WO2012144509A1 - 光学積層体 - Google Patents
光学積層体 Download PDFInfo
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- WO2012144509A1 WO2012144509A1 PCT/JP2012/060421 JP2012060421W WO2012144509A1 WO 2012144509 A1 WO2012144509 A1 WO 2012144509A1 JP 2012060421 W JP2012060421 W JP 2012060421W WO 2012144509 A1 WO2012144509 A1 WO 2012144509A1
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- hard coat
- acrylic resin
- layer
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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
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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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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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
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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
- G02B1/11—Anti-reflection coatings
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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
- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0273—Diffusing elements; Afocal elements characterized by the use
- G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
Definitions
- the present invention relates to an optical laminate.
- Image display devices such as liquid crystal display (LCD), cathode ray tube display device (CRT), plasma display (PDP), electroluminescence display (ELD), etc. are visible when the surface is damaged by external contact. May decrease. For this reason, an optical laminate including a base film and a hard coat layer is used for the purpose of protecting the surface of the image display device.
- a base film of the optical laminate triacetyl cellulose (TAC) is typically used (Patent Document 1).
- TAC triacetyl cellulose
- the base film made of TAC has high moisture permeability. Therefore, when an optical laminate including such a substrate film is used in an LCD, moisture is transmitted through the optical laminate under high temperature and high humidity, resulting in a problem that the optical characteristics of the polarizer are deteriorated.
- LCDs are also frequently used for outdoor use devices such as car navigation systems and personal digital assistants. Even under severe conditions such as high temperature and high humidity, There is a need for a reliable LCD that does not cause problems.
- Patent Literature an optical laminate having a hard coat layer formed by applying and drying a hard coat layer forming composition on a low moisture-permeable acrylic base film.
- Patent Literature 2 an optical laminate having a hard coat layer formed by applying and drying a hard coat layer forming composition on a low moisture-permeable acrylic base film.
- the inventors of the present invention have examined the adhesion between the acrylic base film and the hard coat layer by the anchor effect, and try to improve the adhesion (typically for forming a hard coat layer).
- the base film component was eluted into the hard coat layer, and a new problem was found that the scratch resistance was lowered.
- This invention is made
- the place made into the objective uses the (meth) acrylic-type resin film (base film) containing the (meth) acrylic-type resin of low moisture permeability.
- Another object of the present invention is to provide an optical laminate capable of ensuring adhesion between a (meth) acrylic resin film (base film) and a hard coat layer and preventing a decrease in scratch resistance.
- the optical layered body of the present invention comprises a base layer formed from a (meth) acrylic resin film, and a hard coat layer forming composition containing a curable compound and inorganic nanoparticles in the (meth) acrylic resin film.
- the hard coat layer-forming composition penetrates the (meth) acrylic resin film between the hard coat layer formed by coating and the base material layer and the hard coat layer.
- a permeation layer having a thickness of 1.2 ⁇ m or more, wherein the content ratio of the inorganic nanoparticles is 1.5 wt% to 50 wt% with respect to the total of the curable compound and the inorganic nanoparticles is there.
- the composition for forming a hard coat layer contains a curable compound having 5 or more (meth) acryloyl groups, and contains the curable compound having 5 or more (meth) acryloyl groups. The ratio is 15% by weight to 100% by weight with respect to the total curable compound in the composition for forming a hard coat layer.
- the composition for forming a hard coat layer includes a curable compound having 2 to 4 (meth) acryloyl groups, and the curable compound having 2 to 4 (meth) acryloyl groups. Is 85% by weight or less based on the total amount of the curable compound in the composition for forming a hard coat layer.
- the said hard-coat layer composition further contains a monofunctional monomer, and the content rate of this monofunctional monomer is 40 weight% or less with respect to all the sclerosing
- the monofunctional monomer has a weight average molecular weight of 500 or less.
- the monofunctional monomer has a hydroxyl group.
- the monofunctional monomer is hydroxyalkyl (meth) acrylate and / or N- (2-hydroxyalkyl) (meth) acrylamide.
- permeability of the light in wavelength 380nm of the said (meth) acrylic-type resin film is 15% or less.
- the (meth) acrylic resin forming the (meth) acrylic resin film has a structural unit that exhibits positive birefringence and a structural unit that exhibits negative birefringence.
- the (meth) acrylic resin forming the (meth) acrylic resin film has a weight average molecular weight of 10,000 to 500,000.
- the concentration of the (meth) acrylic resin forming the (meth) acrylic resin film is from the base material layer side of the osmotic layer to the hard coat layer. The layer is continuously lowered to the side opposite to the base layer.
- permeation layer of the said hard-coat layer has an uneven structure.
- the optical layered body of the present invention further includes an antireflection layer on the opposite side of the hard coat layer from the penetration layer.
- a polarizing plate is provided. This polarizing plate includes the optical laminate.
- an image display device is provided. This image display device includes the optical laminate.
- a hard coat layer using a composition for forming a hard coat layer containing inorganic nanoparticles at a specific content, a (meth) acrylic resin film having a low moisture permeability (base film) ), An optical laminate excellent in both the adhesion between the (meth) acrylic resin film (base film) and the hard coat layer and the scratch resistance of the hard coat layer can be obtained.
- (A) is a schematic sectional drawing of the optical laminated body by preferable embodiment of this invention
- (b) is a schematic sectional drawing of the optical laminated body which has the conventional general hard-coat layer.
- FIG. 1A is a schematic cross-sectional view of an optical laminate according to a preferred embodiment of the present invention
- FIG. 1B is an optical laminate having a conventional general hard coat layer.
- FIG. The optical laminated body 100 shown to Fig.1 (a) is equipped with the base material layer 10 formed from a (meth) acrylic-type resin film, the osmosis
- the hard coat layer 30 is formed by applying a composition for forming a hard coat layer containing a curable compound to a (meth) acrylic resin film.
- the permeation layer 20 is formed by permeating the (meth) acrylic resin film with the hard coat layer forming composition.
- the composition for forming a hard coat layer penetrates into the (meth) acrylic resin film in this way, the composition for forming the hard coat layer reaches (penetrates) in the (meth) acrylic resin film. This is the part that did not.
- the permeation layer is not formed.
- Boundary A shown in FIGS. 1A and 1B is a boundary defined by the hard coat layer forming composition coating surface of the (meth) acrylic resin film.
- the boundary A is the boundary between the osmotic layer 20 and the hard coat layer 30 in the optical laminate 100, and the base layer 10 ′ (ie, (meta)) in the optical laminate 200 in which the osmotic layer is not formed.
- This is the boundary between the acrylic resin film) and the hard coat layer 30 '.
- (meth) acryl means acryl and / or methacryl.
- the penetrating layer 20 is formed by penetrating the (meth) acrylic resin film with the hard coat layer forming composition in the optical laminate 100. That is, the osmotic layer 20 is a portion where a hard coat layer component is present in the (meth) acrylic resin film.
- the thickness of the osmotic layer 20 is 1.2 ⁇ m or more.
- permeation layer 20 is the thickness of the part in which the hard-coat layer component exists in the said (meth) acrylic-type resin film, Specifically, a hard-coat layer in a (meth) acrylic-type resin film. The distance between the boundary A and the boundary A between the portion where the component is present (penetrating layer) and the portion where the component is not present (base material layer).
- the composition for forming a hard coat layer used in the present invention further contains inorganic nanoparticles.
- the inorganic nanoparticles 1 are present in the hard coat layer 30 formed by the hard coat layer forming composition. If the hard coat layer 30 containing the inorganic nanoparticles 1 is formed by the hard coat layer forming composition containing inorganic nanoparticles, the components in the (meth) acrylic resin film eluted into the hard coat layer forming composition ( Typically, a resin component in a (meth) acrylic resin film) is prevented from diffusing to the air interface of the hard coat layer when forming the hard coat layer, and an optical laminate having excellent scratch resistance is obtained. Can do.
- any appropriate other layer may be disposed outside the hard coat layer 30 as necessary.
- the other layers are typically disposed via an adhesive layer (not shown).
- the (meth) acrylic resin forming the (meth) acrylic resin film may be eluted in the hard coat layer forming composition, and the (meth) acrylic resin may be present in the hard coat layer. .
- an optical laminate having excellent scratch resistance can be obtained even when the (meth) acrylic resin is present in the hard coat layer.
- the concentration of the (meth) acrylic resin forming the (meth) acrylic resin film is from the base material layer 10 side of the osmotic layer 20 to the base material of the hard coat layer 30. It becomes continuously lower toward the side opposite to the layer 10 (that is, the air side interface of the hard coat layer 30). Since the concentration of the (meth) acrylic resin continuously changes, that is, the interface resulting from the concentration change of the (meth) acrylic resin is not formed, interface reflection can be suppressed, and interference unevenness is small. This is because an optical laminate can be obtained.
- the amplitude of the reflection spectrum of the hard coat layer in the wavelength region of 500 nm to 600 nm of the optical layered body of the present invention is preferably 1.0% or less, more preferably 0.5% or less, and still more preferably 0.8. It is 3% or less, and particularly preferably 0.1% or less. According to the present invention, it is possible to obtain an optical laminated body having a small reflection spectrum amplitude, that is, having little interference unevenness.
- the optical layered body of the present invention has a permeation layer having a predetermined thickness, even if a material having a large refractive index difference is selected as a material for forming the (meth) acrylic resin film and the hard coat layer, occurrence of interference unevenness is prevented. can do.
- the absolute value of the difference between the refractive index of the base material layer and the refractive index of the hard coat layer can be set to 0.01 to 0.15. Of course, it is also possible to set the absolute value of the difference in refractive index to less than 0.01.
