WO2012144508A1 - 光学積層体 - Google Patents
光学積層体 Download PDFInfo
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- WO2012144508A1 WO2012144508A1 PCT/JP2012/060420 JP2012060420W WO2012144508A1 WO 2012144508 A1 WO2012144508 A1 WO 2012144508A1 JP 2012060420 W JP2012060420 W JP 2012060420W WO 2012144508 A1 WO2012144508 A1 WO 2012144508A1
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- coat layer
- hard coat
- optical laminate
- 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
- G02B1/04—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
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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.
- the base film of the optical laminate typically, triacetyl cellulose (TAC) is used.
- 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 Document 1 an optical laminate in which a composition for forming a hard coat layer is applied to a low moisture permeability cycloolefin base film has been proposed.
- a cycloolefin base film has a problem of poor adhesion to the hard coat layer.
- interference unevenness occurs due to a difference in refractive index between the base film and the hard coat layer.
- the above-mentioned cycloolefin base film does not have a sufficient ultraviolet absorbing ability, and an optical laminate using these base films has a problem that the optical properties are deteriorated by external light or the like.
- an optical laminate having a small interference unevenness satisfying sufficient adhesion between the substrate film and the hard coat layer It has not been put into practical use yet.
- the present invention has been made in order to solve the above-described conventional problems.
- the object of the present invention is to provide a (meth) acrylic resin film (base film) having a low moisture permeability and an ultraviolet absorbing ability and a hard film.
- An object of the present invention is to provide an optical laminate having excellent adhesion to a coat layer and suppressing interference unevenness.
- the optical layered body of the present invention includes a base layer formed from a (meth) acrylic resin film, and a hard coat layer formed by applying a hard coat layer forming composition to the (meth) acrylic resin film. And a permeation layer formed by permeating the (meth) acrylic resin film between the base material layer and the hard coat layer.
- the thickness is 1.2 ⁇ m or more.
- permeation layer becomes high continuously from the hard-coat layer side to the base material layer side.
- the amplitude of the reflection spectrum of the hard coat layer in the wavelength region of 500 nm to 600 nm is 0.5% or less.
- the absolute value of the difference between the refractive index of the substrate layer and the refractive index of the hard coat layer is 0.01 to 0.15.
- 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 an aromatic ring in the side chain.
- the composition for forming a hard coat layer contains a curable compound having two or more (meth) acryloyl groups.
- the hard coat layer forming composition further contains a monofunctional monomer.
- 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.
- the said composition for hard-coat layer formation contains the oligomer of urethane (meth) acrylate and / or urethane (meth) acrylate.
- the composition for forming a hard coat layer includes a (meth) acrylic prepolymer having a hydroxyl group.
- the composition for forming a hard coat layer does not contain a solvent.
- 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 film is provided.
- This polarizing film includes the optical laminate.
- an image display device is provided.
- This image display device includes the optical laminate.
- the manufacturing method of an optical laminated body is provided. The method for producing this optical laminate comprises applying a composition for forming a hard coat layer on the (meth) acrylic resin film to form a coating layer, and heating the coating layer at 80 ° C. to 140 ° C. Including.
- a composition for forming a hard coat layer on a (meth) acrylic resin film (base film) and a (meth) acrylic resin
- the base film and the hard coat layer can be used while using a low-moisture permeable (meth) acrylic resin film as the base film.
- An optical laminate that is excellent in adhesiveness and has reduced interference unevenness is provided.
- the optical layered body of the present invention is a (meth) acrylic resin film (base film) without providing an anchor layer and without physically treating the (meth) acrylic resin film (base film).
- a hard-coat layer can be formed with the outstanding adhesiveness also with respect to the (meth) acrylic-type resin film (base film) which has an ultraviolet absorptivity in addition to low moisture permeability.
- (A) is a schematic sectional drawing of the optical laminated body by preferable embodiment of this invention
- (b) is an example of the schematic sectional drawing of the optical laminated body which has the conventional general hard-coat layer.
- It is a schematic sectional drawing of the optical laminated body by another embodiment of this invention.
- It is a fast Fourier transform (FFT) spectrum of the hard-coat layer surface of the laminated body (R1) used for evaluation of an Example.
- 2 is a reflection spectrum of a hard coat layer surface of the optical layered body of Example 1.
- FIG. 2 is an FFT spectrum of a hard coat layer surface of the optical layered body of Example 1.
- 10 is a reflection spectrum of the surface of a hard coat layer of the optical layered body of Comparative Example 3.
- 4 is an FFT spectrum of the hard coat layer surface of the optical layered body of Comparative Example 3.
- 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 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.
- 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. Therefore, 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).
- 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. .
- FIG. 2 is a schematic cross-sectional view of an optical laminate according to another embodiment of the present invention.
- the optical layered body 300 further includes a block layer 40 on the opposite side of the hard coat layer 30 from the osmotic layer 20.
- the (meth) acrylic resin forming the (meth) acrylic resin film elutes in the hardcoat layer forming composition, and the hardcoat layer forming composition is the (meth) acrylic resin. And by causing phase separation.
- the optical laminate including the block layer 40 is excellent in scratch resistance.
- 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 0.5% or less, more preferably 0.3% or less, and still more preferably 0.8. 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. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
- the weight average molecular weight of the (meth) acrylic resin is preferably 10,000 to 500,000. If the weight average molecular weight is too small, the mechanical strength when formed into a film tends to be insufficient. When the weight average molecular weight is too large, the viscosity at the time of melt extrusion is high, the molding processability is lowered, and the productivity of the molded product tends to be lowered.
- 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 excellent in heat resistance 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 to 350 ° C, more preferably 200 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 component 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 2.5 ⁇ 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.
- permeation layer can be measured by observation with electron microscopes, such as a reflection spectrum of a hard-coat layer, or SEM and TEM. Details of the method for measuring the thickness of the osmotic layer based on the reflection spectrum 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, for example, a curable compound that can be cured by heat, light (such as ultraviolet rays), or an electron beam.
- the composition for forming a hard coat layer contains a photocurable curable compound.
- the curable compound may be any of a monomer, an oligomer and a prepolymer.
- the hard coat layer forming composition preferably contains a curable compound having two or more (meth) acryloyl groups.
