WO2021111721A1 - 光学フィルム及びその製造方法、偏光板並びに表示装置 - Google Patents
光学フィルム及びその製造方法、偏光板並びに表示装置 Download PDFInfo
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- WO2021111721A1 WO2021111721A1 PCT/JP2020/037689 JP2020037689W WO2021111721A1 WO 2021111721 A1 WO2021111721 A1 WO 2021111721A1 JP 2020037689 W JP2020037689 W JP 2020037689W WO 2021111721 A1 WO2021111721 A1 WO 2021111721A1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to an optical film, a method for producing the same, a polarizing plate, and a display device. More specifically, the present invention provides an optical film having a sufficiently thin film thickness, a desired optical compensation value (phase difference), and good adhesion to a polarizer, a method for producing the same, and the optical film.
- the present invention relates to a polarizing plate and a display device.
- the protective film is arranged on both sides of the polarizing element by adhesion or the like.
- an optical film in which the phase difference is controlled in order to compensate for the change in the phase difference due to the viewing angle is generally used.
- the optical film is usually a resin film that has been subjected to processing such as uniaxial or biaxial stretching, and the magnitude relationship (refractive index ellipsoid) of the three-dimensional refractive index is controlled according to the usage conditions.
- a cellulosic resin film has been used as a protective film for such a polarizing plate.
- cellulosic resins are vulnerable to environmental changes due to their high moisture permeability, and cycloolefin resins have been attracting attention in recent years.
- the casting method is widely used as a film forming method for an optical film using a cycloolefin resin.
- a means for thinning the cycloolefin resin film there are methods such as reducing the film thickness at the initial stage of casting or increasing the draw ratio of the film.
- the present invention has been made in view of the above problems and situations, and the problem to be solved is that the film thickness is sufficiently thin, a desired optical compensation value (phase difference) can be obtained, and the adhesiveness with a polarizer is improved. It is an object of the present invention to provide a good optical film, particularly an optical film mainly composed of a cycloolefin resin, and a method for producing the same. Further, by using the optical film, it is possible to provide a polarizing plate and a display device in which the thickness is realized while maintaining the performance.
- the present inventor has formed an optical film by combining a cycloolefin resin with a compound having a specific structure in a process of examining the cause of the above problems, thereby reducing the thickness and increasing the phase difference.
- the present invention has been made by finding that an optical film capable of expressing the above can be obtained and having good adhesion to a polarizer can be obtained. That is, the above-mentioned problem according to the present invention is solved by the following means.
- Y represents an aromatic heterocycle having 5 to 20 members.
- X 1 and X 2 each independently represent a substituted or unsubstituted aromatic ring group that forms a single bond with an atom constituting Y.
- n is a valence of Y and is an integer of 2 or more.
- a method for producing an optical film which comprises preparing a dope containing a solvent, casting the dope onto a support to obtain an unstretched film, and stretching the unstretched film.
- a polarizing plate comprising a polarizing element and an optical film according to any one of items 1 to 5 arranged on at least one surface of the polarizing element.
- a display device comprising the optical film according to any one of items 1 to 5.
- an optical film having a sufficiently thin film thickness, a desired optical compensation value (phase difference), and good adhesion to a polarizer, particularly an optical film mainly composed of a cycloolefin resin, can be obtained.
- a film and a method for producing the film can be provided. Further, by using the optical film, it is possible to provide a polarizing plate and a display device in which the thickness is realized while maintaining the performance.
- the optical film of the present invention is characterized by containing a cycloolefin resin and a compound having a structure represented by the above general formula (1) (hereinafter, also referred to as compound (1)).
- compound (1) since the ring Y located at the center of compound (1) is an aromatic heterocycle, compound (1) is easily polarized and easily oriented. Further, in compound (1), X 1 and X 2 , which are substituted or unsubstituted monovalent aromatic ring groups, are located on the ring Y at the farthest distance from the center of Y and the ring constituting X 1, respectively.
- the straight line L 1 connecting the center of the ring positions, the straight line L 2 and the angle formed connecting the center of the ring located away from the most Y among the rings constituting the center and X 2 Y is, 110 ° ⁇ It is combined so that it is within the range of 145 °.
- the optical film of the present invention containing a cycloolefin resin and compound (1) is usually obtained by stretching a composition containing a cycloolefin resin and compound (1).
- the compound (1) has the above-mentioned structure, the compound (1) can physically interact with the cycloolefin resin when the cycloolefin resin is stretched.
- the cycloolefin resin is sufficiently oriented in the stretching direction in the obtained optical film, and the phase difference of the optical film can be improved.
- the compound (1) follows the cycloolefin resin and is uniformly oriented in the stretching direction to improve the adhesiveness to other members, specifically, the polarizer.
- FIG. 5 is an xy coordinate diagram used to determine the center of ring Y (pyridine ring) in compound 1-1.
- FIG. 5 is an xy coordinate diagram used to determine the center of the ring (benzimidazole ring) located farthest from Y in X 1 of compound 1-1. It is a figure which shows the angle ⁇ formed by X 1 and X 2 with respect to a ring Y in compound 1-1.
- FIG. 2 is a cross-sectional view showing a configuration example of the polarizing plate of the present invention.
- the optical film of the present invention is characterized by containing a cycloolefin resin and a compound having a structure represented by the above general formula (1). This feature is a technical feature common to each of the following embodiments.
- At least one of X 1 and X 2 contains an aromatic heterocycle from the viewpoint of further improving the phase difference of the optical film. Further, as an embodiment of the present invention, it is preferable that at least one of X 1 and X 2 contains an aromatic condensed ring from the viewpoint of exhibiting the effect of the present invention.
- the Y is a monocyclic ring having 6 members and 1 heteroatom, and X 1 and X 2 are described above. Are preferably bonded to the carbon atoms on both sides of the heteroatom.
- the cycloolefin resin has a polar group from the viewpoint of adhesiveness to other members, specifically, a polarizer in the optical film.
- a dope containing the compound having the structure represented by the general formula (1) and the cycloolefin resin and a solvent is prepared, and the dope is used as a support.
- the production method comprises casting the unstretched film on the film to obtain the unstretched film and stretching the obtained unstretched film.
- the polarizing plate of the present invention is characterized by comprising a polarizing element and an optical film of the present invention arranged on at least one surface of the polarizing element.
- the display device of the present invention is characterized by comprising the optical film of the present invention.
- the optical film of the present invention is characterized by containing a cycloolefin resin and compound (1).
- compound (1) acts as a retardation enhancer.
- the optical film of the present invention may contain a retardation enhancer other than compound (1). Further, the optical film of the present invention may contain various additives in addition to the retardation increasing agent as long as the effects of the present invention are not impaired.
- the compound (1) is a compound having a structure represented by the following general formula (1).
- the compound having the structure represented by the general formula (1) is also referred to as compound (1).
- formula (X 1) group a group having a structure represented by (X 1).
- the ring represented by Y may be referred to as ring Y.