- the optical laminate of the present invention is applied to, for example, a polarizing film (also referred to as a polarizing plate).
- a polarizing film also referred to as a polarizing plate.
- the optical laminate of the present invention is provided on one or both sides of a polarizer in a polarizing film, and can be suitably used as a protective material for the polarizer.
- the base material layer is formed of a (meth) acrylic resin film. More specifically, as described above, when the base layer is coated with the composition for forming a hard coat layer on the (meth) acrylic resin film, in the (meth) acrylic resin film, This is the part where the forming composition did not reach (penetrate).
- the (meth) acrylic resin film includes a (meth) acrylic resin.
- the (meth) acrylic resin film is obtained, for example, by extruding a molding material containing a resin component containing a (meth) acrylic resin as a main component.
- the moisture permeability of the (meth) acrylic resin film is preferably 200 g / m 2 ⁇ 24 hr or less, and more preferably 80 g / m 2 ⁇ 24 hr or less. According to the present invention, even when a (meth) acrylic resin film having such a high moisture permeability is used, the adhesion between the (meth) acrylic resin film and the hard coat layer is excellent, and interference unevenness is suppressed. An optical laminate can be obtained.
- the moisture permeability can be measured under the test conditions of 40 ° C. and a relative humidity of 92%, for example, by a method according to JIS Z 0208.
- the light transmittance at a wavelength of 380 nm of the (meth) acrylic resin film is preferably 15% or less, more preferably 12% or less, and further preferably 9% or less. If the transmittance of light having a wavelength of 380 nm is in such a range, an excellent ultraviolet absorbing ability is exhibited, so that deterioration of ultraviolet rays due to external light or the like of the optical laminate can be prevented.
- the in-plane retardation Re of the (meth) acrylic resin film is preferably 10 nm or less, more preferably 7 nm or less, still more preferably 5 nm or less, particularly preferably 3 nm or less, and most preferably 1 nm or less.
- the thickness direction retardation Rth of the (meth) acrylic resin film is preferably 15 nm or less, more preferably 10 nm or less, further preferably 5 nm or less, particularly preferably 3 nm or less, and most preferably 1 nm. It is as follows. If the in-plane retardation and the thickness direction retardation are within such ranges, the adverse effect on the display characteristics of the image display apparatus due to the phase difference can be remarkably suppressed.
- a (meth) acrylic resin film having in-plane retardation and thickness direction retardation in such a range can be obtained by using, for example, a (meth) acrylic resin having a glutarimide structure described later.
- nx is the refractive index in the slow axis direction of the (meth) acrylic resin film
- ny is the refractive index in the fast axis direction of the (meth) acrylic resin film
- nz is the (meth) acrylic system. It is the refractive index in the thickness direction of the resin film
- d (nm) is the thickness of the (meth) acrylic resin film.
- the slow axis refers to the direction in which the in-plane refractive index is maximized
- the fast axis refers to the direction perpendicular to the slow axis in the plane.
- Re and Rth are measured using light having a wavelength of 590 nm.
- any appropriate (meth) acrylic resin can be adopted as the (meth) acrylic resin.
- poly (meth) acrylate such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester -(Meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer) And methyl methacrylate- (meth) acrylate norbornyl copolymer).
- poly (meth) acrylate such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid
- poly (meth) acrylate C 1-6 alkyl such as poly (meth) acrylate methyl is used.
- a methyl methacrylate resin containing methyl methacrylate as a main component 50 wt% to 100 wt%, preferably 70 wt% to 100 wt%) can be used.
- the weight average molecular weight of the (meth) acrylic resin is preferably 10,000 to 500,000, more preferably 30,000 to 500,000. According to the present invention, even if a (meth) acrylic resin having a small weight average molecular weight is used, that is, even if a (meth) acrylic resin that is relatively easily dissolved in the hard coat layer is used, the optical laminate has excellent scratch resistance. You can get a body. If a (meth) acrylic resin having a small weight average molecular weight is used, an adhesive layer having a sufficient thickness is formed in the (meth) acrylic resin film, and the adhesion between the (meth) acrylic resin film and the hard coat layer. It is possible to obtain an optical laminated body that is excellent in the quality of the interference and the interference unevenness is suppressed.
- the glass transition temperature of the (meth) acrylic resin is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. When the glass transition temperature is in such a range, a (meth) acrylic resin film excellent in durability and heat resistance can be obtained.
- the upper limit of the glass transition temperature is not particularly limited, but is preferably 170 ° C. or less from the viewpoint of moldability and the like.
- the (meth) acrylic resin preferably has a structural unit that exhibits positive birefringence and a structural unit that exhibits negative birefringence. If these structural units are included, the abundance ratio can be adjusted to control the retardation of the (meth) acrylic resin film, and a (meth) acrylic resin film having a low retardation can be obtained. it can.
- the structural unit exhibiting positive birefringence include a structural unit constituting a lactone ring, polycarbonate, polyvinyl alcohol, cellulose acetate, polyester, polyarylate, polyimide, polyolefin, etc., and a general formula (1) described later. Examples include structural units.
- Examples of the structural unit exhibiting negative birefringence include a structural unit derived from a styrene monomer, a maleimide monomer, a structural unit of polymethyl methacrylate, a structural unit represented by the general formula (3) described later, and the like. Can be mentioned.
- a structural unit that exhibits positive birefringence is a case where a resin having only the structural unit exhibits positive birefringence characteristics (that is, a slow axis appears in the stretching direction of the resin). Means a structural unit.
- a structural unit that develops negative birefringence is when a resin having only the structural unit exhibits negative birefringence characteristics (that is, when a slow axis appears in a direction perpendicular to the stretching direction of the resin).
- a (meth) acrylic resin having a lactone ring structure or a glutarimide structure is preferably used as the (meth) acrylic resin.
- a (meth) acrylic resin having a lactone ring structure or a glutarimide structure is excellent in heat resistance. More preferred is a (meth) acrylic resin having a glutarimide structure. If a (meth) acrylic resin having a glutarimide structure is used, a (meth) acrylic resin film having low moisture permeability and a small retardation and ultraviolet transmittance can be obtained as described above.
- Examples of (meth) acrylic resins having a glutarimide structure include, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A-2006-328329.
- the glutarimide resin includes a structural unit represented by the following general formula (1) (hereinafter also referred to as a glutarimide unit) and a structural unit represented by the following general formula (2) (hereinafter referred to as (meta)). Also referred to as an acrylate unit).
- R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or 3 to 3 carbon atoms.
- 12 a cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.
- R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 6 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or 3 to 3 carbon atoms.
- 12 a cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.
- the glutarimide resin may further contain a structural unit represented by the following general formula (3) (hereinafter also referred to as an aromatic vinyl unit) as necessary.
- R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms
- R 8 is an aryl group having 6 to 10 carbon atoms.
- R 1 and R 2 are each independently hydrogen or a methyl group
- R 3 is hydrogen, a methyl group, a butyl group, or a cyclohexyl group, and more preferably , R 1 is a methyl group, R 2 is hydrogen, and R 3 is a methyl group.
- the glutarimide resin may include only a single type as a glutarimide unit, or may include a plurality of types in which R 1 , R 2 , and R 3 in the general formula (1) are different. Good.
- the glutarimide unit can be formed by imidizing the (meth) acrylic acid ester unit represented by the general formula (2).
- the glutarimide unit may be an acid anhydride such as maleic anhydride, or a half ester of such an acid anhydride and a linear or branched alcohol having 1 to 20 carbon atoms; acrylic acid, methacrylic acid, maleic acid It can also be formed by imidizing an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid such as maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid.
- R 4 and R 5 are each independently hydrogen or a methyl group
- R 6 is hydrogen or a methyl group
- R 4 is hydrogen
- R 5 is a methyl group
- R 6 is a methyl group
- the glutarimide resin may contain only a single type as a (meth) acrylic acid ester unit, or a plurality of types in which R 4 , R 5 and R 6 in the general formula (2) are different. May be included.
- the glutarimide resin preferably contains styrene, ⁇ -methylstyrene, and more preferably styrene as the aromatic vinyl unit represented by the general formula (3).
- aromatic vinyl unit By having such an aromatic vinyl unit, the positive birefringence of the glutarimide structure can be reduced, and a (meth) acrylic resin film having a lower retardation can be obtained.
- the glutarimide resin may contain only a single type as an aromatic vinyl unit, or may contain a plurality of types in which R 7 and R 8 are different.
- the content of the glutarimide unit in the glutarimide resin is preferably changed depending on, for example, the structure of R 3 .
- the content of the glutarimide unit is preferably 1% by weight to 80% by weight, more preferably 1% by weight to 70% by weight, even more preferably 1% by weight, based on the total structural unit of the glutarimide resin. -60% by weight, particularly preferably 1-50% by weight.
- a (meth) acrylic resin film having a low retardation can be obtained.
- the content of the aromatic vinyl unit in the glutarimide resin can be appropriately set according to the purpose and desired characteristics. Depending on the application, the content of the aromatic vinyl unit may be zero.
- the content thereof is preferably 10% by weight to 80% by weight, more preferably 20% by weight to 80% by weight, based on the glutarimide unit of the glutarimide resin. More preferably, it is 20% by weight to 60% by weight, and particularly preferably 20% by weight to 50% by weight.
- a (meth) acrylic resin film having a low retardation, excellent heat resistance and mechanical strength can be obtained.
- the glutarimide resin may be further copolymerized with other structural units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit, if necessary.