- the upper limit of the number of (meth) acryloyl groups contained in the curable compound having two or more (meth) acryloyl groups is preferably 100. Since the curable compound having two or more (meth) acryloyl groups is excellent in compatibility with the (meth) acrylic resin, it easily penetrates and diffuses into the (meth) acrylic resin film during coating.
- “(meth) acryloyl” means methacryloyl and / or acryloyl.
- curable compound having two or more (meth) acryloyl groups examples include tricyclodecane dimethanol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane triacrylate, Pentaerythritol tetra (meth) acrylate, dimethylolpropanthate tetraacrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipropylene glycol diacrylate, isocyanuric acid Examples include li (meth) acrylate, ethoxylated gly,
- the curable compound having two or more (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.
- the curable compound having a hydroxyl group and two or more (meth) acryloyl groups include pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate.
- the content of the curable compound having two or more (meth) acryloyl groups is preferably 30% by weight to 100% by weight with respect to the total amount of the monomer, oligomer and prepolymer in the hard coat layer forming composition. %, More preferably 40% by weight to 95% by weight, and particularly preferably 50% by weight to 95% by weight. If it is such a range, 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. In addition, curing shrinkage of the hard coat layer can be effectively prevented.
- 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. Further, if the hard coat layer-forming composition contains a monofunctional monomer, the heating temperature at the time of forming the hard coat layer can be set low, the heating time can be set short, and the optical laminate in which deformation due to heating is suppressed. Can be produced efficiently.
- 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 30 weight% or less, Most preferably, it is 20 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 composition for forming a hard coat layer preferably contains urethane (meth) acrylate and / or urethane (meth) acrylate oligomer as the curable compound. 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 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 total content of the urethane (meth) acrylate and the urethane (meth) acrylate oligomer is preferably 5% by weight to 70% by weight based on the total amount of the monomer, oligomer and prepolymer in the composition for forming a hard coat layer. %, More preferably 5 to 50% by weight, particularly preferably 5 to 30% by weight. If it is such a range, the hard-coat layer excellent in the balance of hardness, a softness
- the hard coat layer forming composition may contain a (meth) acrylic prepolymer having a hydroxyl group. If the hard coat layer-forming composition contains a (meth) acrylic prepolymer having a hydroxyl group, curing shrinkage can be reduced, and a block layer is formed in the hard coat layer, resulting in scratch resistance. Can be formed. Moreover, when the (meth) acrylic prepolymer has a hydroxyl group, an optical laminate having excellent adhesion between the (meth) acrylic resin film and the hard coat layer can be obtained.
- the (meth) acrylic prepolymer having a hydroxyl group is preferably a polymer polymerized from a hydroxyalkyl (meth) acrylate having a linear or branched alkyl group having 1 to 10 carbon atoms.
- Examples of the (meth) acrylic prepolymer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2 -Polymers polymerized from at least one monomer selected from the group consisting of acryloyloxy-3-hydroxypropyl (meth) acrylate.
- the (meth) acrylic prepolymer having a hydroxyl group may be used alone or in combination.
- the content ratio of the (meth) acrylic prepolymer having a hydroxyl group is preferably 5% by weight to 50% by weight with respect to the total amount of the monomer, oligomer and prepolymer in the hard coat layer forming composition. More preferably, it is 10 to 30% by weight. If it is such a range, the composition for hard-coat layer formation excellent in coating property will be obtained. In addition, curing shrinkage of the formed hard coat layer can be effectively prevented.
- 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 the total amount of the monomer, oligomer and prepolymer in the hard coat layer forming composition. 60% by weight, more preferably 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 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m.
- the (meth) acrylic resin forming the (meth) acrylic resin film is eluted in the hard coat layer forming composition, and the (meth) acrylic resin is present in the hard coat layer. May be.
- the concentration of the (meth) acrylic resin is the base material of the permeation layer. It becomes continuously lower from the layer side to the hard coat layer.
- the interface reflection is suppressed by the fact that 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. And an optical laminated body with less interference unevenness can be obtained.
- the (meth) acrylic resin and the composition for forming a hard coat layer are phase-separated, and a block layer is formed on the opposite side of the hard coat layer from the osmotic layer.
- concentration of the said (meth) acrylic-type resin becomes low continuously from the base material layer side of a osmosis
- the thickness of the block layer is preferably 1 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 5 ⁇ m.
- the thickness of a block layer can be measured by observation with electron microscopes, such as a reflection spectrum of a hard-coat layer, or SEM and TEM.
- 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.
- an optical laminate having excellent adhesion between the (meth) acrylic resin film and the hard coat layer and having suppressed interference unevenness can be obtained.
- coated composition for hard-coat layer formation can be dried by the said heating.
- the heating temperature may be set according to the content ratio of the curable compound having two or more (meth) acryloyl groups and the monofunctional monomer.
- the heating temperature for example, 80 ° C. to 100 ° C.
- the curing process is performed by ultraviolet irradiation.
- the integrated light quantity of ultraviolet irradiation is preferably 200 mJ to 400 mJ.
- Refractive index The refractive index of the base material layer and the hard coat layer was measured using an Abbe refractometer (trade name: DR-M2 / 1550) manufactured by Atago Co., Ltd., selecting monobromonaphthalene as an intermediate solution.
- Thickness of permeation layer A black acrylic plate (Mitsubishi Rayon Co., Ltd., thickness 2 mm) is placed on the base layer side of the optical laminate obtained in Examples and Comparative Examples via an acrylic adhesive having a thickness of 20 ⁇ m. Sticked.
- the reflection spectrum of the hard coat layer was measured under the following conditions using an instantaneous multi-photometry system (trade name: MCPD3700, manufactured by Otsuka Electronics Co., Ltd.).
- -Laminate (R1) 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 60 ° C. Obtained in the same manner as in Example 1.
- Laminate (R2) 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 7.
- the hard coat is obtained from the peak position of the FFT spectrum obtained from the laminate (R1) and the laminate (R2). The thickness of only the layer is measured.
- the thickness of the hard coat layer of Examples 1 to 6, 8, 9 and Comparative Examples 1 to 6 was 5.3 ⁇ m, and the thickness of the hard coat layer of Example 7 was 4.4 ⁇ m.
- the FFT spectrum of the laminate (R1) is shown in FIG. 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.
- interference unevenness 2 was evaluated from the amplitude in the wavelength region of 500 nm to 600 nm of the reflection spectrum of the hard coat layer measured in the evaluation of (2) above.
- 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%.