- Y represents an aromatic heterocycle having 5 to 20 members.
- X 1 and X 2 each independently represent a substituted or unsubstituted aromatic ring group that forms a single bond with an atom constituting Y.
- n is a valence of Y and is an integer of 2 or more.
- a straight line L 1 connecting the center of the ring located away from the most Y among the rings constituting the center and X 1 of Y, located away from the most Y among the rings constituting the center and X 2 of Y The angle formed by the straight line L 2 connecting the center of the ring is also referred to as the angle formed by X 1 and X 2 with respect to the ring Y.
- the angle is also referred to as an angle ⁇ .
- Y is, for example, a monocyclic ring or a condensed ring.
- the "center of Y” is defined as follows in a monocyclic ring and a condensed ring.
- the "center of Y” is a geometric center in the case of a single ring.
- the geometric center is synonymous with the geometric center in mathematics, and belongs to, for example, a figure in a two-dimensional Euclidean space determined by two components of x and y, for example, a hexagonal figure of a 6-membered ring. It is the position of the xy coordinate obtained by arithmetically averaging each xy coordinate at all the vertices.
- the point equidistant from the geometric center of each ring constituting the condensed ring is the "center of Y".
- compound (1) since the ring Y located at the center of compound (1) is an aromatic heterocycle, compound (1) is easily polarized and easily oriented.
- compound (1) binds X 1 and X 2 , which are substituted or unsubstituted monovalent aromatic ring groups, to ring Y, respectively, so that the angle ⁇ formed by these is within the above-mentioned specific range.
- the orientation of the cycloolefin resin in the stretching direction can be promoted.
- the effect of the present invention can be obtained by the action of compound (1).
- Ring Y is an aromatic heterocycle having 5 to 20 members, and may be a monocyclic ring or a condensed ring.
- the number of members of the ring Y is preferably 5 to 10, more preferably 5 or 6.
- hetero atom possessed by the ring Y examples include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a bromine atom and the like, preferably a nitrogen atom, an oxygen atom and a sulfur atom, and nitrogen from the viewpoint of adhesiveness of the obtained optical film. Atoms are particularly preferred.
- the number of heteroatoms contained in the ring Y is preferably 1 to 6, and more preferably 1 to 3.
- Specific examples of the ring Y include the following aromatic heterocycles.
- the monocyclic aromatic heterocycle having 5 members include a furan ring, a pyrrole ring, an imidazole ring, a thiophene ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, and an isothiazole ring.
- 6-membered monocyclic aromatic heterocycle examples include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyran ring, a thiopyran ring, an oxazine ring, and a thiazine ring.
- Specific examples of the 7-membered monocyclic aromatic heterocycle include an azepine ring, an oxepin ring, and a thiopine ring.
- Specific examples of the eight-membered monocyclic aromatic heterocycle include an azocine ring, an oxocine ring, and a thiepine ring.
- Specific examples of the 9-membered monocyclic aromatic heterocycle include an azonine ring, an oxonine ring, and a thionin ring.
- Examples of the two-ring fused ring include a 5-membered ring and a 5-membered fused ring, such as a dihydropyrrolopyrrole ring, a flopyrrole ring, and a thienopyrrole ring.
- Examples of the 6-membered ring and the 6-membered fused ring include a quinoline ring, an isoquinoline ring, a quinazoline ring, a quinosaline ring, a cinnoline ring, a chromium ring, an isochromene ring, a benzopyran ring, a pyridopyrimidine ring, and a pyridopyrazine ring.
- Examples of the three-ring fused ring include a carbazole ring, a dibenzofuran ring, an acridine ring, a phenazine ring, a phenoxazine ring, a phenothiazine ring, and a phenoxatiine ring.
- Y is preferably a monocyclic aromatic heterocycle having 6 members, preferably one heteroatom, and particularly preferably a pyridine ring.
- n represents the valence of ring Y.
- n depends on the type of ring Y shown above. For example, if the ring Y is a pyridine ring, n is 5, and if the ring Y is a triazine ring, n is 3. Since the ring Y is single-bonded to X 1 and X 2 , n is an integer greater than or equal to 2.
- R is a group or atom other than X 1 and X 2 bonded to the ring Y.
- the number of R is the number obtained by subtracting 2 from the valence n of the ring Y, that is, n-2.
- the plurality of Rs may be the same or different.
- R is an alkyl group
- the alkyl group may be linear, branched or cyclic, and may have a structure in which these are combined.
- R is an alkyl group
- a linear alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is preferable.
- X 1 and X 2 are substituted or unsubstituted monovalent aromatic ring groups. It is preferable that at least one of X 1 and X 2 has an aromatic heterocycle, and it is preferable that at least one of X 1 and X 2 has an aromatic condensed ring. More preferably, at least one of X 1 and X 2 is an aromatic condensed ring containing a hetero atom. X 1 and X 2 may be the same or different, and are preferably the same from the viewpoint of optical compensability or ease of manufacture.
- the coupling positions of X 1 and X 2 form a straight line L 1 connecting the center of the ring Y and the center of the ring located farthest from Y among the rings constituting X 1 , and the center of the ring Y and X 2 .
- the angle ⁇ is preferably 110 to 130 °, more preferably 110 to 125 °.
- a compound having an angle ⁇ other than the above range cannot contribute to the orientation of the cycloolefin resin in the optical film, and the orientation of the compound itself due to stretching is not sufficient.
- the rings constituting X 1 and X 2 may be monocyclic or condensed rings. As will be described later, X 1 and X 2 may have an alicyclic ring as long as the ring bonded to the ring Y is an aromatic ring. From the viewpoint of optical compensability, it is preferable that all the rings constituting X 1 and X 2 are aromatic rings.
- the rings constituting X 1 the ring located farthest from Y is hereinafter also referred to as “ring X 1L”.
- the "center of ring X 1L ", which is the ring located farthest from Y among the rings constituting X 1 is defined as follows in the monocyclic ring and the condensed ring.
- the center of the ring X 1L is a point equidistant from the geometric center of each ring constituting the condensed ring.
- the ring located farthest from Y is hereinafter also referred to as “ring X 2L”.
- the "center of ring X 2L " which is the ring located farthest from Y among the rings constituting X 2 , is defined as follows in the monocyclic ring and the condensed ring.
- the center of the ring X 2L is a point equidistant from the geometric center of each ring constituting the condensed ring.
- the angle ⁇ changes depending on the structure of X 1 and X 2 in addition to the coupling position of X 1 and X 2 in the ring Y. Therefore, the angle ⁇ is adjusted to the above range by adjusting the coupling position in the ring Y in consideration of the structures of X 1 and X 2 described below.
- the ring Y is a 6-membered ring, it depends on the structure of X 1 and X 2 , but in order to adjust the angle ⁇ within the above range, it is preferable that X 1 and X 2 are bonded to the meta position, and a hetero atom is formed. It is more preferable to bond the carbon atoms on both sides by sandwiching the film from the viewpoint of the adhesiveness of the obtained optical film.