- other structural units include structures composed of nitrile monomers such as acrylonitrile and methacrylonitrile, and maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Units are listed. These other structural units may be directly copolymerized or graft copolymerized in the glutarimide resin.
- the (meth) acrylic resin film contains an ultraviolet absorber.
- the ultraviolet absorber any appropriate ultraviolet absorber can be adopted as long as the desired characteristics are obtained.
- Representative examples of the above UV absorbers include triazine UV absorbers, benzotriazole UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, benzoxazine UV absorbers, and oxadiazole UV absorbers. Agents. These ultraviolet absorbers may be used alone or in combination.
- the content of the ultraviolet absorber is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin. .
- the content of the ultraviolet absorber is in such a range, ultraviolet rays can be absorbed effectively and the transparency of the film during film formation does not deteriorate.
- the content of the ultraviolet absorber is less than 0.1 parts by weight, the ultraviolet blocking effect tends to be insufficient.
- there is more content of a ultraviolet absorber than 5 weight part there exists a tendency for coloring to become intense or the haze of the film after shaping
- the (meth) acrylic resin film may contain any appropriate additive depending on the purpose.
- additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; Infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents such as anionic, cationic and nonionic surfactants; coloring of inorganic pigments, organic pigments, dyes, etc.
- organic fillers and inorganic fillers resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;
- the kind, combination, content, and the like of the additive to be contained can be appropriately set according to the purpose and desired characteristics.
- (meth) acrylic-type resin film Although it does not specifically limit as a manufacturing method of the said (meth) acrylic-type resin film,
- (meth) acrylic-type resin, an ultraviolet absorber, and other polymers, additives, etc. as needed are sufficiently mixed by any appropriate mixing method to obtain a thermoplastic resin composition in advance, and then this can be formed into a film.
- a (meth) acrylic resin, an ultraviolet absorber, and if necessary, other polymers and additives are mixed in separate solutions to form a uniform mixed solution, and then film forming May be.
- the film raw material is pre-blended with any suitable mixer such as an omni mixer, and then the obtained mixture is extruded and kneaded.
- the mixer used for extrusion kneading is not particularly limited, and for example, any suitable mixer such as an extruder such as a single screw extruder or a twin screw extruder or a pressure kneader may be used. Can do.
- the film forming method examples include any appropriate film forming methods such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method.
- a melt extrusion method is preferred. Since the melt extrusion method does not use a solvent, it is possible to reduce the manufacturing cost and the burden on the global environment and work environment due to the solvent.
- melt extrusion method examples include a T-die method and an inflation method.
- the molding temperature is preferably 150 ° C to 350 ° C, more preferably 200 ° C to 300 ° C.
- a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, and the film extruded into a film is wound to obtain a roll-shaped film Can do.
- simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.
- the (meth) acrylic resin film may be either an unstretched film or a stretched film as long as the desired retardation is obtained.
- a stretched film either a uniaxially stretched film or a biaxially stretched film may be used.
- a biaxially stretched film either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used.
- the stretching temperature is preferably in the vicinity of the glass transition temperature of the thermoplastic resin composition which is a film raw material, and more preferably, (glass transition temperature ⁇ 30 ° C.) to (glass transition temperature + 30 ° C.) Preferably, it is within the range of (glass transition temperature ⁇ 20 ° C.) to (glass transition temperature + 20 ° C.). If the stretching temperature is less than (glass transition temperature ⁇ 30 ° C.), the haze of the resulting film may increase, or the film may be torn or cracked, resulting in failure to obtain a predetermined stretching ratio.
- the stretching ratio is preferably 1.1 to 3 times, more preferably 1.3 to 2.5 times.
- the mechanical properties such as the film elongation, tear propagation strength, and fatigue resistance can be greatly improved.
- the above (meth) acrylic resin film can be subjected to a heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties.
- Arbitrary appropriate conditions can be employ
- the thickness of the (meth) acrylic resin film is preferably 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 100 ⁇ m. There exists a possibility that intensity
- the surface tension of the (meth) acrylic resin film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more.
- the surface wetting tension is at least 40 mN / m or more, the adhesion between the (meth) acrylic resin film and the hard coat layer is further improved.
- Any suitable surface treatment can be applied to adjust the surface wetting tension. Examples of the surface treatment include corona discharge treatment, plasma treatment, ozone spraying, ultraviolet irradiation, flame treatment, and chemical treatment. Of these, corona discharge treatment and plasma treatment are preferable.
- the penetration layer is formed by the penetration of the composition for forming a hard coat layer into the (meth) acrylic resin film as described above.
- the osmotic layer can correspond to a part of the compatibilized region between the (meth) acrylic resin forming the (meth) acrylic resin film and the compound forming the hard coat layer.
- the concentration of the (meth) acrylic resin forming the (meth) acrylic resin film is preferably continuously increased from the hard coat layer side to the base material layer side. Since the concentration of the (meth) acrylic resin continuously changes, that is, the interface resulting from the concentration change of the (meth) acrylic resin is not formed, interface reflection can be suppressed, and interference unevenness is small. This is because an optical laminate can be obtained.
- the lower limit of the thickness of the permeation layer is 1.2 ⁇ m, preferably 1.5 ⁇ m, more preferably 2 ⁇ m, and further preferably 3 ⁇ m.
- the upper limit of the thickness of the permeation layer is preferably ((meth) acrylic resin film thickness ⁇ 70%) ⁇ m, more preferably ((meth) acrylic resin film thickness ⁇ 40%) ⁇ m,
- the thickness is preferably ((meth) acrylic resin film thickness ⁇ 30%) ⁇ m, particularly preferably ((meth) acrylic resin film ⁇ 20%) ⁇ m.
- the thickness of the osmotic layer can be measured by the reflection spectrum of the hard coat layer. Details of the method for measuring the thickness of the permeation layer will be described later as an evaluation method in Examples.
- the hard coat layer is formed by coating the composition for forming a hard coat layer on the (meth) acrylic resin film.
- the composition for forming a hard coat layer includes a curable compound and inorganic nanoparticles.
- the said curable compound can be hardened
- the curable compound is a photocurable type.
- the curable compound may be any of a monomer, an oligomer and a prepolymer.
- the inorganic nanoparticles can be coated with an organic compound (typically, an organic compound having a polymerizable unsaturated group), as described later. However, the inorganic nanoparticles are not included in the “curable compound”.
- the hard coat layer-forming composition preferably contains a curable compound having 5 or more (meth) acryloyl groups.
- the upper limit of the number of (meth) acryloyl groups contained in the curable compound having 5 or more (meth) acryloyl groups is preferably 100. If a composition for forming a hard coat layer containing a curable compound having 5 or more (meth) acryloyl groups is used, a hard coat layer having excellent scratch resistance can be formed.
- “(meth) acryloyl” means methacryloyl and / or acryloyl.
- Examples of the curable compound having 5 or more (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and these. And oligomers or prepolymers thereof. These compounds may be used alone or in combination of two or more.
- “(meth) acrylate” means acrylate and / or methacrylate.
- the curable compound having 5 or more (meth) acryloyl groups may be an oligomer of urethane (meth) acrylate and / or urethane (meth) acrylate. If the composition for forming a hard coat layer contains urethane (meth) acrylate and / or urethane (meth) acrylate oligomer, a hard coat layer having excellent flexibility and adhesion to a (meth) acrylic resin film is formed. be able to.
- the number of functional groups of the urethane (meth) acrylate and urethane (meth) acrylate oligomer is more preferably 9 or more. If the composition for hard-coat layer formation containing the polyfunctional urethane (meth) acrylate and / or urethane (meth) acrylate oligomer is used, the hard-coat layer excellent in abrasion resistance can be formed.
- the urethane (meth) acrylate can be obtained, for example, by reacting hydroxy (meth) acrylate obtained from (meth) acrylic acid or (meth) acrylic acid ester and polyol with diisocyanate.
- Urethane (meth) acrylates and urethane (meth) acrylate oligomers may be used alone or in combination.
- Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
- polyol examples include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, neopentyl hydroxypivalate Glycol ester, tricyclodecane dimethylol, 1,4-cyclohexanediol, spiroglycol, hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, trimethylol ethane, trimethylol Propane, glycerin, 3-methylpentane-1,3,5-triol, pentaeryth
- diisocyanate for example, various aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples of the diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4. -Diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hydrogenated products thereof.
- the weight average molecular weight of the curable compound having 5 or more (meth) acryloyl groups is preferably 200 to 10000, more preferably 500 to 5000, and still more preferably 1000 to 5000.
- the urethane (meth) acrylate oligomer preferably has a weight average molecular weight of 1,000 to 10,000. More preferably, it is 1000 to 5000.
- the content ratio of the curable compound having 5 or more (meth) acryloyl groups is preferably 15% by weight to 100% by weight with respect to the total curable compound in the composition for forming a hard coat layer. It is preferably 20% to 100% by weight, more preferably 40% to 100% by weight, and particularly preferably 40% to 70% by weight. If it is such a range, the optical laminated body which is more excellent in abrasion resistance can be obtained. Moreover, the optical laminated body which was excellent in the adhesiveness of a (meth) acrylic-type resin film and a hard-coat layer, and the interference nonuniformity was suppressed can be obtained.
- the urethane (meth) acrylate and / or urethane (meth) acrylate oligomer are used as the curable compound having 5 or more (meth) acryloyl groups.
- the urethane (meth) acrylate and urethane (meth) acrylate oligomers are used.