- UV curable resin containing 13 parts of isocyanuric acid triacrylate, 16 parts of pentaerythritol triacrylate, 62 parts of dipentaerythritol hexaacrylate, and 9 parts of isophorone diisocyanate polyurethane (trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate 100 parts, leveling agent (manufactured by DIC, trade name: GRANDIC PC-4100) 5 parts, photopolymerization initiator (manufactured by Ciba Japan, trade name: Irgacure 907) 3 parts And it diluted with methyl isobutyl ketone so that solid content concentration might be 50%, and the composition for hard-coat layer formation was prepared.
- leveling agent manufactured by DIC, trade name: GRANDIC PC-4100
- photopolymerization initiator manufactured by Ciba Japan, trade name: Irgacure 907
- the obtained composition for forming a hard coat layer was applied to form a coating layer, and the coating layer was heated at 110 ° C. for 1 minute.
- the coated layer after heating was irradiated with ultraviolet light having an accumulated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp to cure the coated layer to form a base layer, a hard coat layer, and a penetrating layer, thereby obtaining an optical laminate.
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- the actual reflection spectrum obtained by the evaluation of the above (2) is shown in FIG. 4A, and the FFT spectrum is shown in FIG. 4B.
- Example 2 An optical laminate was obtained in the same manner as in Example 1 except that the heating temperature of the coating layer was 120 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- the composition for forming a hard coat layer was prepared by diluting with an aqueous solution.
- the composition of the ultraviolet curable resin (PC1070) is as follows. Urethane acrylate obtained from pentaerythritol acrylate and hydrogenated xylene diisocyanate 100 parts Dipentaerythritol hexaacrylate 49 parts Pentaerythritol tetraacrylate 41 parts Pentaerythritol triacrylate 24 parts, 58 parts of a (meth) acrylic polymer having a 2-hydroxyethyl group and a 2,3-dihydroxypropyl group.
- the obtained composition for forming a hard coat layer was applied onto the base film obtained in Production Example 1.
- a layer was formed, and the coating layer was heated at 120 ° C. for 1 minute.
- the coated layer after heating was irradiated with ultraviolet light having an accumulated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp to cure the coated layer to form a base layer, a hard coat layer, and a penetrating layer, thereby obtaining an optical laminate.
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: PC1070, solid content: 66%, solvent: ethyl acetate, butyl acetate
- PETA pentaerythritol triacrylate
- a leveling agent manufactured by DIC, trade name: GRANDIC PC-4100
- a photoinitiator trade name: Irgacure 907, manufactured by Ciba Japan Co., Ltd.
- a composition for forming a hard coat layer was prepared by diluting with methyl isobutyl ketone so that the solid content concentration was 50%.
- the obtained composition for forming a hard coat layer was applied to form a coating layer, and the coating layer was heated at 100 ° C. for 1 minute.
- the coated layer after heating was irradiated with ultraviolet light having an accumulated light amount of 300 mJ / cm 2 with a high-pressure mercury lamp to cure the coated layer to form a base layer, a hard coat layer, and a penetrating layer, thereby obtaining an optical laminate.
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 5 Instead of using an ultraviolet curable resin (manufactured by DIC, trade name: Unidic 17-806), pentaerythritol triacrylate (PETA) (trade name: Biscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used. An optical laminate was obtained in the same manner as Example 1. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- PETA pentaerythritol triacrylate
- Example 6 Instead of UV curable resin (trade name: Unidic 17-806, manufactured by DIC), pentaerythritol triacrylate (PETA) (trade name: Biscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used. An optical laminate was obtained in the same manner as in Example 1 except that the heating temperature was 100 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- PETA pentaerythritol triacrylate
- Example 7 Instead of 100 parts of UV curable resin (manufactured by DIC, trade name: UNIDIC 17-806), a mixture of 60 parts of urethane acrylic oligomer, 30 parts of pentaerythritol tetraacrylate and 10 parts of pentaerythritol triacrylate (manufactured by Nippon Gosei Co., Ltd.) An optical laminate was obtained in the same manner as in Example 1 except that trade name: UV-7600-B) was used. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 8 An optical laminate was obtained in the same manner as in Example 1 except that the composition for forming a hard coat layer was prepared by diluting with isopropyl alcohol instead of methyl isobutyl ketone. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 9 Instead of 100 parts of UV curable resin (DIC, trade name: UNIDIC 17-806), 30 parts of dipentaerythritol hexaacrylate (DPHA) (trade name: A-DPH, made by Shin-Nakamura Chemical Co., Ltd.), penta Hard coat layer using a mixture of 55 parts of erythritol triacrylate (PETA) (trade name: Viscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 15 parts of acryloylmorpholine (ACMO) (manufactured by Kojin Co., Ltd.) without using a solvent.
- An optical laminate was obtained in the same manner as Example 1 except that the forming composition was prepared. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 10> Instead of 100 parts of UV curable resin (DIC, trade name: UNIDIC 17-806), 30 parts of dipentaerythritol hexaacrylate (DPHA) (trade name: A-DPH, made by Shin-Nakamura Chemical Co., Ltd.), penta Hard coat layer using a mixture of 55 parts of erythritol triacrylate (PETA) (trade name: Viscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 15 parts of acryloylmorpholine (ACMO) (manufactured by Kojin Co., Ltd.) without using a solvent.
- DPHA dipentaerythritol hexaacrylate
- A-DPH erythritol triacrylate
- ACMO acryloylmorpholine
- An optical layered body was obtained in the same manner as in Example 1 except that a forming composition was prepared and the heating temperature of the coating layer was 95 ° C.