- X 1 is a substituted or unsubstituted monovalent aromatic ring group.
- X 1 may have at least a structure in which the aromatic ring is single-bonded to Y, and the hydrogen atom bonded to the aromatic ring may be substituted with a substituent.
- X 1 is, for example, have an aromatic ring group represented by X 11 to bind to Y, is substituted with aromatic group or an alicyclic group
- X 11 is represented by X 12, further X 12 is represented by X 13
- It may be a structure in which a plurality of ring structures are bonded by a single bond, such as being substituted with an aromatic ring group or an alicyclic group.
- X 1 of a structure in which a plurality of ring structures are bonded by a single bond can be represented by, for example, the following equation (X).
- Equation (X) -X 11- X 12 -...- X 1L-1 -X 1L
- X 11 is a divalent aromatic ring group bonded to ring Y
- X 12 and X 1L-1 are divalent aromatic ring groups or alicyclic groups
- X 1L is monovalent. It is an aromatic ring group or an alicyclic group.
- L indicates the number of rings of the group represented by the formula (X).
- X 1L is the terminal ring and is the ring located farthest from Y.
- the number of rings including the aromatic ring of X 1 may be one or two or more.
- the number of rings contained in X 1 containing the aromatic ring is preferably 1 to 3, and more preferably 1 to 2.
- Y in the compound (1), cut in X 1, X 2, the number of rings equal in X 1, X 2, or the difference in the number of ring X 1 and X 2 are isolate to be 1 .. That is, in compound (1), ring Y is a ring located substantially at the center of the ring constituting compound (1).
- the ring X 1 has, for example, X 11 ⁇ X 1L in Formula (X), it is preferable that all of them are aromatic.
- the one or two or more aromatic rings contained in X 1 may be a monocyclic ring or a condensed ring. From the viewpoint of optical compensability, it is preferable that at least one of the aromatic rings is a fused ring.
- the aromatic ring may contain a hetero atom, preferably contains a hetero atom.
- the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and a nitrogen atom is particularly preferable from the viewpoint of optical compensation.
- the number of heteroatoms per aromatic ring is preferably 1 to 5, and more preferably 1 to 2. It is preferable that X 1 has a heteroatom because the compound (1) itself is easily oriented in the optical film when it is made into an optical film.
- X 11 to X 1L are a monocyclic ring or a condensed ring, and it is preferable that any one of them is a condensed ring, and it is particularly preferable that X 11 is a condensed ring.
- X 11 to X 1L can each contain preferably 1 to 5, more preferably 1 to 2 heteroatoms, respectively.
- X 11 preferably has a heteroatom next to the carbon atom bonded to Y.
- X 11 preferably has a structure in which a hetero atom is bonded to Y.
- a hydrogen atom bonded to the aromatic ring may be substituted by a substituent.
- substituents include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, an amino group and the like.
- the alkyl group contained in the alkyl group and the alkoxy group may be linear or branched, and may have a structure in which these are combined.
- the substituent is an alkyl group or an alkoxy group, the number of carbon atoms is more preferably 1 to 5.
- X 1 preferably has no substituent from the viewpoint of heat resistance.
- Examples of the aromatic ring contained in X 1 include a benzene ring and the like as a monocyclic aromatic ring containing no heteroatom, and a naphthalene ring, an anthracene ring and the like as an aromatic condensed ring.
- Examples of the aromatic ring containing a hetero atom include the aromatic heterocycle exemplified as Y above.
- X 1 has an aromatic ring containing a hetero atom, it is preferable that X 1 has a hetero atom next to the carbon atom bonded to the ring Y.
- X 1 preferably has a structure in which a hetero atom is bonded to Y.
- compounds 1-1 to 1-6 whose structures are represented by the following formulas 1-1 to 1-6 are preferable.
- a straight line L 1 connecting the center of Y and the center of the ring located farthest from Y among the rings constituting X 1 in such compounds 1-1 to 1-6, and the center of Y and X 2 are formed.
- the angle formed by the straight line L 2 connecting the center of the ring located farthest from Y, that is, the angle ⁇ formed by X 1 and X 2 with respect to the ring Y will be described below.
- the ring Y is a pyridine ring.
- X 1 an aromatic ring group which is located to the left of the pyridine ring in, when the aromatic ring group on the right side and X 2, both X 1 and X 2 is 2-position a bond benzimidazole It is an aromatic ring group. Then, there is one ring each constituting X 1 and X 2 , and the ring is the ring located farthest from Y among the rings constituting X 1 and X 2.
- FIG. 1A shows an xy coordinate diagram used to determine the center of ring Y (pyridine ring) in compound 1-1.
- the center Yc of the pyridine ring is the geometric center of the hexagonal pyridine ring, and the respective xy coordinates at all the vertices belonging to the hexagon, that is, (x 1 , y 1 ), (x 2 , y 2 ),. It is the position of the xy coordinate obtained by arithmetically averaging (x 3 , y 3 ), (x 4 , y 4 ), (x 5 , y 5 ), and (x 6 , y 6).
- the x coordinate at the center Yc of the pyridine ring is indicated by (x 1 + x 2 + x 3 + x 4 + x 5 + x 6 ) / 6, and the y coordinate is (y 1 + y 2 + y 3 + y 4 + y 5). + Y 6 ) / 6.
- FIG. 1B shows an xy coordinate diagram used to determine the center of the ring (benzimidazole ring) located farthest from Y in X 1 of compound 1-1.
- the coordinates of each vertex belonging to the benzimidazole ring are (x 1 , y 1 ), (x 2 , y 2 ), (x 3 , y 3 ), (x 4 , y 4 ), (x 5 , y 5 ).
- the geometric center X 1 b c of the benzene ring and the geometric center X 1 a c of the imidazole ring are obtained in the same manner as described above.
- the x coordinate at the geometric center X 1 bc of the benzene ring is indicated by (x 4 + x 5 + x 6 + x 7 + x 8 + x 9 ) / 6
- the y coordinate is (y 4 + y 5 + y 6 + y). It is indicated by 7 + y 8 + y 9) / 6.
- X-coordinate of the geometric center X 1a c of the imidazole ring is indicated by (x 1 + x 2 + x 3 + x 4 + x 5) / 5, y coordinates are represented by (y 1 + y 2 + y 3 + y 4 + y 5/5 it is.
- the center X 2 c of the ring (benzimidazole ring) located farthest from Y in X 2 of compound 1-1 is also the geometric center X 2 bc and the imidazole ring of the benzene ring in X 2 as in the case of X 1 above. seeking the geometric center X 2a c, draw a straight line connecting the two points, the point bisecting the straight line and the center X 2 c of the benzimidazole ring in X 2.
- the angle ⁇ formed by X 1 and X 2 with respect to the ring Y is a straight line L connecting the center Yc of the pyridine ring and the center X 1 c of the benzoimidazole ring located on the left side thereof, as shown in FIG. 1C.
