい。オキセタン系化合物を添加することにより、接着剤組成物の粘度を低減させたり、硬化速度を高めたりすることができる。
接着剤組成物に含まれるウレタン系化合物として、活性水素を有する化合物やイソシアネート化合物といった従来から用いられている化合物を利用することができる。活性水素を有する化合物としては、ポリオール化合物が挙げられる。ポリオール化合物としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリアクリルポリオール及びポリカーボネートポリオールなどの高分子ポリオール化合物が挙げられる。また、高分子ポリオール化合物としては、末端を水酸基としたウレタンプレポリマーを用いることができる。また、活性水素を有する化合物として、カルボン酸を有するものやアミノ基を有する化合物を挙げることもできる。イソシアネート化合物としては、2,4-/2,6-トリレンジイソシアネート、4,4-ジフェニルメタンジイソシアネート、へキサメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、テトラキシリレンジイソシアネートなどが挙げられる。高分子イソシアネート化合物として、分子末端にイソシアネート基を持ったポリマー化合物が挙げられる。また、必要に応じて鎖延長剤として短鎖のポリオールやポリアミンを用いることができる。さらには、シリカ、炭酸カルシウム、アルミナ、酸化チタン、クレーなどに代表される無機充填剤や、スズ系化合物、アミン化合物に代表される反応触媒、またレベリング剤、可塑剤などの添加剤を加えることもできる。
接着剤組成物に含まれる化合物がアクリル系化合物又はエポキシ系化合物の場合には、重合開始剤として、公知の重合開始剤を用いることができる。本発明においては、重合開始剤として光重合開始剤を用いることがより好ましい。光重合開始剤を用いることにより、光によって重合反応を生じさせることができるため、本発明において用いられる接着剤組成物の接着力及び状態の制御が容易になるとともに、貼り合わされる光学フィルム積層体及び画像表示装置用パネルの劣化や破壊を生じさせることがない。光重合開始剤として、例えば、アルキルフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤、チタノセン系光重合開始剤、カチオン系光重合開始剤を挙げることができる。紫外線を用いる光重合開始剤としては、例えば、ベンゾイン系光重合開始剤、ベンゾフェノン系光重合開始剤、アントラキノン系光重合開始剤、キサントン系光重合開始剤、チオキサントン系光重合開始剤、ケタール系光重合開始剤といった各種の光重合開始剤を挙げることができる。
接着剤組成物におけるアクリル系化合物又はエポキシ系化合物と重合開始剤との混合割合は、特に限定されるものではない。ただし、重合開始剤の割合が多すぎると、重合反応の進行が速すぎて反応の制御が難しくなる、接着剤組成物が着色する、重合開始剤の分散性が悪くなるといった問題が生じることがある。重合開始剤の割合が少なすぎると、重合反応に時間がかかり、接着剤組成物を用いて貼り合わせるプロセスの生産性が低下するため好ましくない。例えば、アクリル系化合物としてヒドロキシエチルアクリルアミド(HEAA)を用い、重合開始剤としてアシルホスフォンオキサイド系光重合開始剤を用いた場合には、接着剤組成物は、接着剤組成物中におけるHEAA100部に対して、重合開始剤0.3~3部を含有することが好ましい。