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 11 Instead of 100 parts of UV curable resin (manufactured by DIC, trade name: UNIDIC 17-806), UNIDIC 17-806 (100 parts) and pentaerythritol triacrylate (PET) (manufactured by Osaka Organic Chemical Industry Co., Ltd., product) Name: Biscoat # 300)
- An optical laminate was obtained in the same manner as in Example 1 except that 40 parts of mixed resin was used and the heating temperature of the coating layer was set to 100 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 12 In place of 100 parts of UV curable resin (manufactured by DIC, trade name: UNIDIC 17-806), a mixture of UNIDIC 17-806 (100 parts) and 20 parts of acryloylmorpholine (ACMO) (manufactured by Kojin Co., Ltd.) An optical laminate was obtained in the same manner as in Example 1 except that a resin was used and the heating temperature of the coating layer was set to 100 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 13 In place of 100 parts of UV curable resin (manufactured by DIC, trade name: UNIDIC 17-806), a mixture of UNIDIC 17-806 (100 parts) and 20 parts of acryloylmorpholine (ACMO) (manufactured by Kojin Co., Ltd.) An optical laminate was obtained in the same manner as in Example 1 except that the resin was used and the heating temperature of the coating layer was 95 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- 4-HBA 4-hydroxybutyl acrylate
- a leveling agent manufactured by DIC, trade name: GRANDIC PC-4100
- a photopolymerization initiator manufactured by Ciba Japan, trade name: Irgacure 907
- An optical laminate was obtained in the same manner as in Example 1 except that the hard coat layer forming composition prepared by diluting with methyl isobutyl ketone was used and the heating temperature of the coating layer was 90 ° C. .
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- HEAA N- (2-hydroxyethyl) acrylamide
- 20 parts 5 parts of a leveling agent (manufactured by DIC, trade name: GRANDIC PC-4100) and 3 parts of a photopolymerization initiator (manufactured by Ciba Japan, trade name: Irgacure 907) are mixed, and the solid content concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the hard coat layer forming composition prepared by diluting with methyl isobutyl ketone was used and the heating temperature of the coating layer was 90 ° C. .
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 16 80 parts of “UV-7600-B” manufactured by Nippon Gosei Co., Ltd., 20 parts of 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), leveling agent (manufactured by DIC, trade name: GRANDIC PC-4100 ) 5 parts, 3 parts of photopolymerization initiator (Ciba Japan Co., Ltd., trade name: Irgacure 907) are mixed, and the hard coat layer is prepared by diluting with methyl isobutyl ketone so that the solid content concentration becomes 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the forming composition was used and the heating temperature of the coating layer was 90 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 17 80 parts of “UV-7600-B” manufactured by Nippon Gosei Co., Ltd., 20 parts of N- (2-hydroxyethyl) acrylamide (HEAA) (manufactured by Kojin Co., Ltd.), leveling agent (manufactured by DIC, trade name: GRANDIC PC-4100 ) 5 parts, 3 parts of photopolymerization initiator (Ciba Japan Co., Ltd., trade name: Irgacure 907) are mixed, and the hard coat layer is prepared by diluting with methyl isobutyl ketone so that the solid content concentration becomes 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the forming composition was used and the heating temperature of the coating layer was 90 ° C. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: UNIDIC 17-806, solid content: 80%, solvent: butyl acetate
- 106 parts 4-hydroxybutyl acrylate (4-HBA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 15 parts, 5 parts of a leveling agent (manufactured by DIC, product name: GRANDIC PC-4100) and 3 parts of a photopolymerization initiator (manufactured by Ciba Japan, product name: Irgacure 907) are mixed, and the solid content concentration is 50%.
- 4-HBA 4-hydroxybutyl acrylate
- a leveling agent manufactured by DIC, product name: GRANDIC PC-4100
- 3 parts of a photopolymerization initiator manufactured by Ciba Japan, product name: Irgacure 907
- An optical laminate was obtained in the same manner as in Example 1 except that the hard coat layer forming composition prepared by diluting with methyl isobutyl ketone was used and the heating temperature of the coating layer was 90 ° C. .
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- 106 parts N- (2-hydroxyethyl) acrylamide (HEAA) (manufactured by Kojin Co., Ltd.) 15 parts
- 5 parts of a leveling agent manufactured by DIC, product name: GRANDIC PC-4100
- 3 parts of a photopolymerization initiator manufactured by Ciba Japan, product name: Irgacure 907 are mixed, and the solid content concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the hard coat layer forming composition prepared by diluting with methyl isobutyl ketone was used and the heating temperature of the coating layer was 90 ° C. .
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- UV curable resin manufactured by DIC, trade name: Unidic 17-806, solid content: 80%, solvent: butyl acetate
- 4-HBA 4-hydroxybutyl acrylate
- 30 parts, 5 parts of a leveling agent manufactured by DIC, product name: GRANDIC PC-4100
- 3 parts of a photopolymerization initiator manufactured by Ciba Japan, product name: Irgacure 907 are mixed, and the solid content concentration is 50%.
- An optical laminate was obtained in the same manner as in Example 1 except that the hard coat layer forming composition prepared by diluting with methyl isobutyl ketone was used and the heating temperature of the coating layer was 90 ° C. .
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- Example 21 80 parts of pentaerythritol triacrylate (PETA) (trade name: Biscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 20 parts of 4-hydroxybutyl acrylate (4-HBA) (produced by Osaka Organic Chemical Industry Co., Ltd.), leveling agent (DIC) 5 parts by product, trade name: GRANDIC PC-4100) and 3 parts by photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Japan Co., Ltd.) are mixed so that the solid content concentration becomes 50%.
- PETA pentaerythritol triacrylate
- 4-HBA 4-hydroxybutyl acrylate
- DIC leveling agent
- GRANDIC PC-4100 trade name: GRANDIC PC-4100
- photopolymerization initiator trade name: Irgacure 907, manufactured by Ciba Japan Co., Ltd.
- An optical laminate was obtained in the same manner as in Example 1 except that the composition for forming a hard coat layer prepared by diluting with a ketone was used and the heating temperature of the coating layer was set to 90 ° C.
- This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- ⁇ Comparative Example 2> Instead of the base film A obtained in Production Example 1, a triacetyl cellulose (TAC) base material (manufactured by Fuji Film, trade name: TD80UL) was used, and the heating temperature of the coating layer was set to 60 ° C. An optical laminate was obtained in the same manner as Example 1. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below.
- TAC triacetyl cellulose
- ⁇ Comparative Example 3> An optical laminate in the same manner as in Example 1 except that a triacetyl cellulose (TAC) substrate (manufactured by Fuji Film, trade name: TD80UL) was used instead of the substrate film A obtained in Production Example 1. Got. This optical laminate was subjected to the evaluations (2) to (5) above. The results are shown in Table 1 below. Moreover, the actual reflection spectrum obtained by the evaluation of the above (2) is shown in FIG. 5A, and the FFT spectrum is shown in FIG. 5B.
- TAC triacetyl cellulose
- the optical laminate of the present invention has excellent adhesion to the base film ((meth) acrylic resin film) and the hard coat layer by having a permeation layer having a predetermined thickness. In addition, interference unevenness is suppressed.