- 1 is an angle of a straight line L 2 connecting the centers Yc pyridine ring and the center X 2 c of the benzimidazole ring, located on the right side.
- the angle ⁇ in the compound 1-1 thus obtained is 112 °.
- the ring Y in compound 1-2 is a pyridine ring, and the aromatic ring group located on the left side of the pyridine ring is X 1 and the aromatic ring group located on the right side is X 2 .
- X 1 is composed of two benzimidazole rings and X 2 is composed of two benzene rings.
- the angle ⁇ formed by X 1 and X 2 with respect to ring Y is located farthest from the pyridine ring among the two benzoimidazole rings constituting X 1 located at the center of the pyridine ring and to the left of the center.
- ring Y is a condensed ring.
- the ring Y in compound 1-3 is a pyrazolo [1,5-a] pyrimidine ring, and the aromatic ring group located on the left side (5th position) of the pyrazolo [1,5-a] pyrimidine ring is X 1 and the right side (2).
- X 1 is a 2-pyridyl group and X 2 is a phenyl group.
- the angle ⁇ formed by X 1 and X 2 with respect to ring Y is a straight line L 1 connecting the center of the pyrazolo [1,5-a] pyrimidine ring and the center of the pyridine ring located on the left side thereof. it is an angle of a straight line L 2 connecting the center of the benzene ring located pyrazolo [1,5-a] central pyrimidine ring and its right.
- the angle ⁇ in the compound 1-3 thus obtained is 144 °.
- angles ⁇ obtained for compounds 1-4 to 1-6 in the same manner as described above are 120 ° for compound 1-4, 115 ° for compound 1-5, and 123 ° for compound 1-6.
- compounds 1 to which Y is a pyridine ring and at least one of X 1 and X 2 contains a condensed ring in that a high phase difference, for example, a phase difference value Ro can be obtained.
- Compound 1-2 and compound 1-4 are preferable.
- Compound 1-1 and compound 1-1 in which X 1 and X 2 are bonded to carbon atoms on both sides of the nitrogen atom of the pyridine ring, and at least one of them contains a condensed ring, in that a higher phase difference, for example, a phase difference value Ro can be obtained.
- Compound 1-2 is preferred. Further, compound 1-2 is particularly preferable from the viewpoint of better adhesiveness.
- one type of compound (1) may be used alone, or two or more types may be used in combination.
- the compound (1) has, for example, 0.5 to 10 with respect to the cycloolefin resin (100% by mass) which is the main raw material of the optical film from the viewpoint of bleed-out and prevention of precipitation while exhibiting the above-mentioned effects of the present invention. It is added in a proportion of% by mass, preferably in the range of 2 to 6% by mass.
- compound (1) acts as a retardation enhancer.
- the compound (1) and other retardation enhancers other than the compound (1) may be used in combination as long as the effects of the present invention are not impaired.
- the other phase difference increasing agent include those composed of a disk-shaped or rod-shaped compound.
- a compound having at least two aromatic rings can be preferably used as the phase difference increasing agent.
- the retardation enhancer preferably has maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.
- the optical film of the present invention contains a cycloolefin resin as a resin mainly constituting the optical film.
- the optical film of the present invention may contain a resin other than the cycloolefin resin as long as the effects of the present invention are not impaired, but the resin is preferably only the cycloolefin resin.
- the cycloolefin resin used in the present invention include (co) polymers having a structure represented by the following general formula (4).
- R 1 to R 4 are independently hydrogen atoms, hydrocarbon groups, halogen atoms, hydroxy groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, silyl groups, or polar groups ( That is, it is a hydrocarbon group substituted with a halogen atom, a hydroxy group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, or a silyl group).
- R 1 to R 4 two or more of them may be bonded to each other to form an unsaturated bond, a monocyclic ring or a polycyclic ring, and the monocyclic or polycyclic ring has a double bond.
- an aromatic ring may be formed.
- the alkylidene group may be formed by R 1 and R 2 or by R 3 and R 4.
- p and m are integers of 0 or more.
- the cycloolefin resin according to the present invention preferably has a polar group.
- R 1 and R 3 are hydrogen atoms or carbon atoms 1 to 10, more preferably 1 to 4, Particularly preferably, it is 1 to 2 hydrocarbon groups, R 2 and R 4 are hydrogen atoms or monovalent organic groups, and at least one of R 2 and R 4 has a polarity other than a hydrogen atom and a hydrocarbon group.
- M is an integer of 0 to 3
- Those having 0 are preferable.
- Examples of the polar group of the specific monomer include a carboxy group, a hydroxy group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group and the like, and these polar groups include a linking group such as a methylene group. They may be combined via. Further, a hydrocarbon group in which a polar divalent organic group such as a carbonyl group, an ether group, a silyl ether group, a thioether group or an imino group is bonded as a linking group is also mentioned as a polar group. Among these, a carboxy group, a hydroxy group, an alkoxycarbonyl group or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is particularly preferable.
- the monomer in which at least one of R 2 and R 4 is a polar group represented by the formula- (CH 2 ) n COOR 10 is a material in which the obtained cycloolefin resin has a high glass transition temperature and low hygroscopicity. It is preferable in that it has excellent adhesion to and from.
- R 10 is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, a hydrocarbon group, preferably an alkyl group.
- n is an integer of 0 to 5, preferably 0 to 2.
- copolymerizable monomer examples include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.
- the number of carbon atoms of the cycloolefin is preferably 4 to 20, and more preferably 5 to 12.
- one type of cycloolefin resin can be used alone, or two or more types can be used in combination.
- the preferred molecular weight of the cycloolefin resin according to the present invention is 0.2 to 5 dL / g, more preferably 0.3 to 3 dLl / g, and particularly preferably 0.4 to 1.5 dL / g at an intrinsic viscosity [ ⁇ ] inh.
- the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw). Is preferably in the range of 20000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably 40,000 to 200,000.
- the heat resistance, water resistance, chemical resistance and mechanical properties of the cycloolefin resin and the molding process as the optical film of the present invention are obtained.
- the property becomes good.
- the glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110 ° C. or higher, preferably 110 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 220 ° C.
- Tg is less than 110 ° C., it is not preferable because it may be deformed by use under high temperature conditions or secondary processing such as coating and printing.
- Tg exceeds 350 ° C., the molding process becomes difficult, and the possibility that the resin is deteriorated by the heat during the molding process increases.
- the cycloolefin resin is a specific hydrocarbon-based resin described in JP-A-9-2215777 and JP-A-10-287732, or a known thermoplastic, as long as the effects of the present invention are not impaired.
- Resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles and the like may be blended, and additives such as specific wavelength dispersants, hydrocarbon compounds and rubber particles may be included.
- the optical film of the present invention may contain a conventionally known retardation enhancer other than the compound (1) as long as the effects of the present invention are not impaired.
- the optical film of the present invention can further contain various additives other than the retardation enhancer. Examples of the additive include a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent and the like.
- a plasticizer in the optical film of the present invention, can also be used in order to improve the fluidity of the composition during production and the flexibility of the optical film.