接着剤組成物には、アクリル系化合物、エポキシ系化合物、又はウレタン系化合物、及び、重合開始剤の他に、以下に示されるように添加剤が含まれてもよい。例えば、接着剤組成物には、画像表示装置用パネルの基板と光学フィルム積層体との接着性を高めるために、各種のSiカップリング剤又は架橋剤を添加することができる。また、接着剤組成物には、暗反応を防止したり、可使時間を増大させたりするといった観点から、重合禁止剤を添加することもできる。さらに、接着剤組成物に、光学フィルム積層体の透過波長に合わせた光増感剤を添加することによって、光学フィルム積層体の透過波長と異なる光吸収波長の重合開始剤を用いた場合でも本発明の効果を達成することもできる。さらにまた、接着剤組成物には、導電性を付与するための導電性材料を添加したり、位相差を付与するための複屈折を有する微粒子を添加したり、表面のレベリング性を上げるための界面活性剤を添加したりすることもできる。さらにまた、接着剤組成物には、各種の硬化剤を添加することもできる。硬化剤としては、フェノール樹脂、各種イミダゾール系化合物及びその誘導体、ヒドラジド化合物、ジシアンジアミド、イソシアネート系化合物及びこれらをマイクロカプセル化したもの等が挙げられ、例えば、硬化剤としてフェノール樹脂が添加された場合は、さらに硬化促進剤としてトリフェニルフォスフィン等のリン系化合物等を併用することもできる。
接着剤層20又は70の厚みは、20μm以下であることが好ましく、10μm以下であることがより好ましい。接着剤層の厚みが20μmより厚い場合には、接着剤層の硬化による収縮力が大きくなることによって、特に大型の画像表示装置用ユニットの場合にはパネルに反りの力が加わるため、表示不良になる可能性がある。
本発明に係る画像表示装置用ユニットの製造方法は、以下の工程を含むものとすることができる。まず、PVA系樹脂からなる偏光子12又は52と偏光子保護機能層14又は54とを積層して、偏光子の片面又は両面に偏光子保護機能層が積層された光学フィルム積層体を準備する。片面のみに偏光子保護機能層14が積層された光学フィルム積層体には、偏光子保護機能層14とは反対側の面に、仮保護用フィルムを積層しておくことが好ましい。
本発明を具体的に説明するために、厚みの異なる以下の6種類の光学フィルム積層体を準備した。
光学フィルム積層体1は、偏光子保護機能層であるトリアセチルセルロースフィルム(TACフィルム)、偏光子、TACフィルム、及び表面保護層であるハードコート層(HC層)が、この順に積層されたものである。全体の厚みは188μmであり、偏光子が22μm、TACフィルムが80μm、HC層が3μmである。この光学フィルム積層体のHC層表面における硬度は、鉛筆硬度で3Hであった。
光学フィルム積層体2は、アクリル系フィルム、偏光子、TACフィルム、及びHC層が、この順に積層されたものである。全体の厚みは137μmであり、アクリル系フィルムが40μm、偏光子が25μm、TACフィルムが60μm、HC層が12μmである。この光学フィルム積層体のHC層表面における硬度は、鉛筆硬度で2Hであった。
光学フィルム積層体3は、アクリル系フィルム、偏光子、TACフィルム、及びHC層が、この順に積層されたものである。全体の厚みは88μmであり、アクリル系フィルムが20μm、偏光子が22μm、TACフィルムが40μm、HC層が6μmである。この光学フィルム積層体のHC層表面における硬度は、鉛筆硬度で3Hであった。
<偏光子の作成>
重合度2400、ケン化度99.9%、厚み75μmのポリビニルアルコールフィルム(クラレ製、VF-PS-N#7500)の片面を30℃の温水に60秒間浸漬して膨潤(膨潤浴)させ、2倍に延伸した。次いで、ヨウ素/ヨウ化カリウム(重量比=1/7)の濃度3.2%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した(染色浴)。次いで、ホウ酸3%、ヨウ化カリウム3%の水溶液中に20秒間浸漬し、3.6倍まで延伸させた(架橋浴)。次いで、60℃のホウ酸4%、ヨウ化カリウム5%の水溶液中で6.0倍まで延伸し(延伸浴)、ヨウ化カリウム3%の溶液中でヨウ素イオン含浸処理をした。最後に、60℃のオーブンで4分間乾燥を行い、偏光子を得た。