- a hard coat layer-forming composition containing no solvent Examples 9 and 10
- the base film A ((meth) acrylic resin film) used in the examples has low moisture permeability.
- the base film A has a moisture permeability of 61 g / m 2 ⁇ 24 hr as described above.
- a TAC substrate having the same thickness manufactured by Konica Minolta, trade name: KC4UY, moisture permeability: 800 g / M 2 ⁇ 24 hr
- the adhesiveness between the base film and the hard coat layer is excellent and interference unevenness is suppressed.
- An optical laminate can be obtained.
- 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、上記浸透層において、(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、ハードコート層側から基材層側へ連続的に高くなる。
好ましい実施形態においては、500nm~600nmの波長領域におけるハードコート層の反射スペクトルの振幅が、0.5%以下である。
好ましい実施形態においては、上記基材層の屈折率と、ハードコート層の屈折率との差の絶対値が、0.01~0.15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)アクリル系樹脂が、側鎖に芳香環を有する。
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む。
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、単官能モノマーをさらに含む。
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、上記ハードコート層形成用組成物が、ウレタン(メタ)アクリレートおよび/またはウレタン(メタ)アクリレートのオリゴマーを含む。
1つの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、水酸基を有する(メタ)アクリル系プレポリマーを含む。
1つの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、溶媒を含まない。
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、偏光フィルムが提供される。この偏光フィルム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。
本発明のさらに別の局面によれば、光学積層体の製造方法が提供される。この光学積層体の製造方法は、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布して塗布層を形成し、該塗布層を80℃~140℃で加熱することを含む。
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成分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、例えば、熱、光(紫外線等)または電子線等により硬化し得る硬化性化合物を含む。好ましくは、ハードコート層形成用組成物は、光硬化型の硬化性化合物を含む。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、ブロック層の厚みは、ハードコート層の反射スペクトル、またはSEM、TEM等の電子顕微鏡による観察により測定することができる。
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。
基材層およびハードコート層の屈折率を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。
(2)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、上記(1)で測定した値を用いた。
・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:2~15μm
膜厚分解能:24nm
また、実施例1~6、8、9および比較例1~6のハードコート層の厚みは、下記積層体(R1)についての上記反射スペクトル測定により評価した。実施例7のハードコート層の厚みは、下記積層体(R2)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(R1):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1と同様にして得た。
・積層体(R2):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7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(R1)および積層体(R2)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、実施例1~6、8、9および比較例1~6のハードコート層の厚みは5.3μm、実施例7のハードコート層の厚みは4.4μmであった。積層体(R1)のFFTスペクトルを図3に示す。
((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、FFTスペクトルによれば浸透層の厚みが0μmとなる場合(比較例1および4)においては、光学積層体の断面をSEMにて観察し、浸透層が形成されていないことを実際に確認した。
(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1
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)干渉ムラ2
実施例および比較例で得られた光学積層体について、上記(2)の評価で測定したハードコート層の反射スペクトルの500nm~600nmの波長領域における振幅から、干渉ムラを評価した。
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)社製の分光光度計(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。
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部およびイソホロンジイソシアネートポリウレタン9部を含む紫外線硬化型樹脂(DIC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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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。
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(2)~(5)の評価に供した。結果を下記表1に示す。また、上記(2)の評価で得られた実際の反射スペクトルを図4Aに、FFTスペクトルを図4Bに示す。
塗布層の加熱温度を120℃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(2)~(5)の評価に供した。結果を下記表1に示す。
ペンタエリスリトール系アクリレートと水添キシレンジイソシアネートとから得られるウレタンアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、2-ヒドロキシエチル基および2、3-ジヒドロキシプロピル基を有する(メタ)アクリルポリマー、および光反応開始剤(チバ・ジャパン社製、商品名:イルガキュア184;BASF社製、商品名:ルシリンTPO)を含む紫外線硬化型樹脂(DIC社製、商品名:PC1070、固形分:66%、溶媒:酢酸エチル、酢酸ブチル)100部およびレベリング剤(DIC社製、商品名:GRANDIC PC-4100)5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、上記紫外線硬化型樹脂(PC1070)の組成は以下のとおりである。
ペンタエリスリトール系アクリレートと水添キシレンジイソシアネートとから得られるウレタンアクリレート 100部
ジペンタエリスリトールヘキサアクリレート 49部
ペンタエリスリトールテトラアクリレート 41部
ペンタエリスリトールトリアクリレート 24部、
2-ヒドロキシエチル基および2、3-ジヒドロキシプロピル基を有する(メタ)アクリルポリマー 58部
製造例1で得られた基材フィルム上に、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120℃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(2)~(5)の評価に供した。結果を下記表1に示す。
上記紫外線硬化型樹脂(DIC社製、商品名:PC1070、固形分:66%、溶媒:酢酸エチル、酢酸ブチル)100部、ペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)40部、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部および光反応開始剤(チバ・ジャパン社製、商品名:イルガキュア907)1.2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。
製造例1で得られた基材フィルム上に、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100℃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(2)~(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(DIC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(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)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(2)~(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(DIC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(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)を用い、塗布層の加熱温度を100℃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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、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(日本合成社製、商品名:UV-7600-B)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(2)~(5)の評価に供した。結果を下記表1に示す。