- the total content of is preferably 20% by weight to 100% by weight and more preferably 20% by weight to 70% by weight with respect to the total curable compound in the composition for forming a hard coat layer. Within such a range, it is possible to form a hard coat layer that is more excellent in scratch resistance and excellent in balance of hardness, flexibility, and adhesion. Moreover, the optical laminated body by which interference nonuniformity was suppressed can be obtained.
- the hard coat layer forming composition may contain a curable compound having 2 to 4 (meth) acryloyl groups.
- curable compound having 2 to 4 (meth) acryloyl groups examples include polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, and 1,6-hexanediol diester. Acrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, isocyanuric acid triacrylate Etc. Further, urethane (meth) acrylate and / or urethane (meth) acrylate oligomer may be used as the curable compound having 2 to 4 (meth) acryloyl groups.
- the weight average molecular weight of the curable compound having 2 to 4 (meth) acryloyl groups is preferably 200 to 1500, and more preferably 200 to 1000. If the hard coat layer-forming composition contains a curable compound having 2 to 4 (meth) acryloyl groups having a weight average molecular weight of 1500 or less, the (meth) acrylic resin film and the hard coat layer It is possible to obtain an optical layered body that has excellent adhesion and suppresses interference unevenness.
- the curable compound having 2 to 4 (meth) acryloyl groups preferably has a hydroxyl group. If the composition for forming a hard coat layer contains such a curable compound, the heating temperature at the time of forming the hard coat layer can be set lower, the heating time can be set shorter, and deformation due to heating can be suppressed.
- the produced optical laminate can be produced efficiently. Moreover, the optical laminated body excellent in the adhesiveness of a (meth) acrylic-type resin film and a hard-coat layer can be obtained.
- Examples of the curable compound having a hydroxyl group and 2 to 4 (meth) acryloyl groups include pentaerythritol tri (meth) acrylate.
- the content of the curable compound having 2 to 4 (meth) acryloyl groups is Preferably it is 85 weight% or less with respect to all the sclerosing
- the content of the curable compound having 2 to 4 (meth) acryloyl groups is more than 85% by weight, desired hardness and scratch resistance may not be obtained.
- the hard coat layer forming composition may contain a monofunctional monomer as a curable compound. Since the monofunctional monomer easily penetrates into the (meth) acrylic resin film, if the monofunctional monomer is included, the adhesion between the (meth) acrylic resin film and the hard coat layer is excellent, and interference unevenness is also achieved. Can be obtained.
- the content ratio of the monofunctional monomer is preferably 40% by weight or less with respect to the total curable compound in the hard coat layer forming composition, More preferably, it is 20% by weight or less. When the content ratio of the monofunctional monomer is more than 40% by weight, desired hardness and scratch resistance may not be obtained.
- the weight average molecular weight of the monofunctional monomer is preferably 500 or less. With such a monofunctional monomer, it easily penetrates and diffuses into the (meth) acrylic resin film.
- monofunctional monomers include ethoxylated o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, Isostearyl acrylate, cyclohexyl acrylate, isophoryl acrylate, benzyl acrylate, 2-hydroxy-3-phenoxy acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminopropylacrylamide, N- (2-hydroxyethyl) (meth) acrylamide and the like can be mentioned
- the monofunctional monomer preferably has a hydroxyl group.
- the heating temperature at the time of forming the hard coat layer can be set lower, the heating time can be set shorter, and an optical laminate in which deformation due to heating is suppressed can be efficiently produced. it can.
- the said composition for hard-coat layer formation contains the monofunctional monomer which has a hydroxyl group, the optical laminated body excellent in the adhesiveness of a (meth) acrylic-type resin film and a hard-coat layer can be obtained.
- Examples of such monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy acrylate, 1,4 -Hydroxyalkyl (meth) acrylates such as cyclohexane methanol monoacrylate; N- (2-hydroxyalkyl) (meth) acrylamides such as N- (2-hydroxyethyl) (meth) acrylamide, N-methylol (meth) acrylamide, etc. Can be mentioned. Of these, 4-hydroxybutyl acrylate and N- (2-hydroxyethyl) acrylamide are preferable.
- the boiling point of the monofunctional monomer is preferably higher than the heating temperature (described later) of the coating layer when forming the hard coat layer.
- the boiling point of the monofunctional monomer is, for example, preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher. If it is such a range, it can prevent that a monofunctional monomer volatilizes by the heating at the time of hard-coat layer formation, and a monofunctional monomer can fully osmose
- the hard coat layer forming composition includes inorganic nanoparticles. If a hard coat layer forming composition containing inorganic nanoparticles is applied to form a hard coat layer, the inorganic nanoparticles in the (meth) acrylic resin film eluted into the hard coat layer forming composition. It is possible to prevent components (typically, resin components in the (meth) acrylic resin film) from diffusing to the air interface of the hard coat layer when the hard coat layer is formed. As a result, an optical laminate having excellent scratch resistance can be obtained.
- components typically, resin components in the (meth) acrylic resin film
- the inorganic nanoparticles include metal oxide fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide (alumina), zinc oxide, tin oxide, and zirconium oxide (zirconia). These may be used alone or in combination. Among these, fine particles of silicon oxide (silica), aluminum oxide (alumina) or zirconium oxide (zirconia) are preferable, and silicon oxide (silica) is more preferable. This is because the curing shrinkage of the composition for forming a hard coat layer can be reduced and the hard coat layer can have a high hardness.
- metal oxide fine particles such as silicon oxide (silica), titanium oxide, aluminum oxide (alumina), zinc oxide, tin oxide, and zirconium oxide (zirconia). These may be used alone or in combination. Among these, fine particles of silicon oxide (silica), aluminum oxide (alumina) or zirconium oxide (zirconia) are preferable, and silicon oxide (silica) is more preferable. This is because the curing shrinkage of the composition for forming
- the inorganic nanoparticles are preferably coated with an organic compound on at least a part of the surface thereof.
- Inorganic nanoparticles with at least a part of the surface coated with an organic compound are excellent in dispersibility in the hard coat layer forming composition, so that the hard coat layer forming component of the (meth) acrylic resin film is used. Diffusion into the composition (as a result, diffusion into the hard coat layer) can be effectively prevented, and a hard coat layer with better scratch resistance can be obtained.
- the dispersibility is excellent, it is possible to prevent the light scattering and transmittance of the hard coat layer from decreasing and to obtain an optical laminate having excellent transparency.
- the inorganic nanoparticle is a metal oxide fine particle
- the organic compound reacts with a hydroxyl group present on the surface of the metal oxide fine particle.
- the organic compound that coats the inorganic nanoparticles preferably has a functional group that can chemically bond with a functional group present on the surface of the inorganic nanoparticle under dispersion conditions.
- functional groups include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, acrylamide group, carboxyl group, phosphate group, acid anhydride Group, acid chloride group, acid amide group, ester group, imino group, nitrile group, isonitrile group, hydroxyl group, thiol group, epoxy group, primary amino group, secondary amino group, tertiary amino group, Si -OH group, hydrolyzable residue of silane and the like.
- the functional group of the organic compound covering the inorganic nanoparticle can be bonded to the functional group present on the surface of the inorganic nanoparticle by a covalent bond, an ionic bond, a coordinate bond, or a hydrogen bond. More preferably, they can be bonded by a bond or a coordinate bond.
- covers the said inorganic nanoparticle may be used independently, and may be used in combination of multiple.
- the organic compound covering the inorganic nanoparticles preferably has a polymerizable unsaturated group.
- the hardness of the hard coat layer can be improved by the reaction of the polymerizable unsaturated group with the curable compound in the hard coat layer forming composition.
- the polymerizable unsaturated group for example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group are preferable.
- the polymerizable unsaturated group is also preferably a photosensitive group.
- organic compound that coats the inorganic nanoparticles examples include polysiloxanes such as polydimethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, and polymethylhydrogensiloxane; ⁇ -glycidyloxypropyltrimethoxysilane (GPTS), ⁇ -Glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- [N '-(2'-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxysilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimeth,
- the inorganic nanoparticles coated with the organic compound having a photosensitive group can be obtained, for example, by treating the inorganic nanoparticles with a silane coupling agent having a photosensitive group.
- a method for producing a silane coupling agent having a photosensitive group is described, for example, in JP-A-9-100111.
- the silane coupling agent having a photosensitive group include (i) an addition reaction between a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group, (ii) Reaction of a compound having an alkoxysilyl group and an isocyanate group in the molecule with an active hydrogen group-containing polymerizable unsaturated compound, (iii) a compound having a polymerizable unsaturated group and an isocyanate group in the molecule, mercaptoalkoxysilane, It can be obtained by the addition reaction of
- the shape of the inorganic nanoparticles may be a spherical shape, a rectangular parallelepiped shape, a needle shape, or a plate shape.
- the weight average particle diameter of the inorganic nanoparticles is preferably 100 nm or less, more preferably 1 nm to 50 nm, and more preferably 1 nm to 20 nm. If it is such a range, the light scattering of a hard-coat layer can be prevented, the fall of the transmittance
- the weight average particle diameter of the inorganic nanoparticles can be measured by, for example, a Coulter count method.
- the content of the inorganic nanoparticles is 1.5% by weight to 50% by weight with respect to the total of the curable compound and the inorganic nanoparticles in the hard coat layer forming composition. Within such a range, diffusion of components in the (meth) acrylic resin film into the hard coat layer forming composition (as a result, diffusion into the hard coat layer) can be effectively prevented, and scratch resistance is achieved. A hard coat layer having excellent properties can be obtained.