- the plasticizer include a phthalate ester type, a fatty acid ester type, a trimellitic acid ester type, a phosphoric acid ester type, a polyester type, an epoxy type and the like.
- polyester-based and phthalate-based plasticizers are preferably used.
- Polyester-based plasticizers are superior in non-migration and extraction resistance to phthalate-based plasticizers such as dioctyl phthalate, but are slightly inferior in plasticizing effect and compatibility.
- plasticizers According to the application, it can be applied to a wide range of applications.
- the polyester-based plasticizer is a reaction product of a monovalent to tetravalent carboxylic acid and a monovalent to hexavalent alcohol, and a product obtained by reacting a divalent carboxylic acid with a glycol is mainly used. ..
- Typical divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
- glycol examples include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene and dipropylene. These divalent carboxylic acids and glycols may be used alone or in combination.
- the ester-based plasticizer may be in the form of ester, oligoester, or polyester, and the molecular weight is preferably in the range of 100 to 10000, more preferably in the range of 600 to 3000. If the molecular weight is in this range, the plasticizing effect is large.
- the molecular weight of polyester is a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC).
- the viscosity of the plasticizer correlates with the molecular structure and molecular weight, but in the case of an adipic acid-based plasticizer, the range of 200 to 5000 mPa ⁇ s (25 ° C.) is preferable from the relationship of compatibility and plasticization efficiency. Furthermore, some polyester-based plasticizers may be used in combination.
- the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the cycloolefin resin which is the main raw material of the optical film of the present invention. If the amount of the plasticizer added exceeds 30 parts by mass, the surface becomes sticky, which is not practically preferable.
- the optical film of the present invention preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole-based, 2-hydroxybenzophenone-based, and phenyl salicylate-based ones.
- the ultraviolet absorber used include benzotriazole-based, 2-hydroxybenzophenone-based, and phenyl salicylate-based ones.
- the ultraviolet absorber having a molecular weight of 400 or more is hard to volatilize at a high boiling point and is hard to scatter even during high-temperature molding, so that the weather resistance is effectively improved by adding a relatively small amount. be able to.
- Examples of ultraviolet absorbers having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1). 1,3,3-Tetrabutyl) -6- (2H-benzotriazole-2-yl) phenol] and other benzotriazoles, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, as well as 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid.
- 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3-) Tetrabutyl) -6- (2H-benzotriazole-2-yl) phenol] is particularly preferred.
- the ultraviolet absorber has an effect as an ultraviolet absorber, and from the viewpoint of preventing bleed-out and precipitation, for example, 0.1 to 5.0% by mass with respect to the cycloolefin resin which is the main raw material of the optical film. It is preferably added in the range of 0.5 to 5.0% by mass.
- antioxidant a commonly known antioxidant can be used for an optical film.
- lactone-based, sulfur-based, phenol-based, double-bonded, hindered amine-based, and phosphorus-based compounds can be preferably used.
- those commercially available from BASF Japan Ltd. under the trade names IrgafosXP40 and IrgafosXP60 are preferable.
- the phenolic compound preferably has a structure of 2,6-dialkylphenol, and is commercially available from BASF Japan Ltd., for example, from Irganox1076, Irganox1010, and ADEKA Corporation under the trade name of ADEKA STAB AO-50. Those are preferable.
- the phosphorus compounds are, for example, from Sumitomo Chemical Co., Ltd., SumilizerGP, from ADEKA Corporation to ADK STAB PEP-24G, ADK STAB PEP-36 and ADK STAB 3010, from BASF Japan Co., Ltd. IRGAFOS P-EPQ, Sakai Chemical Industry Co., Ltd. It is preferable that the product is commercially available from the company under the trade name GSY-P101.
- the hindered amine compounds are preferably commercially available from BASF Japan Ltd. under the trade names of Tinuvin 144 and Tinuvin 770, and from ADEKA Corporation under the trade names of ADK STAB LA-52.
- the sulfur compounds are preferably those commercially available from Sumitomo Chemical Co., Ltd. under the trade names of Sumilizer TPL-R and Sumilizer TP-D.
- the double bond compound is commercially available from Sumitomo Chemical Co., Ltd. under the trade names of Sumilizer GM and Sumilizer GS.
- the amount of these antioxidants to be added is appropriately determined according to the process of regeneration and use, and is, for example, 0.05 to 20% by mass with respect to the cycloolefin resin which is the main raw material of the optical film. , Preferably added in the range of 0.1 to 1% by mass.
- antioxidants can obtain a synergistic effect by using several kinds of compounds of different systems in combination rather than using only one kind.
- the combined use of lactone-based, phosphorus-based, phenol-based and double-bonding compounds is preferable.
- the optical film may be composed of one layer (single layer) or a plurality of layers, but it should be a single layer because there is little display unevenness and it is possible to reduce the thickness. Is preferable.
- the physical characteristics of the optical film of the present invention are preferably 30 ⁇ m or less from the viewpoint of thinning the film thickness. Further, from the viewpoint of strength, uniformity and productivity, the optical film film thickness is more preferably 5 to 30 ⁇ m.
- the in-plane retardation value Ro (nm) of the optical film of the present invention defined by the following formula (i) is preferably 30 nm or more, and the thickness direction retardation value Rt defined by the following formula (ii).
- (Nm) is preferably 100 nm or more.
- n x is the refractive index of the optical film in the slow axis direction in the film plane.
- n y is the refractive index in the direction (fast axis direction) perpendicular to the optical film, the slow axis in the film plane
- nz is the refractive index in the thickness direction of the optical film.
- d is the film thickness (nm) of the optical film.
- the refractive index is a refractive index measured at a wavelength of 550 nm in an environment of 23 ° C. and 55% RH.
- the in-plane retardation value Ro and the thickness direction retardation value Rt of the optical film can be measured by the following methods.
- the optical film is humidity-controlled for 24 hours in an environment of 23 ° C. and 55% RH.
- the average refractive index of the obtained optical film is measured with an Abbe refractometer. Further, the thickness d of the optical film is measured using a commercially available micrometer.
- the retardation value Ro and the retardation value Rt of the optical film after humidity control at a measurement wavelength of 550 nm are measured in an environment of 23 ° C. and 55% RH using an automatic birefringence meter Axoscan (manufactured by Axometrics), respectively. Measure below. Specifically, the measurement is performed by the following methods i) to iii).
- phase difference value Ro when light having a measurement wavelength of 550 nm is incident parallel to the normal direction of the surface of the sample piece is measured by Axoscan.
- the in-plane slow-phase axis of the sample piece is set as the tilt axis (rotation axis), and the measurement wavelength is 550 nm from the angle of ⁇ (incident angle ( ⁇ )) with respect to the normal of the surface of the sample piece.
- the phase difference value R ( ⁇ ) when light is incident is measured.
- the phase difference value R ( ⁇ ) is measured at 6 points every 10 ° in the range where ⁇ is 0 ° to 50 °.