メチルイソブチルケトンに代えて、イソプロピルアルコールで希釈してハードコート層形成用組成物を調製した以外は、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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、ジペンタエリスリトールヘキサアクリレート(DPHA)(新中村化学社製、商品名:A-DPH)30部、ペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)55部、アクリロイルモルホリン(ACMO)(興人社製)15部の混合物を用い、溶剤を用いずにハードコート層形成用組成物を調製した以外は、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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、ジペンタエリスリトールヘキサアクリレート(DPHA)(新中村化学社製、商品名:A-DPH)30部、ペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)55部、アクリロイルモルホリン(ACMO)(興人社製)15部の混合物を用い、溶剤を用いずにハードコート層形成用組成物を調製し、塗布層の加熱温度を95℃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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、ユニディック17-806(100部)とペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)40部との混合樹脂を用い、塗布層の加熱温度を100℃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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、ユニディック17-806(100部)とアクリロイルモルホリン(ACMO)(興人社製)20部との混合樹脂を用い、塗布層の加熱温度を100℃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(2)~(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(DIC社製、商品名:ユニディック17-806)100部に代えて、ユニディック17-806(100部)とアクリロイルモルホリン(ACMO)(興人社製)20部との混合樹脂を用い、塗布層の加熱温度を95℃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(2)~(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(DIC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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(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(DIC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、N-(2-ヒドロキシエチル)アクリルアミド(HEAA)(興人社製)20部、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(5)の評価に供した。結果を下記表1に示す。
上記日本合成社製「UV-7600-B」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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(5)の評価に供した。結果を下記表1に示す。
上記日本合成社製「UV-7600-B」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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(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(DIC社製、商品名:ユニディック17-806、固形分:80%、溶媒:酢酸ブチル)106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)15部、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(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(DIC社製、商品名:ユニディック17-806、固形分:80%、溶媒:酢酸ブチル)106部、N-(2-ヒドロキシエチル)アクリルアミド(HEAA)(興人社製)15部、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(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(DIC社製、商品名:ユニディック17-806、固形分:80%、溶媒:酢酸ブチル)88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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(5)の評価に供した。結果を下記表1に示す。
ペンタエリスリトールトリアクリレート(PETA)(大阪有機化学工業社製、商品名:ビスコート#300)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、レベリング剤(DIC社製、商品名:GRANDIC PC-4100)5部、光重合開始剤(チバ・ジャパン社製、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製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(2)~(5)の評価に供した。結果を下記表1に示す。
製造例1で得られた基材フィルムAに代えて、シクロオレフィン系基材(日本ゼオン社製、商品名:ゼオノアZF14)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(2)~(5)の評価に供した。結果を下記表1に示す。
製造例1で得られた基材フィルムAに代えて、トリアセチルセルロース(TAC)基材(富士フイルム社製、商品名:TD80UL)を用い、塗布層の加熱温度を60℃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(2)~(5)の評価に供した。結果を下記表1に示す。
製造例1で得られた基材フィルムAに代えて、トリアセチルセルロース(TAC)基材(富士フイルム社製、商品名:TD80UL)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(2)~(5)の評価に供した。結果を下記表1に示す。また、上記(2)の評価で得られた実際の反射スペクトルを図5Aに、FFTスペクトルを図5Bに示す。
塗布層の加熱温度を60℃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(2)~(5)の評価に供した。結果を下記表1に示す。
塗布層の加熱温度を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(2)~(5)の評価に供した。結果を下記表1に示す。
塗布層の加熱温度を100℃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(2)~(5)の評価に供した。結果を下記表1に示す。
20 浸透層
30 ハードコート層
40 ブロック層
100、200、300 光学積層体
Claims (19)
- (メタ)アクリル系樹脂フィルムから形成される基材層と、
該(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浸透層とを備え、
該浸透層の厚みが1.2μm以上である、
光学積層体。 - 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、前記ハードコート層側から前記基材層側へ連続的に高くなる、請求項1に記載の光学積層体。
- 500nm~600nmの波長領域における前記ハードコート層の反射スペクトルの振幅が、0.5%以下である、請求項1または2に記載の光学積層体。
- 前記基材層の屈折率と、前記ハードコート層の屈折率との差の絶対値が、0.01~0.15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(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4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5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む、請求項1から6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、単官能モノマーをさらに含む、請求項7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8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8または9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10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、ウレタン(メタ)アクリレートおよび/またはウレタン(メタ)アクリレートのオリゴマーを含む、請求項1から11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、水酸基を有する(メタ)アクリル系プレポリマーを含む、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形成用組成物が、溶媒を含まない、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。
- (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80℃~140℃で加熱することを含む、請求項1から16のいずれかに記載の光学積層体の製造方法。