次に、得られた偏光子の一方の面に偏光子保護機能層となるトリアセチルセルロース(TAC)フィルム(富士フィルム製、TD80UL)を貼り合わせて、光学フィルム積層体を得た。なお、この時点では、偏光子の他方の面に、剥離可能な仮保護用フィルムとしてPETフィルムを重ねた。偏光子とTACフィルムとを貼り合わせるための接着剤として、アセトアセチル基を有するポリビニルアルコール系樹脂(平均重合度:1200、ケン化度98.5モル%、アセトアセチル化度:5モル%)100部に対し、メチロールメラニン20部を30℃の条件下に純水に溶解し、固形分濃度3.2%に調整した水溶液を調製したものを用いた。偏光子とTACフィルムとは、この接着剤を用い、30℃の温度条件下でロール機を用いて貼り合わせた後、60℃で5分間乾燥させることによって行った。接着剤は、偏光子とTACの間にのみ使用した。光学フィルム積層体から仮保護用PETフィルムを剥離し、剥離面に市販のハードコート剤を厚み8μmになるように塗布し、UV照射して硬化させた。得られた光学フィルム積層体4は、TACフィルム、偏光子、HC層が、この順で積層されたものである。全体の厚みは113μmであり、偏光子が25μm、TACフィルムが80μm、HC層が8μmである。この光学フィルム積層体のHC層表面における硬度は、鉛筆硬度で3Hであった。
光学フィルム積層体5は、TACフィルム、偏光子、HC層が、この順で積層されたものである。全体の厚みは50μmであり、偏光子が5μm、TACフィルムが40μm、HC層が5μmである。光学フィルム積層体5の偏光子は、特許第4691205号公報に記載の方法を用いて作成した。この光学フィルム積層体のHC層表面における硬度は、鉛筆硬度で3Hであった。
光学フィルム積層体4の偏光子と同じ方法で作成された偏光子の一方の面に偏光子保護機能層となる厚み50μmのフィルム状ガラスを貼り合わせて、光学フィルム積層体を得た。なお、この時点では、偏光子の他方の面に、剥離可能な仮保護用フィルムとしてPETフィルムを重ねた。偏光子とフィルム状ガラスとを貼り合わせるための接着剤として、2-ヒドロキシエチルアクリルアミドモノマー(HEAA)(興人製)100部に光重合開始剤(BASF製、イルガキュア819)0.5部を添加し、溶解速度を速めるために50℃で加熱しながら超音波をかけて溶解して、接着剤を調整した。接着剤には、さらに、ガラスとの密着性を上げるために、シランカップリング剤(信越シリコーン製、KBM5103)を、混合モノマー100部に対して0.5部添加した。フィルム状ガラスにスポイトで上記接着剤を滴下し、偏光子とフィルム状ガラスをラミネータを用いてロール間で貼り合わせた。偏光子のフィルム状ガラスとは反対側の面には、仮保護用のPETフィルムを接着剤を使用せずに重ねた。この積層体に対して、紫外線照射装置(アイグラフィックス製 UBX0801-01 出力8kW(高圧水銀ランプ))によって紫外線をガラス側から照射し、接着剤組成物を硬化させた。照射条件は、波長365nm、照射強度30mW/cm2、照射時間30秒間とした。接着剤は、偏光子とフィルム状ガラスの間にのみ使用した。得られた光学フィルム積層体6全体の厚みは75μmであり、偏光子の厚みが25μm、フィルム状ガラスの厚みが50μmである。この光学フィルム積層体6のフィルム状ガラス表面における硬度は、鉛筆硬度で9H以上であった。
アクリル系化合物を含むエネルギー硬化型接着剤組成物のモノマーとして、以下の材料を表1に示される割合(重量比)で混合した混合モノマーを用いた。各々の混合割合は、硬化後の25℃における弾性率がそれぞれ異なるように決定した。
HEAA;2-ヒドロキシエチルアクリルアミド(興人製)
4-HBA:4-ヒドロキシブチルアクリレート(大阪有機化学工業製)
ACMO:アクリロイルモルホリン(興人製)
THFA:アクリル酸テトラヒドロフルフリル(東京化成工業製)
変形モード 引っ張り
周波数 1Hz
初期ひずみ 0.1%
温度 -40℃~200℃
昇温速度10℃/min