- the in-plane slow-phase axis of the sample piece can be confirmed by axoscan.
- axoscan From the measured retardation value Ro and retardation value R ( ⁇ ), and the above-mentioned average refractive index and thickness, Axoscan calculated n x , n y, and n z , and used the above equation (ii). Based on this, the phase difference value Rt at the measurement wavelength of 550 nm is calculated.
- the optical film of the present invention can obtain a high optical compensation value (phase difference) even when the film thickness is reduced in response to the thinner display device.
- the retardation value Ro when the film thickness is 20 ⁇ m is preferably 80 nm or more, more preferably 145 nm or more.
- the optical film of the present invention preferably has high transparency.
- the haze of the optical film is preferably 4.0% or less, more preferably 2.0% or less, and even more preferably 1.0% or less.
- Haze can be measured according to JIS K-6714 with a haze meter (HGM-2DP, Suga Test Instruments) at 25 ° C. and 60% RH for a sample of 40 mm ⁇ 80 mm.
- Examples of the method for molding the optical film of the present invention include a molding method including a known stretching step such as a melt casting method, a solution casting method, and a calender molding method. It is preferably used in the melt casting method and the solution casting method, and the solution casting method is particularly preferable.
- a production method including the following steps (1) to (3) is used.
- (1) A step of preparing a dope containing a compound having a structure represented by the above general formula (1), a cycloolefin resin and a solvent (hereinafter, referred to as “dope preparation step”).
- (2) A step of casting the dope obtained in (1) on a support to obtain an unstretched film (hereinafter referred to as “casting step”).
- casting step an unstretched film
- stretch step A step of stretching the unstretched film obtained in (2).
- the stretching step of (3) usually includes a step of drying the solvent from the unstretched film obtained in (2) (hereinafter referred to as “drying step”). Further, the optical film obtained by the stretching step is usually wound into a roll shape.
- drying step a step of drying the solvent from the unstretched film obtained in (2)
- winding process a step of winding the optical film obtained by the stretching step.
- Dope preparation step In an organic solvent mainly containing a good solvent for the cycloolefin resin according to the present invention, the cycloolefin resin and the compound (1) according to the present invention, and in some cases, other resins or additions are added to the organic solvent.
- the above compound (1) and, in some cases, other additives are contained in the step of dissolving the agent with stirring to prepare a dope, or in the cycloolefin resin solution (which may contain other resins in some cases). This is a step of mixing the solutions to prepare a dope which is the main solution.
- the organic solvent useful for forming the dope dissolves the cycloolefin resin according to the present invention, the compound (1) according to the present invention and other compounds at the same time. Anything that can be used can be used without limitation.
- organic solvent used examples include chlorine-based solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n-butanol, 2-butanol, and the like.
- Alcohol-based solvents methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethylsulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; and the like. Only one of these solvents may be used, or two or more of these solvents may be used in combination.
- MEK methyl ethyl ketone
- the organic solvent used in the present invention is preferably a mixed solvent of a good solvent and a poor solvent, and the good solvent is, for example, dichloromethane as a chlorine-based organic solvent and methyl acetate as a non-chlorine-based organic solvent.
- the good solvent is preferably
- the poor solvent is preferably an alcohol solvent, and it is preferable that the alcohol solvent is selected from methanol, ethanol and butanol from the viewpoint of improving the peelability and enabling high-speed casting. Of these, it is preferable to use methanol or ethanol.
- the web the dope film formed by spreading the dope on the casting support is called the web
- the proportion of alcohol is small, it also has a role of promoting the dissolution of cycloolefin resin and other compounds in a non-chlorine organic solvent system.
- the cycloolefin resin according to the present invention, the compound (1) according to the present invention, and other compounds are dissolved at normal pressure, below the boiling point of the main solvent, or pressurized above the boiling point of the main solvent.
- Various dissolution methods such as a method of performing at high pressure can be used, but a method of pressurizing above the boiling point of the main solvent is particularly preferable.
- the concentration of the cycloolefin resin according to the present invention in the dope is preferably in the range of 10 to 40% by mass.
- Compound (1) and other additives are added to the dope during or after dissolution in a predetermined amount shown above with respect to, for example, a cycloolefin resin, dissolved and dispersed, and then filtered through a filter medium to defoam. And send it to the next process with a liquid feed pump.
- a main filter provided with a leaf disk filter
- a filter medium having a 90% collection particle size of, for example, 10 to 100 times the average particle size of the fine particles.
- the filter medium used for filtration preferably has a low absolute filtration accuracy, but if the absolute filtration accuracy is too small, the filter medium is likely to be clogged, and the filter medium must be replaced frequently. , There is a problem of reducing productivity.
- the filter medium used for the dope containing the cycloolefin resin and the compound (1) is preferably an absolute filtration accuracy of 0.008 mm or less, more preferably 0.001 to 0.008 mm. , 0.003 to 0.006 mm, more preferably filter media.
- the material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a filter medium made of plastic fibers such as polypropylene and Teflon (registered trademark) and a metal filter medium such as stainless steel fibers may fall off. It is preferable because there is no such thing.
- the dope flow rate during filtration is preferably 10 to 80 kg / (h ⁇ m 2 ), preferably 20 to 60 kg / (h ⁇ m 2 ).
- the dope flow rate during filtration is 10 kg / (h ⁇ m 2 ) or more, efficient productivity is achieved, and the dope flow rate during filtration is within 80 kg / (h ⁇ m 2 ). If this is the case, the pressure applied to the filter medium becomes appropriate and the filter medium is not damaged, which is preferable.
- the filter pressure is preferably 3500 kPa or less, more preferably 3000 kPa or less, and further preferably 2500 kPa or less.
- the filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area.
- the main dope may contain about 10 to 50% by mass of the return material.
- the return material is, for example, a finely crushed optical film of the present invention, in which both side portions of the film are cut off, which is generated when the optical film is formed, or a specified value of the film is determined by scratches or the like.
- Exceeded optical film raw fabric is included.
- a resin obtained by pre-pelling the cycloolefin resin or the like according to the present invention can also be preferably used.
- the metal support in the casting process is preferably a mirror-finished surface, and the metal support is preferably a stainless steel belt or a drum whose surface is plated with a casting.
- the width of the cast can be in the range of 1 to 4 m, preferably in the range of 1.3 to 3 m, more preferably in the range of 1.5 to 2.8 m.
- the surface temperature of the metal support in the casting step is set in the range of ⁇ 50 ° C. to below the temperature at which the solvent does not boil and foam, and more preferably in the range of ⁇ 30 to 0 ° C. A higher temperature is preferable because the drying speed of the web can be increased, but if it is too high, the web may foam or the flatness may deteriorate.
- the preferred support temperature is appropriately determined from 0 to 100 ° C, and more preferably in the range of 5 to 30 ° C.
- the method of controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air and a method of bringing hot water into contact with the back side of the metal support. It is preferable to use hot water because the heat transfer is more efficient and the time until the temperature of the metal support becomes constant is short.