Priority Applications (4)
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US14/111,866 US9720134B2 (en) | 2011-04-22 | 2012-04-18 | Optical laminate comprising hard coat layer comprised of cured product of composition comprising (meth)acrylic prepolymer having hydroxyl group |
CN201280019681.5A CN103492913B (zh) | 2011-04-22 | 2012-04-18 | 光学层叠体 |
KR1020137030671A KR101931400B1 (ko) | 2011-04-22 | 2012-04-18 | 광학 적층체 |
US15/664,747 US10203430B2 (en) | 2011-04-22 | 2017-07-31 | Method of producing optical laminate comprising hard coat layer comprised of cured product of composition comprising (meth)acrylic prepolymer having hydroxyl group |
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US14/111,866 A-371-Of-International US9720134B2 (en) | 2011-04-22 | 2012-04-18 | Optical laminate comprising hard coat layer comprised of cured product of composition comprising (meth)acrylic prepolymer having hydroxyl group |
US15/664,747 Division US10203430B2 (en) | 2011-04-22 | 2017-07-31 | Method of producing optical laminate comprising hard coat layer comprised of cured product of composition comprising (meth)acrylic prepolymer having hydroxyl group |
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JP (1) | JP6128576B2 (ja) |
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006126802A (ja) * | 2004-09-30 | 2006-05-18 | Dainippon Printing Co Ltd | 光学積層体 |
WO2006106757A1 (ja) * | 2005-03-30 | 2006-10-12 | Dai Nippon Printing Co., Ltd. | 防眩性光学積層体 |
JP2007090656A (ja) * | 2005-09-28 | 2007-04-12 | Dainippon Printing Co Ltd | 透光性物品 |
JP2007254706A (ja) * | 2005-11-10 | 2007-10-04 | Jsr Corp | 硬化性樹脂組成物及び反射防止膜 |
JP2008012675A (ja) * | 2006-06-30 | 2008-01-24 | Dainippon Printing Co Ltd | 光学積層体、及びその製造方法 |
WO2008032813A1 (fr) * | 2006-09-15 | 2008-03-20 | Toray Industries, Inc. | Filtre d'affichage plasma |
JP2008165041A (ja) * | 2006-12-28 | 2008-07-17 | Dainippon Printing Co Ltd | ハードコートフィルム、及びその製造方法 |
JP2010065109A (ja) * | 2008-09-10 | 2010-03-25 | Nippon Shokubai Co Ltd | 熱可塑性樹脂組成物とそれを用いたフィルム |
JP2010122323A (ja) * | 2008-11-17 | 2010-06-03 | Dainippon Printing Co Ltd | 光学シート及び光学シートの製造方法 |
JP2010237648A (ja) * | 2009-03-09 | 2010-10-21 | Toppan Printing Co Ltd | 反射防止フィルム及びその製造方法、偏光板、透過型液晶ディスプレイ |
JP2011033948A (ja) * | 2009-08-04 | 2011-02-17 | Dainippon Printing Co Ltd | 光学積層体、偏光板及び画像表示装置 |
Family Cites Families (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06184267A (ja) | 1992-12-17 | 1994-07-05 | Mitsui Toatsu Chem Inc | 密着性に優れた光硬化型樹脂組成物 |
JP2002036436A (ja) | 2000-07-19 | 2002-02-05 | Fuji Photo Film Co Ltd | ハードコートフイルム及び機能性薄膜付きハードコートフイルム |
TW200307733A (en) | 2002-02-01 | 2003-12-16 | Natoco Co Ltd | Composition curable with actinic energy ray and use thereof |
JP3953829B2 (ja) | 2002-02-20 | 2007-08-08 | 大日本印刷株式会社 | 表面が強化された反射防止層、反射防止材、および反射防止体 |
JP3982377B2 (ja) | 2002-10-08 | 2007-09-26 | Jsr株式会社 | 光硬化性樹脂組成物及び光学部材 |
JP4475016B2 (ja) * | 2003-06-30 | 2010-06-09 | 東レ株式会社 | ハードコートフィルム、反射防止フィルムおよび画像表示装置 |
JP2005097371A (ja) * | 2003-09-22 | 2005-04-14 | Fuji Photo Film Co Ltd | フッ素含有樹脂組成物及び光学物品、並びにそれを用いた画像表示装置 |
JP2005133026A (ja) | 2003-10-31 | 2005-05-26 | Lintec Corp | コーティング用組成物、ハードコートフィルムおよび光ディスク |
CN101421432A (zh) | 2003-12-18 | 2009-04-29 | 北美Agc平板玻璃公司 | 用于光学涂层的具有增强的抗腐蚀性和抗划伤性的防护层 |
JP4479260B2 (ja) | 2004-02-04 | 2010-06-09 | コニカミノルタオプト株式会社 | 光学フィルムの製造方法 |
US20070243364A1 (en) | 2004-04-28 | 2007-10-18 | Shigetoshi Maekawa | Acrylic Resin Films and Process for Producing the Same |
WO2006016592A1 (en) * | 2004-08-12 | 2006-02-16 | Fujifilm Corporation | Anti-reflection film |
US7585560B2 (en) | 2004-09-30 | 2009-09-08 | Dai Nippon Printing Co., Ltd. | Optical laminate |
JP2006110875A (ja) | 2004-10-15 | 2006-04-27 | Toppan Printing Co Ltd | ハードコートフィルムおよび表示媒体 |
JP4746863B2 (ja) | 2004-11-11 | 2011-08-10 | リンテック株式会社 | 防眩性ハードコート層形成用材料及び防眩性ハードコートフィルム |
US7622194B2 (en) * | 2004-12-28 | 2009-11-24 | Fujifilm Corporation | Optical film, anti-reflection film, polarizing plate, and image display device |
JP2006205545A (ja) | 2005-01-28 | 2006-08-10 | Toray Ind Inc | ハードコートフィルム |
JP2006274119A (ja) | 2005-03-30 | 2006-10-12 | Mitsui Chemicals Inc | 熱可塑性エラストマー組成物及びその積層成形品 |
US20100168363A1 (en) | 2005-08-04 | 2010-07-01 | Ueda Ken-Ichi | Low Birefringent Copolymers |
JP5015462B2 (ja) | 2006-01-11 | 2012-08-29 | 株式会社ダイセル | 防眩性フィルム及びその製造方法 |
JP5024287B2 (ja) * | 2006-03-31 | 2012-09-12 | 大日本印刷株式会社 | 光学積層体及び光学積層体の製造方法 |
US7700255B2 (en) | 2006-04-28 | 2010-04-20 | Konica Minolta Business Technologies, Inc. | Intermediate transfer material, image forming method and image forming apparatus |
JP2008165205A (ja) | 2006-12-05 | 2008-07-17 | Fujifilm Corp | 光学フィルム、反射防止フィルム、それを用いた偏光板およびディスプレイ装置 |
JP2008181078A (ja) * | 2006-12-27 | 2008-08-07 | Nitto Denko Corp | 偏光子保護フィルム、偏光板、および画像表示装置 |
JP5125118B2 (ja) * | 2007-01-29 | 2013-01-23 | 大日本印刷株式会社 | コーティング組成物、硬化膜、光学積層体及びその製造方法 |
JP5063141B2 (ja) * | 2007-02-28 | 2012-10-31 | リンテック株式会社 | 防眩性ハードコートフィルムの製造方法 |
US20080284950A1 (en) * | 2007-04-02 | 2008-11-20 | Dai Nippon Printing Co., Ltd. | Composition, single layer, member or laminate for realizing an antistatic (and hardcoat) features |