- the content of the inorganic nanoparticles is preferably 1.5% by weight to 30% by weight, more preferably 8%, based on the total of the curable compound and the inorganic nanoparticles in the hard coat layer forming composition. % By weight to 30% by weight, more preferably 20% by weight to 30% by weight. If it is such a range, since it can prevent that an inorganic nanoparticle forms what is called a particle layer, an optical laminated body with few interference nonuniformities can be obtained.
- the hard coat layer forming composition preferably contains any appropriate photopolymerization initiator.
- the photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethyl Ketals, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, thioxanthone compounds, etc. Can be mentioned.
- the surface of the hard coat layer opposite to the base material layer has an uneven structure. If the surface of the hard coat layer has a concavo-convex structure, antiglare properties can be imparted to the optical laminate.
- Examples of a method for forming such a concavo-convex structure include a method in which fine particles are contained in the hard coat layer forming composition.
- the fine particles may be inorganic fine particles or organic fine particles.
- Examples of the inorganic fine particles include silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, and calcium sulfate fine particles.
- organic fine particles examples include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, and polyester resin powder. , Polyamide resin powder, polyimide resin powder, polyfluorinated ethylene resin powder, and the like. These fine particles may be used alone or in combination.
- any appropriate shape can be adopted as the shape of the fine particles. It is preferably a substantially spherical shape, more preferably a substantially spherical shape having an aspect ratio of 1.5 or less.
- the weight average particle diameter of the fine particles is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 20 ⁇ m.
- the weight average particle diameter of the fine particles can be measured by, for example, a Coulter count method.
- the content ratio of the fine particles is preferably 1% by weight to 60% by weight with respect to the total curable compound in the hard coat layer forming composition. More preferably, it is 2 to 50% by weight.
- the hard coat layer forming composition may further contain any appropriate additive.
- additives include leveling agents, anti-blocking agents, dispersion stabilizers, thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, fillers, and lubricants. And antistatic agents.
- the leveling agent examples include a fluorine-based or silicone-based leveling agent, and a silicone-based leveling agent is preferable.
- the silicone leveling agent examples include reactive silicone, polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane. Of these, reactive silicone is preferable. If reactive silicone is added, the surface of the hard coat layer is provided with slipperiness and the scratch resistance is maintained for a long period of time.
- the content of the leveling agent is preferably 5% by weight or less, more preferably 0.01% by weight to 5% by weight with respect to the total amount of monomers, oligomers and prepolymers in the hard coat layer forming composition. %.
- the hard coat layer forming composition may or may not contain a solvent.
- the solvent include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone (MEK).
- a hard coat layer-forming composition containing no solvent, or a hard coat layer-forming composition containing only a poor solvent for the (meth) acrylic resin film-forming material as a solvent can be used.
- the forming composition can permeate the (meth) acrylic resin film to form a permeation layer having a desired thickness.
- the thickness of the hard coat layer is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 7 ⁇ m to 20 ⁇ m. If it is such a range, the optical laminated body which is excellent in abrasion resistance can be obtained. Moreover, since the optical laminated body of this invention suppresses the spreading
- any appropriate other layer may be disposed outside the hard coat layer as necessary.
- Typical examples include an antireflection layer and an antiglare layer.
- an antireflection layer and an antiglare layer usually used in the art can be adopted.
- the method for producing an optical laminate of the present invention comprises applying a composition for forming a hard coat layer on a (meth) acrylic resin film to form a coating layer, and heating the coating layer. including.
- the hard coat layer is formed by curing the coating layer after heating.
- Arbitrary appropriate methods can be employ
- examples thereof include a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, a fountain coating method, and a comma coating method.
- the heating temperature of the coating layer can be set to an appropriate temperature according to the composition of the hard coat layer forming composition, and preferably set to be equal to or lower than the glass transition temperature of the resin contained in the (meth) acrylic resin film. Is done. When heated at a temperature not higher than the glass transition temperature of the resin contained in the (meth) acrylic resin film, an optical layered body in which deformation due to heating is suppressed can be obtained.
- the heating temperature of the coating layer is, for example, 80 ° C. to 140 ° C. When heated at such a temperature, the monomer, oligomer and / or prepolymer in the composition for forming a hard coat layer penetrates and diffuses well into the (meth) acrylic resin film.
- the permeation layer described in the above section C is formed by the hard coat layer forming composition and the (meth) acrylic resin film forming material that has permeated through the heating and the subsequent curing treatment.
- the heating temperature of the said coating layer can be set so low that the compound contained in the composition for hard-coat layer formation is low molecular weight.
- the heating temperature of the coating layer can be set low by adding a monofunctional monomer to the hard coat layer forming composition (for example, 80 ° C. to 100 ° C.), and the content of the monofunctional monomer is large. It can be set as low as possible.
- coated composition for hard-coat layer formation can be dried by the said heating.
- the curing process is performed by ultraviolet irradiation.
- the integrated light quantity of ultraviolet irradiation is preferably 200 mJ to 400 mJ.
- the refractive index was measured using an Abbe refractometer (trade name: DR-M2 / 1550) manufactured by Atago Co., Ltd., selecting monobromonaphthalene as an intermediate solution.
- Reflection spectrum measurement conditions Reference: Mirror Algorithm: FFT method Calculation wavelength: 450 nm to 850 nm ⁇ Detection conditions Exposure time: 20 ms Lamp gain: Normal Integration count: 10 times / FFT method Film thickness range: 2 to 15 ⁇ m Film thickness resolution: 24nm Moreover, the thickness of the hard coat layer was evaluated by measuring the reflection spectrum of the laminate (R) below.
- Laminate (R) Implemented except that a PET base material (trade name: U48-3, refractive index: 1.60) manufactured by Toray Industries, Inc. was used as the base film, and the heating temperature of the coating layer was set to 60 ° C. Obtained in the same manner as in Example 6.
- the thickness of only the hard coat layer is measured from the peak position of the FFT spectrum obtained from the laminate (R). Is done. As a result of the evaluation, the thickness of the hard coat layer was 5.3 ⁇ m.
- a positive value calculated from (thickness of (hard coat layer + penetration layer)) ⁇ (thickness of (hard coat layer)) was taken as the thickness of the permeation layer.
- a negative value is calculated according to the definition formula, it can be determined that the permeation layer is not formed, and the negative value indicates that the base film forming material is eluted in the hard coat layer. It can be judged that it is the thickness of the layer formed.
- two FFT spectrum peaks are detected and two positive and negative values are calculated according to the definition formula, it can be determined that the positive value is the thickness of the permeation layer.
- the base film A thus obtained had a light transmittance of 8.5% at a wavelength of 380 nm, an in-plane retardation Re of 0.4 nm, and a thickness direction retardation Rth of 0.78 nm.
- the moisture permeability of the obtained base film A was 61 g / m 2 ⁇ 24 hr.
- the light transmittance was measured by measuring a transmittance spectrum in a wavelength range of 200 nm to 800 nm using a spectrophotometer (device name: U-4100) manufactured by Hitachi High-Tech Co., Ltd., and reading the transmittance at a wavelength of 380 nm.
- the phase difference value was measured at a wavelength of 590 nm and 23 ° C. using a trade name “KOBRA21-ADH” manufactured by Oji Scientific Instruments.
- the moisture permeability was measured by a method according to JIS K 0208 under conditions of a temperature of 40 ° C. and a relative humidity of 92%.
- ⁇ Production Example 2 Production of zirconia dispersion 100 parts of zirconia beads (manufactured by Tosoh Corporation), 10 parts of zirconia particles (manufactured by Daiichi Rare Element Co., Ltd., trade name: UEP-100), phosphate ester dispersant (Bic Chemie Japan) 5 parts of DISPERBYK-142) and 15 parts of methyl isobutyl ketone are mixed and dispersed for 3 hours with a disperser (trade name: Disperser DAS H200-K, manufactured by LAU) to give a zirconia dispersion (zirconia 33). %).
- UV curable resin manufactured by Dainippon Ink and Chemicals, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- organic-inorganic hybrid resin containing inorganic nanoparticles manufactured by JSR, Product name: Opstar Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone
- leveling agent manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content: 10%
- the organic-inorganic hybrid resin (OPSTAR Z7540) is made of (1-1) dipentaerythritol hexaacrylate, (1-2) isophorone diisocyanate polyurethane acrylate, and (2) an organic compound having a polymerizable unsaturated group.
- the curable compounds contained in the ultraviolet curable resin (Unidic 17-806) and their contents are as follows.