- warm air in consideration of the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, air at a temperature higher than the target temperature may be used while preventing foaming. ..
- the die is preferably a pressure die in which the slit shape of the die base portion can be adjusted and the film thickness can be easily made uniform.
- the pressure die includes a coat hanger die, a T die, and the like, and any of them is preferably used.
- the surface of the metal support is a mirror surface. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the doping amount may be divided and laminated.
- a method of blowing wind from the web side there are a method of blowing wind from the web side, a method of transferring heat from the back surface of the support with a liquid, a method of transferring heat from the front and back surfaces with radiant heat, etc. Is good and preferable.
- a method of combining them is also preferably used. It is preferable to dry the web on the support after casting in an atmosphere of 30 to 100 ° C. on the support. In order to maintain the atmosphere at 30 to 100 ° C., it is preferable to blow warm air at this temperature on the upper surface of the web or heat it by means such as infrared rays.
- the temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.
- the solvent in the web is evaporated in the solvent evaporation step, but the amount of the residual solvent in the web on the metal support at the time of peeling is preferably in the range of 15 to 100% by mass.
- the amount of residual solvent is preferably controlled by the drying temperature and drying time in the solvent evaporation step.
- the amount of the residual solvent is 15% by mass or more, the drying time is not long and the productivity is improved in the drying process on the support. Further, when the amount of the residual solvent is 100% by mass or less, the unstretched film has self-supporting property, poor peeling of the unstretched film can be avoided, and the mechanical strength of the unstretched film can be maintained. The flatness is improved, and the occurrence of slippage and vertical streaks due to peeling tension can be suppressed.
- the amount of residual solvent in the web or unstretched film is defined by the following formula (Z).
- Residual solvent amount (%) (mass before heat treatment of web or unstretched film-mass after heat treatment of web or unstretched film) / (mass after heat treatment of web or unstretched film) ⁇ 100
- the heat treatment for measuring the amount of residual solvent means that the heat treatment is performed at 115 ° C. for 1 hour.
- the peeling tension when peeling the web from the metal support to form an unstretched film is usually in the range of 196 to 245 N / m, but when wrinkles are likely to occur during peeling, the tension is 190 N / m or less. It is preferable to peel off with.
- the temperature at the peeling position on the metal support is preferably in the range of ⁇ 50 to 40 ° C., more preferably in the range of 10 to 40 ° C., and in the range of 15 to 30 ° C. Is the most preferable.
- the drying step can be divided into a preliminary drying step (first drying step) and a main drying step (second drying step).
- Pre-drying step The unstretched film obtained by peeling the web from the metal support is pre-dried in the first drying apparatus.
- the film may be dried while being conveyed by a large number of rollers arranged vertically, or may be dried while being conveyed by fixing both ends of the film with clips as in a tenter dryer. Good.
- the means for drying the unstretched film is not particularly limited, and generally, hot air, infrared rays, heating rollers, microwaves, etc. can be used, but from the viewpoint of simplicity, hot air is preferable.
- the drying temperature in the pre-drying step of the unstretched film is preferably ⁇ 5 ° C. or lower at the glass transition point of the unstretched film, and it is effective to perform heat treatment at a temperature of 30 ° C. or higher for 1 minute or longer and 30 minutes or shorter. ..
- the drying temperature is in the range of 40 to 150 ° C., more preferably in the range of 50 to 100 ° C.
- the amount of residual solvent may be adjusted at the initial stage of the stretching step.
- the amount of residual solvent is preferably controlled by the drying temperature and drying time in the pre-drying step.
- (3-2) Stretching Step In the method for producing an optical film of the present invention, a stretching device is used to stretch an unstretched film having a specific residual solvent amount at a low stretching ratio, so that the film surface is microscopic. It is possible to suppress the occurrence of various crazes. Further, at the time of the stretching, the compound (1) itself is oriented, and the compound (1) acts as described above to control the orientation of the cycloolefin resin in the film, thereby aiming at a low stretching ratio. The phase difference value Ro and the phase difference value Rt can be obtained.
- the amount of residual solvent at the start of stretching is 1% by mass or more and less than 15% by mass in the step of stretching the unstretched film. More preferably, the amount of residual solvent is in the range of 2 to 10% by mass.
- the amount of residual solvent at the start of stretching is less than 1% by mass, excessive stress is applied during stretching, and minute crazes are likely to occur near the film surface, which may deteriorate the adhesiveness with UV glue.
- the amount of the residual solvent is 15% by mass or more, stress is less likely to be applied during stretching, so that the compound (1) and the cycloolefin resin in the film are less likely to be sufficiently oriented.
- the optical film of the present invention is produced by stretching the unstretched film in the longitudinal direction (also referred to as MD direction and casting direction) and / or the width direction (also referred to as TD direction), and at least by a stretching device. , It is preferable to produce by stretching in the width direction.
- the stretching operation may be performed in multiple stages. Further, when biaxial stretching is performed, simultaneous biaxial stretching may be performed, or biaxial stretching may be performed step by step.
- stepwise means, for example, that stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any of the steps. Is also possible.
- Stretching in the longitudinal direction ⁇ Stretching in the width direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the width direction ⁇ Stretching in the width direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction ⁇ Stretching in the longitudinal direction Also includes the case of stretching in one direction and contracting the other by relaxing the tension.
- the glass transition temperature of the unstretched film is set to Tg in the longitudinal direction and / or the width direction, preferably in the width direction, so that the film thickness after stretching is within a desired range.
- Tg in the longitudinal direction and / or the width direction, preferably in the width direction.
- the stretching temperature is preferably in the range of (Tg + 10) to (Tg + 40) ° C.
- the glass transition temperature Tg referred to here is an intermediate point glass transition temperature (Tmg) obtained by measuring at a heating rate of 20 ° C./min using a commercially available differential scanning calorimetry device and obtaining it according to JIS K7121 (1987). Is.
- a specific method for measuring the glass transition temperature Tg of an optical film is to measure it using a differential scanning calorimeter DSC220 manufactured by Seiko Instruments Inc. in accordance with JIS K7121 (1987).
- the optical film of the present invention it is preferable to stretch the unstretched film at least in the width direction at a stretching ratio within the range of 10 to 100% with respect to the original width, and further, in the longitudinal direction and the width direction of the film. It is more preferable to stretch each at a stretching ratio in the range of 5 to 60%. Within the above range, the generation of minute crazes in the vicinity of the film due to high-magnification stretching is suppressed, and in particular, by containing the compound (1), the desired retardation value Ro and retardation value Rt can be obtained.
- the optical film can be thinned.
- the stretching ratio as used in the present invention is a change from the length d 11 of the length d 12 of the length or width of the optical film after stretching with respect to the length d 11 of the length or width of the unstretched film before stretching.
- the ratio of quantity (%) is a change from the length d 11 of the length d 12 of the length or width of the optical film after stretching with respect to the length d 11 of the length or width of the unstretched film before stretching.