JP4958609B2 (ja) * | 2007-04-06 | 2012-06-20 | リンテック株式会社 | 防眩性ハードコートフィルム及びその製造方法 |
KR101197459B1 (ko) | 2007-08-10 | 2012-11-09 | 다이니폰 인사츠 가부시키가이샤 | 하드 코트 필름 |
JP5186834B2 (ja) | 2007-08-10 | 2013-04-24 | 大日本印刷株式会社 | ハードコートフィルム |
JP5078520B2 (ja) * | 2007-09-19 | 2012-11-21 | リンテック株式会社 | 防眩性ハードコートフィルム及びその製造方法 |
JP5568832B2 (ja) | 2007-09-28 | 2014-08-13 | 大日本印刷株式会社 | 硬化性樹脂組成物及びハードコートフィルム |
JP5504605B2 (ja) | 2007-10-30 | 2014-05-28 | 大日本印刷株式会社 | ハードコート層用硬化性樹脂組成物、及びハードコートフィルム |
JP5291919B2 (ja) | 2007-11-20 | 2013-09-18 | 富士フイルム株式会社 | ディスプレイ表面に用いる偏光板用保護フィルム又は画像表示装置前面板用フィルム |
US20100272971A1 (en) | 2007-12-28 | 2010-10-28 | Nippon Shokubai Co., Ltd. | Optical film and image display apparatus having the same |
JP2009161609A (ja) | 2007-12-28 | 2009-07-23 | Three M Innovative Properties Co | ハードコートフィルム及び印刷体 |
JP2009185282A (ja) | 2008-01-11 | 2009-08-20 | Nitto Denko Corp | ハードコートフィルム、ハードコートフィルムの製造方法、光学素子および画像表示装置 |
JP2009262148A (ja) | 2008-03-31 | 2009-11-12 | Dainippon Printing Co Ltd | 多層塗工膜の製造方法 |
JP2010039418A (ja) | 2008-08-08 | 2010-02-18 | Konica Minolta Opto Inc | 反射防止フィルム、反射防止フィルムの製造方法、偏光板及び画像表示装置 |
JP5235557B2 (ja) | 2008-08-11 | 2013-07-10 | 名阪真空工業株式会社 | ディスプレイ面板用透明多層シート |
JP2010082564A (ja) * | 2008-09-30 | 2010-04-15 | Dainippon Printing Co Ltd | 微小気泡を利用した多層塗工膜の製造方法 |
US20110304817A1 (en) * | 2009-04-20 | 2011-12-15 | Shunichiro Nakatsukasa | Coating composition |
JP2012234164A (ja) * | 2011-04-22 | 2012-11-29 | Nitto Denko Corp | 光学積層体 |
JP6128576B2 (ja) * | 2011-04-22 | 2017-05-17 | 日東電工株式会社 | 光学積層体 |
JP6128629B2 (ja) * | 2011-04-22 | 2017-05-17 | 日東電工株式会社 | 光学積層体 |
-
2012
- 2012-04-16 JP JP2012093002A patent/JP6128576B2/ja active Active
- 2012-04-18 CN CN201280019681.5A patent/CN103492913B/zh active Active
- 2012-04-18 US US14/111,866 patent/US9720134B2/en active Active
- 2012-04-18 WO PCT/JP2012/060420 patent/WO2012144508A1/ja active Application Filing
- 2012-04-18 KR KR1020137030671A patent/KR101931400B1/ko active IP Right Grant
- 2012-04-20 TW TW101114322A patent/TWI592303B/zh active
-
2017
- 2017-07-31 US US15/664,747 patent/US10203430B2/en not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006126802A (ja) * | 2004-09-30 | 2006-05-18 | Dainippon Printing Co Ltd | 光学積層体 |
WO2006106757A1 (ja) * | 2005-03-30 | 2006-10-12 | Dai Nippon Printing Co., Ltd. | 防眩性光学積層体 |
JP2007090656A (ja) * | 2005-09-28 | 2007-04-12 | Dainippon Printing Co Ltd | 透光性物品 |
JP2007254706A (ja) * | 2005-11-10 | 2007-10-04 | Jsr Corp | 硬化性樹脂組成物及び反射防止膜 |
JP2008012675A (ja) * | 2006-06-30 | 2008-01-24 | Dainippon Printing Co Ltd | 光学積層体、及びその製造方法 |
WO2008032813A1 (fr) * | 2006-09-15 | 2008-03-20 | Toray Industries, Inc. | Filtre d'affichage plasma |
JP2008165041A (ja) * | 2006-12-28 | 2008-07-17 | Dainippon Printing Co Ltd | ハードコートフィルム、及びその製造方法 |
JP2010065109A (ja) * | 2008-09-10 | 2010-03-25 | Nippon Shokubai Co Ltd | 熱可塑性樹脂組成物とそれを用いたフィルム |
JP2010122323A (ja) * | 2008-11-17 | 2010-06-03 | Dainippon Printing Co Ltd | 光学シート及び光学シートの製造方法 |
JP2010237648A (ja) * | 2009-03-09 | 2010-10-21 | Toppan Printing Co Ltd | 反射防止フィルム及びその製造方法、偏光板、透過型液晶ディスプレイ |
JP2011033948A (ja) * | 2009-08-04 | 2011-02-17 | Dainippon Printing Co Ltd | 光学積層体、偏光板及び画像表示装置 |
Cited By (22)
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CN109536046A (zh) * | 2013-08-30 | 2019-03-29 | 日东电工株式会社 | 偏振膜用固化型胶粘剂、偏振膜、光学膜和图像显示装置 |
WO2015068483A1 (ja) * | 2013-11-07 | 2015-05-14 | 日東電工株式会社 | 光学積層体 |
WO2016147776A1 (ja) * | 2015-03-18 | 2016-09-22 | リケンテクノス株式会社 | ハードコート積層フィルム |
US11065852B2 (en) | 2015-03-18 | 2021-07-20 | Riken Technos Corporation | Adhesive film |
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US11433651B2 (en) | 2015-03-18 | 2022-09-06 | Riken Technos Corporation | Hard coat laminated film |
US11352473B2 (en) | 2015-03-18 | 2022-06-07 | Riken Technos Corporation | Hard coat laminated film and method for producing same |
JP2017097322A (ja) * | 2015-11-16 | 2017-06-01 | 富士フイルム株式会社 | 光学フィルム、画像表示装置、および光学フィルムの製造方法 |
JP2020013154A (ja) * | 2015-11-16 | 2020-01-23 | 富士フイルム株式会社 | 光学フィルム、画像表示装置、および光学フィルムの製造方法 |
WO2017086141A1 (ja) * | 2015-11-16 | 2017-05-26 | 富士フイルム株式会社 | 光学フィルム、画像表示装置、および光学フィルムの製造方法 |
US11241866B2 (en) | 2015-11-25 | 2022-02-08 | Riken Technos Corporation | Door body |
US11774166B2 (en) | 2015-11-25 | 2023-10-03 | Riken Technos Corporation | Door body |
US10816700B2 (en) | 2015-12-08 | 2020-10-27 | Riken Technos Corporation | Hard coat layered film |
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Also Published As
Publication number | Publication date |
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US20140227482A1 (en) | 2014-08-14 |
US9720134B2 (en) | 2017-08-01 |
US10203430B2 (en) | 2019-02-12 |
JP6128576B2 (ja) | 2017-05-17 |
US20170329050A1 (en) | 2017-11-16 |
TW201300236A (zh) | 2013-01-01 |
CN103492913B (zh) | 2017-03-15 |
KR20140037093A (ko) | 2014-03-26 |
TWI592303B (zh) | 2017-07-21 |
JP2012234163A (ja) | 2012-11-29 |
CN103492913A (zh) | 2014-01-01 |
KR101931400B1 (ko) | 2018-12-20 |
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