エポキシ系化合物を含むエネルギー硬化型接着剤組成物の主成分として、以下の材料を用いた。
エポライト80MF(共栄社化学製)
エポライト100MF(共栄社化学製)
エポライト40E(共栄社化学製)
これらの材料の各々90部に対して、オキセタン化合物10部を添加し、3種類の混合物を得た。オキセタン化合物は、東亞合成製のOXT221を用いた。さらに、これらの混合物100部の各々に、以下の光酸発生剤3部及び増感剤0.5部を混合して、接着剤組成物9~接着剤組成物11を調製した。
ウレタン系化合物を含むエネルギー硬化型接着剤組成物として、以下のものを用い、接着剤組成物12~接着剤組成物14とした。
W-6020(三井化学製)
W-405(三井化学製)
W-6061(三井化学製)
接着剤組成物12~接着剤組成物14を、上述の光学フィルム積層体1~6の各々に種々の厚みとなるように塗布し、110℃の熱で1時間加熱した。次に、これらの光学フィルム積層体をガラスと貼り合わせた。接着剤組成物12~接着剤組成物14の硬化後の25℃における弾性率は、表3に示すとおりである。弾性率は、接着剤組成物1~接着剤組成物8と同様に測定した。
アクリル系粘着剤は、以下のとおり調製した。まず、ブチルアクリレート95重量部、アクリル酸3.0重量部、2-ヒドロキシエチルアクリレート0.10重量部、2,2-アゾビスイソブチロニトリル0.050重量部、及び酢酸エチル200重量部を、窒素導入管及び冷却管を備えた4つ口フラスコに投入し、充分に窒素置換した後、窒素気流下で撹拌しながら55℃で20時間重合反応を行い、重量平均分子量157万の高分子量のアクリル系ポリマーAの溶液を得た。次に上記アクリル系ポリマーAの溶液(固形分)100重量部に対して、ジベンゾイルパーオキシド(1分間半減期:130.0℃)0.15重量部、シランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.080重量部、架橋剤としてトリメチロールプロパンのトリレンジイソシアネート付加物からなるイソシアネート系架橋剤(コロネートL、日本ポリウレタン製)0.60重量部を均一に混合して、粘着剤組成物を調製した。上記粘着剤組成物を、シリコーン剥離処理した厚さ38μmのポリエチレンテレフタレートフィルム(三菱ポリエステル社製、MRF38(付加反応型シリコーン))に塗布し、150℃で2分間乾燥および過酸化物分解処理を行った。弾性率は、TAインスツルメンツ製固体粘弾性装置RSAIIIを用いて測定し、3.41×105Paであった。なお、粘着剤は弾性率が低く、短冊状のサンプルに引っ張り応力をかけて弾性率を測定することができないため、ねじりせん断応力をかけて弾性率を測定した。
光学フィルム積層体1~5を構成する各層の弾性率をテンシロンで測定した。弾性率は、試料が変形する直前における最大弾性(SSカーブの最大傾斜の接線の一次式)から求めた。偏光子保護機能層であるTACフィルムは、フジフィルム製TD80ULである。アクリル系フィルムは、下記一般式(1)中、R1は水素原子、R2及びR3はメチル基であるラクトン環構造を有する(メタ)アクリル系樹脂[共重合モノマーの重量比:メタクリル酸メチル/2-(ヒドロキシメチル)アクリル酸メチル=8/2;ラクトン環化率約100%]を押出成膜した後、二軸延伸した透明保護フィルム(厚さ40μm)である。
光学フィルム積層体1~6の各々とガラスとを、種々の厚みの接着組成物1~14又は粘着剤を用いて貼り合せて、積層体ユニットを作成した。接着剤組成物1~14とガラスとの貼り合わせ方法は、上述のとおりである。光学フィルム積層体1~6とガラスとの積層体ユニットの各々について、積層体の最外面(すなわち、HC層又はフィルム状ガラス)の表面硬度を測定した。表面硬度は、JIS K5600-5-4(引っかき硬度(鉛筆法))に準じて、積層体の表面を引っかき、表面に塑性変形(押し傷)が生じない鉛筆硬度の上限として評価した。測定結果をプロットしたグラフを図3~図7に示す。図3~図7はそれぞれ、光学フィルム積層体1~5を用いた積層体ユニットについての測定結果である。各々の図において、横軸は接着剤層の弾性率を示し、縦軸は接着剤層の厚みを示す。各々の図における各点は、接着剤層の種類及び厚みが異なる積層体ユニットについての測定点である。図における凡例のF、H、2H、及び3Hは、鉛筆硬度を示す。