- Example 2 Instead of 5 parts of an organic-inorganic hybrid resin (trade name: Opster Z7540, manufactured by JSR), a dispersion containing 30% of alumina whose surface is coated with an organic compound (manufactured by BYK Japan, NANOBYK-3610, solid content: An optical laminate was obtained in the same manner as in Example 1 except that 10 parts of 37% by weight, solvent: propylene glycol monomethyl ether acetate) were used. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 3 An optical laminate was prepared in the same manner as in Example 1 except that 10 parts of the zirconia dispersion obtained in Production Example 2 was used instead of 5 parts of the organic-inorganic hybrid resin (manufactured by JSR, trade name: Opster Z7540). Obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 4 Organic-inorganic hybrid using dipentaerythritol hexaacrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) instead of ultraviolet curable resin (Dainippon Ink Chemical Co., Ltd., trade name: Unidic 17-806)
- An optical laminate was obtained in the same manner as in Example 1 except that the content of resin (JSR, trade name: Opster Z7540) was changed to 6 parts. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 5 Organic-inorganic hybrid using dipentaerythritol hexaacrylate (made by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH) instead of ultraviolet curable resin (Dainippon Ink Chemical Co., Ltd., trade name: Unidic 17-806)
- An optical laminate was obtained in the same manner as in Example 1 except that the content of resin (JSR, trade name: Opster Z7540) was changed to 125 parts. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 6 Instead of 100 parts of UV curable resin (Dainippon Ink & Chemicals, trade name: Unidic 17-806), 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate Example 1 except that a mixture (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV-7600B) was used and the content of organic / inorganic hybrid resin (manufactured by JSR, trade name: Opster Z7540) was changed to 6 parts. In the same manner, an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 7 Instead of 100 parts of UV curable resin (Dainippon Ink & Chemicals, trade name: Unidic 17-806), 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate Example 1 except that a mixture (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Shikou UV-7600B) was used, and the content of the organic-inorganic hybrid resin (manufactured by JSR, trade name: Opster Z7540) was changed to 125 parts. In the same manner, an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 8> Instead of 100 parts of UV curable resin (Dainippon Ink & Chemicals, trade name: Unidic 17-806), 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate Example 1 except that a mixture (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Shikou UV-7600B) was used and the content of organic-inorganic hybrid resin (manufactured by JSR, trade name: Opster Z7540) was changed to 750 parts. In the same manner, an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 9 Instead of 100 parts of UV curable resin (Dainippon Ink & Chemicals, trade name: Unidic 17-806), 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate Using a mixture (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Shikou UV-7600B), instead of 5 parts of organic-inorganic hybrid resin (trade name: Opster Z7540, manufactured by JSR Corporation), alumina whose surface is coated with an organic compound is used.
- UV curable resin Dainippon Ink & Chemicals, trade name: Unidic 17-806
- 60 parts of a hexafunctional urethane acrylic oligomer 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pen
- An optical laminate was obtained in the same manner as in Example 1, except that 10 parts of a dispersion containing 30% (NAKBYK-3610, manufactured by BYK Japan) was used. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- Example 10 Instead of 100 parts of UV curable resin (Dainippon Ink & Chemicals, trade name: Unidic 17-806), 60 parts of a hexafunctional urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate
- a zirconia dispersion 10 obtained in Production Example 2 was used instead of 5 parts of an organic-inorganic hybrid resin (manufactured by JSR Corporation, trade name: Opster Z7540) using a mixture (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV-7600B).
- An optical laminate was obtained in the same manner as in Example 1 except that the part was used. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by Dainippon Ink and Chemicals, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- 4-HBA 4-hydroxybutyl acrylate
- organic-inorganic hybrid resin containing inorganic nanoparticles manufactured by JSR, trade name: OPSTAR Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone
- leveling agent Dainippon Ink Chemical Co., Ltd.
- GRANDIC PC-4100 solid content: 10%
- Example 13 70 parts of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: A-DPH), 30 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), organic inorganic including inorganic nanoparticles Hybrid resin (manufactured by JSR, trade name: OPSTAR Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone) 125 parts, leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content) : 10%) 5 parts, 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) are mixed and diluted with methyl isobutyl ketone so that the solid content concentration is 50%.
- 4-HBA
- Example 2 Similar to Example 1 except that the adjusted composition for forming a hard coat layer was used and the heating temperature of the coating layer was 90 ° C. Thus, an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown in Table 2 below.
- Example 14 80 parts of “Nippon Gosei UV-7600B” manufactured by Nippon Synthetic Chemical Co., Ltd. 20 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), organic-inorganic hybrid resin containing inorganic nanoparticles (manufactured by JSR, Product name: OPSTAR Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone) 6 parts, leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content: 10%),
- For hard coat layer formation prepared by mixing 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) and diluting with methyl isobutyl ketone so that the solids concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the composition
- Example 15 70 parts of "Nippon Gosei UV-7600B” manufactured by Nippon Synthetic Chemical Co., Ltd., 30 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), organic-inorganic hybrid resin containing inorganic nanoparticles (manufactured by JSR, Product name: Opstar Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone) 125 parts, leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content: 10%),
- For hard coat layer formation prepared by mixing 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) and diluting with methyl isobutyl ketone so that the solids concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the
- Example 16 60 parts of "Nippon Gosei UV-7600B” manufactured by Nippon Synthetic Chemical Co., Ltd., 40 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), organic-inorganic hybrid resin containing inorganic nanoparticles (manufactured by JSR, Product name: Opstar Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone) 125 parts, leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content: 10%),
- For hard coat layer formation prepared by mixing 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) and diluting with methyl isobutyl ketone so that the solids concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the
- Example 17 80 parts of “Nippon Synthetic Chemical Co., Ltd.” “purple UV-7600B”, 20 parts of N- (2-hydroxyethyl) acrylamide (HEAA) (manufactured by Kojin Co., Ltd.), organic-inorganic hybrid resin containing inorganic nanoparticles (manufactured by JSR, Product name: Opstar Z7540, solid content: 56%, solvent: butyl acetate / methyl ethyl ketone) 125 parts, leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid content: 10%),
- For hard coat layer formation prepared by mixing 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) and diluting with methyl isobutyl ketone so that the solids concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the composition was used and the heating
- Example 18 Dispersion containing 30 parts of “Shikko UV-7600B” manufactured by Nippon Synthetic Chemical Co., Ltd., 30 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 30% alumina whose surface is coated with an organic compound Liquid (by Big Chemie Japan, NANOBYK-3610, solid content: 37% by weight, solvent: propylene glycol monomethyl ether acetate), leveling agent (manufactured by Dainippon Ink & Chemicals, trade name: GRANDIC PC-4100, solid) (Minute: 10%) 5 parts, 3 parts of photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907) are mixed and diluted with methyl isobutyl ketone so that the solid content concentration is 50%.
- 4-HBA 4-hydroxybutyl acrylate
- alumina whose surface is coated with an organic compound Liquid
- Example 19 70 parts of “Nippon Gosei UV-7600B” manufactured by Nippon Synthetic Chemical Co., Ltd., 30 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 10 parts of the zirconia dispersion obtained in Production Example 2, leveling 5 parts of an additive (Dainippon Ink Chemical Co., Ltd., trade name: GRANDIC PC-4100, solid content: 10%) and 3 parts of a photopolymerization initiator (Ciba Specialty Chemicals, trade name: Irgacure 907)
- the composition for forming a hard coat layer prepared by diluting with methyl isobutyl ketone so as to have a solid content concentration of 50% was used, and the heating temperature of the coating layer was set to 90 ° C.
- an optical laminate was obtained. This optical laminate was subjected to the evaluations (1) to (5) above. The results are shown
- the optical layered body of the present invention has a permeation layer having a predetermined thickness, thereby improving the adhesion between the base film ((meth) acrylic resin film) and the hard coat layer. Excellent.
- the optical layered body of the present invention has a hard coat layer formed of a composition for forming a hard coat layer containing a specific amount of inorganic nanoparticles. Excellent in properties. Further, if the content ratio of the inorganic nanoparticles in the composition for forming a hard coat layer is further adjusted and an infiltration layer having a predetermined thickness is formed, in addition to excellent adhesion and scratch resistance, interference unevenness Can be obtained (Examples 1 to 7, 9 to 19).
- the optical layered body of the present invention can be suitably used for an image display device.
- the optical layered body of the present invention can be suitably used as a front plate of an image display device or a protective material for a polarizer, and particularly suitably used as a front plate of a liquid crystal display device (in particular, a three-dimensional liquid crystal display device). obtain.