10、50 光学フィルム積層体
12、52 偏光子
14、54 偏光子保護機能層
16、56 表面保護層
20、70 接着剤層
30、80 画像表示装置用パネル
Claims (8)
- 偏光子、該偏光子の一方の面側に積層された偏光子保護機能層、及び該偏光子の前記偏光子保護機能層が接する面とは反対側の面側に積層された表面保護層を含む、光学フィルム積層体と、前記偏光子保護機能層の前記偏光子が接する面とは反対側の面側に積層された接着剤層と、該接着剤層の前記偏光子保護機能層が接する面とは反対側の面側に積層された画像表示装置用パネルとを含み、
前記光学フィルム積層体の厚みが120μm以下であり、
硬化後の前記接着剤層の25℃における弾性率が、前記光学フィルム積層体に含まれる各層のうち弾性率が最も小さい層の弾性率の50分の1以上である
ことを特徴とする、画像表示装置用ユニット。 - 偏光子、該偏光子の両面に積層された偏光子保護機能層、及び該偏光子保護機能層の一方の前記偏光子が接する面とは反対側の面側に積層された表面保護層を含む、光学フィルム積層体と、前記偏光子保護機能層の他方の前記偏光子が接する面とは反対側の面側に積層された接着剤層と、該接着剤層の前記偏光子保護機能層が接する面とは反対側の面側に積層された画像表示装置用パネルとを含み、
前記光学フィルム積層体の厚みが120μm以下であり、
硬化後の前記接着剤層の25℃における弾性率が、前記光学フィルム積層体に含まれる各層のうち弾性率が最も小さい層の弾性率の50分の1以上である
ことを特徴とする、画像表示装置用ユニット。 - 硬化後の前記接着剤層の25℃における弾性率が、前記光学フィルム積層体に含まれる各層のうち弾性率が最も小さい層の弾性率の10分の1以上であることを特徴とする、請求項1又は請求項2に記載の画像表示装置用ユニット。
- 前記光学フィルム積層体の厚みが100μm以下であることを特徴とする、請求項1又は請求項2に記載の画像表示装置用ユニット。
- 前記光学フィルム積層体の厚みが100μm以下であることを特徴とする、請求項3に記載の画像表示装置用ユニット。
- 硬化後の前記接着剤層の25℃における弾性率が、1×108Pa~1×1010Paであることを特徴とする、請求項4又は請求項5に記載の画像表示装置用ユニット。
- 前記光学フィルム積層体の前記表面保護層の露出面における鉛筆硬度が、前記光学フィルム積層体単体で測定したときの前記表面保護層の露出面における鉛筆硬度と同じであるか、又は、前記光学フィルム積層体単体で測定したときの前記表面保護層の露出面における鉛筆硬度より1ランク低いことを特徴とする、請求項1から請求項6のいずれかの請求項に記載の画像表示装置用ユニット。
- 請求項1から請求項7までのいずれかの請求項に記載の画像表示装置用ユニットを用いたことを特徴とする画像表示装置。
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CN103858158A (zh) | 2014-06-11 |
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TWI627068B (zh) | 2018-06-21 |
CN103858158B (zh) | 2018-09-28 |
US20140300965A1 (en) | 2014-10-09 |
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