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Abstract
Description
好ましい実施形態においては、上記無機ナノ粒子の表面の少なくとも一部が有機化合物で被覆されている。
好ましい実施形態においては、上記有機化合物が、重合性不飽和基を有する有機化合物である。
好ましい実施形態においては、上記無機ナノ粒子の含有割合が、上記硬化性化合物および上記無機ナノ粒子の合計に対して1.5重量%~30重量%である。
好ましい実施形態においては、上記ハードコート層形成用組成物が、5個以上の(メタ)アクリロイル基を有する硬化性化合物を含み、該5個以上の(メタ)アクリロイル基を有する硬化性化合物の含有割合が、該ハードコート層形成用組成物中の全硬化性化合物に対して、15重量%~100重量%である。
好ましい実施形態においては、上記ハードコート層形成用組成物が、2~4個の(メタ)アクリロイル基を有する硬化性化合物を含み、該2~4個の(メタ)アクリロイル基を有する硬化性化合物の含有割合が、該ハードコート層形成用組成物中の全硬化性化合物に対して、85重量%以下である。
好ましい実施形態においては、上記ハードコート層組成物が単官能モノマーをさらに含み、該単官能モノマーの含有割合が、ハードコート層形成用組成物中の全硬化性化合物に対して、40重量%以下である。
好ましい実施形態においては、上記単官能モノマーの重量平均分子量が、500以下である。
好ましい実施形態においては、上記単官能モノマーが、水酸基を有する。
好ましい実施形態においては、上記単官能モノマーが、ヒドロキシアルキル(メタ)アクリレートおよび/またはN-(2-ヒドロキシアルキル)(メタ)アクリルアミドである。
好ましい実施形態においては、上記(メタ)アクリル系樹脂フィルムの波長380nmにおける光の透過率が、15%以下である。
好ましい実施形態においては、上記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂が、正の複屈折を発現する構造単位と負の複屈折を発現する構造単位とを有する。
好ましい実施形態においては、上記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂の重量平均分子量が、10000~500000である。
好ましい実施形態においては、上記ハードコート層および上記浸透層において、上記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂の濃度が、該浸透層の上記基材層側から該ハードコート層の上記基材層とは反対側へ、連続的に低くなる。
好ましい実施形態においては、上記ハードコート層の上記浸透層とは反対側の表面が、凹凸構造を有する。
好ましい実施形態においては、本発明の光学積層体は、上記ハードコート層の上記浸透層とは反対側に、反射防止層をさらに備える。
本発明の別の局面によれば、偏光板が提供される。この偏光板は上記光学積層体を含む。
本発明のさらに別の局面によれば、画像表示装置が提供される。この画像表示装置は上記光学積層体を含む。
A.光学積層体の全体構成
図1(a)は、本発明の好ましい実施形態による光学積層体の概略断面図であり、図1(b)は、従来の一般的なハードコート層を有する光学積層体の概略断面図である。図1(a)に示す光学積層体100は、(メタ)アクリル系樹脂フィルムから形成される基材層10と、浸透層20と、ハードコート層30とをこの順に備える。ハードコート層30は、(メタ)アクリル系樹脂フィルムに硬化性化合物を含むハードコート層形成用組成物を塗工して形成される。浸透層20は、ハードコート層形成用組成物が(メタ)アクリル系樹脂フィルムに浸透して形成される。基材層10は、このようにハードコート層形成用組成物が(メタ)アクリル系樹脂フィルムに浸透した際に、(メタ)アクリル系樹脂フィルムにおいてハードコート層形成用組成物が到達(浸透)しなかった部分である。一方、図1(b)に示す光学積層体200は、浸透層が形成されていない。図1(a)および(b)に示す境界Aは、(メタ)アクリル系樹脂フィルムのハードコート層形成用組成物塗工面により規定される境界である。したがって、境界Aは、光学積層体100においては浸透層20とハードコート層30との境界であり、浸透層が形成されていない光学積層体200においては基材層10’(すなわち、(メタ)アクリル系樹脂フィルム)とハードコート層30’との境界である。なお、本明細書において、「(メタ)アクリル」とはアクリルおよび/またはメタクリルを意味する。
上記基材層は、(メタ)アクリル系樹脂フィルムから形成される。より詳細には、上記のように、基材層は、(メタ)アクリル系樹脂フィルムにハードコート層形成用組成物を塗工した際に、(メタ)アクリル系樹脂フィルムにおいて、当該ハードコート層形成用組成物が到達(浸透)しなかった部分である。
Re=(nx-ny)×d
Rth=(nx-nz)×d
ここで、nxは(メタ)アクリル系樹脂フィルムの遅相軸方向の屈折率であり、nyは(メタ)アクリル系樹脂フィルムの進相軸方向の屈折率であり、nzは(メタ)アクリル系樹脂フィルムの厚み方向の屈折率であり、d(nm)は(メタ)アクリル系樹脂フィルムの厚みである。遅相軸は、フィルム面内の屈折率が最大になる方向をいい、進相軸は、面内で遅相軸に垂直な方向をいう。代表的には、ReおよびRthは、波長590nmの光を用いて測定される。
式(1)において、R1およびR2は、それぞれ独立して、水素または炭素数1~8のアルキル基であり、R3は、水素、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、または炭素数5~15の芳香環を含む置換基である。式(2)において、R4およびR5は、それぞれ独立して、水素または炭素数1~8のアルキル基であり、R6は、水素、炭素数1~18のアルキル基、炭素数3~12のシクロアルキル基、または炭素数5~15の芳香環を含む置換基である。
式(3)において、R7は、水素または炭素数1~8のアルキル基であり、R8は、炭素数6~10のアリール基である。
上記浸透層は、上記のとおり、(メタ)アクリル系樹脂フィルムにハードコート層形成用組成物が浸透することにより形成される。言い換えれば、浸透層は(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂とハードコート層を形成する化合物との相溶化領域の一部に対応し得る。
ハードコート層は、上記のとおり、上記(メタ)アクリル系樹脂フィルム上にハードコート層形成用組成物を塗工して形成される。ハードコート層形成用組成物は、硬化性化合物および無機ナノ粒子を含む。上記硬化性化合物は、例えば、熱、光(紫外線等)または電子線等により硬化し得る。好ましくは、上記硬化性化合物は、光硬化型である。硬化性化合物は、モノマー、オリゴマーおよびプレポリマーのいずれであってもよい。なお、上記無機ナノ粒子は、後述のように、有機化合物(代表的には重合性不飽和基を有する有機化合物)で被覆され得るが、本明細書においては、このような無機ナノ粒子であっても、当該無機ナノ粒子を「硬化性化合物」に含まない。
本発明の光学積層体は、必要に応じて、ハードコート層の外側に任意の適切なその他の層が配置され得る。代表例としては、反射防止層およびアンチグレア層が挙げられる。反射防止層およびアンチグレア層としては、当業界で通常用いられている反射防止層およびアンチグレア層が採用され得る。
本発明の光学積層体の製造方法は、(メタ)アクリル系樹脂フィルム上にハードコート層形成用組成物を塗布して塗布層を形成し、該塗布層を加熱することを含む。好ましくは、ハードコート層は、加熱後の塗布層を硬化処理して形成される。
実施例および比較例で得られた光学積層体を幅11mm、長さ100mmの大きさに切断し、基材層を下にしてガラス板に載せた。次いで、当該光学積層体のハードコート層側表面上で、直径11mmの円柱の断面に取り付けたスチールウール#0000を、荷重400g、100mm/secで10往復させた。その後のハードコート層側表面を目視観察し、以下の基準で評価した。
また、荷重を600gとした以外は、上記と同様の評価を行った。
4:傷が全くない
3:わずかに傷がつく
2:細かい傷が残る
1:傷が著しい
(2)鉛筆硬度
実施例および比較例で得られた光学積層体のハードコート層側表面について、JIS K 5400に準じて(荷重500g)、鉛筆硬度を評価した。
(3)ハードコート層の密着性
ハードコート層の基材フィルムに対する密着性を、JIS K-5400の碁盤目剥離試験(基板目数:100個)に準じて評価した。
(4)干渉ムラ
実施例および比較例で得られた光学積層体の基材フィルム側に、黒色アクリル板(三菱レイヨン社製、厚み2mm)をアクリル系粘着剤を介して貼着した後、3波長蛍光灯下で、干渉ムラを目視観察し、以下の基準で評価した。
4:干渉ムラの発生無し
3:少し干渉ムラの発生が認められるが、実用上の問題はない
2:多くの干渉ムラの発生が認められる
1:顕著な干渉ムラの発生が認められる
(5)浸透層の厚み
実施例および比較例で得られた光学積層体の基材層側に、黒色アクリル板(三菱レイヨン社製、厚み2mm)を、厚み20μmのアクリル系粘着剤を介して貼着した。次いで、ハードコート層の反射スペクトルを、瞬間マルチ測光システム(大塚電子社製、商品名:MCPD3700)を用いて以下の条件で測定し、FFTスペクトルのピーク位置から、(ハードコート層+浸透層)の厚みを評価した。なお屈折率は、アタゴ社製のアッベ屈折率計(商品名:DR-M2/1550)を用い、中間液としてモノブロモナフタレンを選択して測定した。
・反射スペクトル測定条件
リファレンス:ミラー
アルゴリズム:FFT法
計算波長:450nm~850nm
・検出条件
露光時間:20ms
ランプゲイン:ノーマル
積算回数:10回
・FFT法
膜厚値の範囲:2μm~15μm
膜厚分解能:24nm
また、ハードコート層の厚みは、下記積層体(R)についての上記反射スペクトル測定により評価した。
・積層体(R):基材フィルムとしてPET基材(東レ社製、商品名:U48-3、屈折率:1.60)を用い、塗布層の加熱温度を60℃とした以外は、実施例6と同様にして得た。
なお、これらの積層体に用いられるPET基材には、ハードコート層形成用組成物が浸透しないので、積層体(R)から得られるFFTスペクトルのピーク位置から、ハードコート層のみの厚みが測定される。当該評価の結果、ハードコート層の厚みは5.3μmであった。
((ハードコート層+浸透層)の厚み)-((ハードコート層)の厚み)から算出される正の値を浸透層の厚みとした。なお、当該定義式により負の値のみが算出される場合、浸透層は形成されていないと判断することができるとともに、当該負の値は基材フィルム形成材料がハードコート層中に溶出して形成される層の厚みであると判断することができる。また、FFTスペクトルのピークが2本検出されて、当該定義式により、正負2つの値が算出される場合、正の値が浸透層の厚みであると判断できる。
特開2010-284840号公報の製造例1に記載のイミド化MS樹脂100重量部およびトリアジン系紫外線吸収剤(アデカ社製、商品名:T-712)0.62重量部を、2軸混練機にて220℃にて混合し、樹脂ペレットを作製した。得られた樹脂ペレットを、100.5kPa、100℃で12時間乾燥させ、単軸の押出機にてダイス温度270℃でTダイから押出してフィルム状に成形した(厚み160μm)。さらに当該フィルムを、その搬送方向に150℃の雰囲気下に延伸し(厚み80μm)、次いでフィルム搬送方向と直交する方向に150℃の雰囲気下に延伸して、厚み40μmの基材フィルムA((メタ)アクリル系樹脂フィルム)を得た。得られた基材フィルムAの波長380nmの光の透過率は8.5%、面内位相差Reは0.4nm、厚み方向位相差Rthは0.78nmであった。また得られた基材フィルムAの透湿度は、61g/m2・24hrであった。なお、光透過率は、日立ハイテク(株)製の分光光度計(装置名称;U-4100)を用いて波長範囲200nm~800nmで透過率スペクトルを測定し、波長380nmにおける透過率を読み取った。また、位相差値は、王子計測機器(株)製 商品名「KOBRA21-ADH」を用いて、波長590nm、23℃で測定した。透湿度は、JIS K 0208に準じた方法により、温度40℃、相対湿度92%の条件で測定した。
ジルコニアビーズ(東ソー社製)100部、ジルコニア粒子(第一稀元素社製、商品名:UEP-100)10部、リン酸エステル分散剤(ビックケミー・ジャパン社製、DISPERBYK-142)5部、およびメチルイソブチルケトン15部を混合し、分散機(LAU社製、商品名:Disperser DAS H200-K)で3時間分散処理することにより、ジルコニア分散液(ジルコニア33%)を得た。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806、固形分:80%、溶媒:酢酸ブチル)100部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)5部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して、ハードコート層形成用組成物を調製した。なお、上記有機無機ハイブリッド樹脂(オプスターZ7540)は、(1-1)ジペンタエリスリトールヘキサアクリレート、(1-2)イソホロンジイソシアネート系ポリウレタンアクリレート、および(2)重合性不飽和基を有する有機化合物で表面が被覆されたシリカ微粒子(重量平均粒径100nm以下)を、重量比(1-1):(1-2):(2)=66:34:150で含有する。また、上記紫外線硬化型樹脂(ユニディック17-806)に含まれる硬化性化合物およびその含有量は以下のとおりである。
イソシアヌル酸トリアクリレート13部
ペンタエリスリトールトリアクリレート16部
ジペンタエリスリトールヘキサアクリレート62部
イソホロンジイソシアネート系ポリウレタンアクリレート9部
製造例1で得られた基材フィルムA上に、得られたハードコート層形成用組成物を塗布して塗布層を形成し、当該塗布層を110℃で1分間加熱した。加熱後の塗布層に高圧水銀ランプにて積算光量300mJ/cm2の紫外線を照射して塗布層を硬化させて、基材層、ハードコート層および浸透層を形成し、光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)5部に代えて、有機化合物で表面が被覆されたアルミナを30%含む分散液(ビックケミー・ジャパン社製、NANOBYK-3610、固形分:37重量%、溶媒:プロピレングリコールモノメチルエーテルアセテート)10部を用いた以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)5部に代えて、製造例2で得られたジルコニア分散液10部を用いた以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えてジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を6部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えてジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を125部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を6部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を125部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を750部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)5部に代えて、有機化合物で表面が被覆されたアルミナを30%含む分散液(ビックケミー・ジャパン社製、NANOBYK-3610)10部を用いた以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)5部に代えて製造例2で得られたジルコニア分散液10部を用いた以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えてペンタエリスリトールトリアクリレート(大阪有機化学工業社製、商品名:ビスコート#300)とジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)との混合物(重量混合比ビスコート#300:A-DPH=8:2)100部を用い、有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を36部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表1に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806、固形分:80%、溶媒:酢酸ブチル)100部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)20部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)125部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
ジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)70部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)30部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)125部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」80部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)20部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)6部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」70部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)30部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)125部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」60部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)40部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)125部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」80部、N-(2-ヒドロキシエチル)アクリルアミド(HEAA)(興人社製)20部、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)125部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」70部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)30部、有機化合物で表面が被覆されたアルミナを30%含む分散液(ビックケミー・ジャパン社製、NANOBYK-3610、固形分:37重量%、溶媒:プロピレングリコールモノメチルエーテルアセテート)10部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
上記日本合成化学社製「紫光UV-7600B」70部、4-ヒドロキシブチルアクリレート(4-HBA)(大阪有機化学工業社製)30部、製造例2で得られたジルコニア分散液10部、レベリング剤(大日本インキ化学工業社製、商品名:GRANDIC PC-4100、固形分:10%)5部、光重合開始剤(チバ・スペシャリティ・ケミカルズ社製、商品名:イルガキュア907)3部を混合し、固形分濃度が50%となるように、メチルイソブチルケトンで希釈して調整したハードコート層形成用組成物を用い、塗布層の加熱温度を90℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表2に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えてペンタエリスリトールトリアクリレート(大阪有機化学工業社製、商品名:ビスコート#300)を用い、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)を添加しなかった以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えてジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)を用い、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)を添加しなかった以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)を添加しなかった以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)を添加しなかった以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えてジペンタエリスリトールヘキサアクリレート(新中村化学社製、商品名:A-DPH)を用い、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を2000部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)に代えて6官能ウレタンアクリレートオリゴマー(日本合成化学社製、商品名:紫光UV-7600B)を用い、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540)の含有量5部を2000部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)を用いず、無機ナノ粒子を含む有機無機ハイブリッド樹脂(JSR社製、商品名:オプスターZ7540、固形分:56%、溶媒:酢酸ブチル/メチルエチルケトン)の含有量5部を100部とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
紫外線硬化型樹脂(大日本インキ化学工業社製、商品名:ユニディック17-806)100部に代えて、6官能ウレタンアクリルオリゴマー60部、ペンタエリスリトールテトラアクリレート30部およびペンタエリスリトールトリアクリレート10部の混合物(日本合成化学社製、商品名:紫光UV-7600B)を用い、塗布層加熱温度を80℃とした以外は、実施例1と同様にして光学積層体を得た。この光学積層体を上記(1)~(5)の評価に供した。結果を下記表3に示す。
10 基材層
20 浸透層
30 ハードコート層
100、200 光学積層体
Claims (18)
- (メタ)アクリル系樹脂フィルムから形成された基材層と、
該(メタ)アクリル系樹脂フィルムに、硬化性化合物および無機ナノ粒子を含むハードコート層形成用組成物を、塗工して形成されたハードコート層と、
該基材層と該ハードコート層との間に、該ハードコート層形成用組成物が該(メタ)アクリル系樹脂フィルムに浸透して形成された、厚みが1.2μm以上の浸透層とを備え、
該無機ナノ粒子の含有割合が、該硬化性化合物および該無機ナノ粒子の合計に対して、1.5重量%~50重量%である、
光学積層体。 - 前記無機ナノ粒子の表面の少なくとも一部が有機化合物で被覆されている、請求項1に記載の光学積層体。
- 前記有機化合物が、重合性不飽和基を有する有機化合物である、請求項2に記載の光学積層体。
- 前記無機ナノ粒子の含有割合が前記硬化性化合物および前記無機ナノ粒子の合計に対して、1.5重量%~30重量%である、請求項1から3のいずれかに記載の光学積層体。
- 前記ハードコート層形成用組成物が、5個以上の(メタ)アクリロイル基を有する硬化性化合物を含み、該5個以上の(メタ)アクリロイル基を有する硬化性化合物の含有割合が、該ハードコート層形成用組成物中の全硬化性化合物に対して、15重量%~100重量%である、請求項1から4のいずれかに記載の光学積層体。
- 前記ハードコート層形成用組成物が、2~4個の(メタ)アクリロイル基を有する硬化性化合物を含み、該2~4個の(メタ)アクリロイル基を有する硬化性化合物の含有割合が、該ハードコート層形成用組成物中の全硬化性化合物に対して、85重量%以下である、請求項1から5のいずれかに記載の光学積層体。
- 前記ハードコート層組成物が単官能モノマーをさらに含み、該単官能モノマーの含有割合が、ハードコート層形成用組成物中の全硬化性化合物に対して、40重量%以下である、請求項5または6に記載の光学積層体。
- 前記単官能モノマーの重量平均分子量が、500以下である、請求項7に記載の光学積層体。
- 前記単官能モノマーが、水酸基を有する、請求項7または8に記載の光学積層体。
- 前記単官能モノマーが、ヒドロキシアルキル(メタ)アクリレートおよび/またはN-(2-ヒドロキシアルキル)(メタ)アクリルアミドである、請求項9に記載の光学積層体。
- 前記(メタ)アクリル系樹脂フィルムの波長380nmにおける光の透過率が、15%以下である、請求項1から10のいずれかに記載の光学積層体。
- 前記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂が、正の複屈折を発現する構造単位と負の複屈折を発現する構造単位とを有する、請求項1から11のいずれかに記載の光学積層体。
- 前記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂の重量平均分子量が、10000~500000である、請求項1から12のいずれかに記載の光学積層体。
- 前記ハードコート層および前記浸透層において、前記(メタ)アクリル系樹脂フィルムを形成する(メタ)アクリル系樹脂の濃度が、該浸透層の前記基材層側から該ハードコート層の前記基材層とは反対側へ、連続的に低くなる、請求項1から13のいずれかに記載の光学積層体。
- 前記ハードコート層の前記浸透層とは反対側の表面が、凹凸構造を有する、請求項1から14のいずれかに記載の光学積層体。
- 前記ハードコート層の前記浸透層とは反対側に、反射防止層をさらに備える、請求項1から15のいずれかに記載の光学積層体。
- 請求項1から16のいずれかに記載の光学積層体を含む、偏光フィルム。
- 請求項1から16のいずれかに記載の光学積層体を含む、画像表示装置。
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CN109192879A (zh) * | 2018-08-31 | 2019-01-11 | 京东方科技集团股份有限公司 | 柔性显示用盖板及其制备方法和柔性显示装置 |
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Also Published As
Publication number | Publication date |
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KR20180112074A (ko) | 2018-10-11 |
CN103492912B (zh) | 2016-08-17 |
US10139525B2 (en) | 2018-11-27 |
JP2012234164A (ja) | 2012-11-29 |
KR20140037091A (ko) | 2014-03-26 |
US20140247486A1 (en) | 2014-09-04 |
TW201247753A (en) | 2012-12-01 |
TWI550001B (zh) | 2016-09-21 |
KR102120575B1 (ko) | 2020-06-08 |
CN103492912A (zh) | 2014-01-01 |
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