- the method of stretching in the longitudinal direction For example, a method of making a difference in peripheral speed between multiple rolls and stretching in the vertical direction using the difference in peripheral speed between rolls, fixing both ends of the unstretched film with clips or pins, and moving the distance between the clips and pins in the traveling direction.
- Examples thereof include a method of spreading in the vertical direction and stretching in the vertical direction, and a method of spreading in the vertical and horizontal directions at the same time and stretching in both the vertical and horizontal directions. Of course, these methods may be used in combination.
- JP-A-62-46625 In order to stretch in the width direction, for example, all or part of the drying process as shown in JP-A-62-46625 is held in the width direction with clips or pins at both ends of the width of the web. While drying (called a tenter method), a tenter method using a clip and a pin tenter method using a pin are preferably used.
- the stretching speed is 250% / min or more, the flatness is improved and the film can be processed at high speed, which is preferable from the viewpoint of production suitability.
- the stretching speed is 500% / min or less, the film breaks. It can be processed without any problem, which is preferable.
- the preferable stretching speed is in the range of 300 to 400% / min, which is effective when stretching at a low magnification.
- the stretching speed is defined by the following formula 1.
- holding and relaxation are usually performed after stretching. That is, in this step, it is preferable to perform a stretching step of stretching the unstretched film, a holding step of holding the obtained stretched film in a stretched state, and a relaxing step of relaxing the stretched film in the stretched direction in these orders.
- the stretching at the stretching rate achieved in the stretching step is held at the stretching temperature in the stretching step.
- the relaxation step the stretching in the stretching step is held in the holding step, and then the tension for stretching is released to relax the stretching.
- the relaxation step may be performed at a temperature equal to or lower than the stretching temperature in the stretching step.
- the stretched film after stretching is heated and dried by a second drying device.
- a means for preventing the mixing of used hot air by installing a nozzle capable of exhausting used hot air (air containing a solvent or wet air) is also preferably used.
- the hot air temperature is more preferably in the range of 40 to 350 ° C.
- the drying time is preferably about 5 seconds to 60 minutes, more preferably 10 seconds to 30 minutes.
- the heating and drying means is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, etc. can be used. From the viewpoint of simplicity, it is preferable to dry the film with hot air or the like while transporting the film with the transport rollers arranged in a staggered pattern.
- the drying temperature is more preferably in the range of 40 to 350 ° C. in consideration of the amount of residual solvent, the expansion / contraction rate during transportation, and the like.
- the drying step it is preferable to dry the stretched film until the amount of residual solvent is 0.5% by mass or less. As a result, the optical film of the present invention can be obtained.
- Winding Step (4-1) Knurling After a predetermined heat treatment or cooling treatment, it is preferable to provide a slitter on the optical film before winding to cut off the end portion in order to obtain a good winding shape. Further, it is preferable to perform knurling on both ends of the width.
- the knurling process can be formed by pressing a heated embossed roller against the width end of the optical film. Fine irregularities are formed on the embossed roller, and by pressing the irregularities, the optical film can be formed with irregularities and the edges can be made bulky.
- the height of the knurling at both ends of the width of the optical film of the present invention is preferably 4 to 20 ⁇ m and 5 to 20 mm in width.
- the above knurling process is performed in the film forming process after the completion of drying and before winding.
- the winding method a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.
- the polarizing plate of the present invention is characterized by comprising a polarizing element and an optical film of the present invention arranged on at least one surface of the polarizing element.
- the polarizing plate has, for example, a polarizing element and two protective films arranged on both sides of the polarizing element, and at least one of the two protective films is the optical film of the present invention.
- FIG. 2 is a cross-sectional view showing a configuration example of the polarizing plate of the present invention.
- the polarizing plate 10 has a polarizing element 1 and protective films 2 and 3 arranged on both surfaces of the polarizing element 1. At least one of the protective films 2 and 3 is the optical film of the present invention.
- the polarizer 1 and the protective films 2 and 3 are bonded to each other via an arbitrary adhesive layer (not shown).
- any suitable polarizer can be used.
- a dichroic substance such as iodine or a bicolor dye is adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer system partially saponified film.
- a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer system partially saponified film.
- examples thereof include uniaxially stretched films, polyene-based oriented films such as a dehydrated product of polyvinyl alcohol and a dehydrogenated product of polyvinyl chloride.
- a polarizer in which a dichroic substance such as iodine is adsorbed on a polyvinyl alcohol-based film and uniaxially stretched is particularly preferable because of its high polarization
- a polarizer obtained by adsorbing iodine on a polyvinyl alcohol-based film and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times the original length. .. If necessary, boric acid, zinc sulfate, zinc chloride and the like may be contained, or the mixture may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing.
- the polyvinyl alcohol-based film be washed with water to clean the surface of the polyvinyl alcohol-based film and anti-blocking agents, but the swelling of the polyvinyl alcohol-based film also has the effect of preventing non-uniformity such as uneven dyeing. is there.
- Stretching may be performed after dyeing with iodine, or may be stretched while dyeing. Alternatively, it may be stretched and then stained with iodine. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.
- the polarizer preferably satisfies 0.030 ⁇ Rpva ⁇ 0.040.
- Rpva is more preferably 0.030 ⁇ Rpva ⁇ 0.039, and particularly preferably 0.030 ⁇ Rpva ⁇ 0.035. It is presumed that such characteristics are satisfied by increasing the amount of crystals that do not contribute to the orientation in the polarizer (typically, the orientation is low).
- Rpva is a polarizer in such a range, it can have excellent dimensional stability and optical durability in a high temperature and high humidity environment. As a result, even when the polarizer is used for a polarizing plate in which an optical film is provided on only one side of the polarizer, dimensional change and deterioration of optical characteristics are unlikely to occur, and practically acceptable dimensional stability and optical durability. Sex can be realized.
- the dichromatic ratio DR of the polarizer is preferably 160 or more, more preferably 160 to 220, particularly preferably 170 to 210, and most preferably 175 to 185.
- a liquid crystal panel and a liquid crystal display device having high front contrast can be obtained by using the polarizing plate of the present invention.
- Such liquid crystal panels and liquid crystal display devices are suitable for, for example, television applications.
- the two-color ratio DR can be calculated from the following formula.
- Two-color ratio DR log (0.919 / k2) / log (0.919 / k1)
- k1 is the transmittance of the polarizer in the transmission axis direction
- k2 is the transmittance of the polarizer in the absorption axis direction
- the constant 0.919 is the interfacial reflectance.
- the transmittance (single transmittance) Ts of the polarizer is preferably 42% or more, more preferably 42.0% or more and 44.0% or less, and particularly preferably 42.5% or more and 43.0% or less. Is.
- a liquid crystal panel or a liquid crystal display device having high brightness can be obtained by using the polarizing plate of the present invention.
- Such liquid crystal panels and liquid crystal display devices are suitable for, for example, television applications.
- the transmittance of the polarizing plate can be obtained from the following formula.
- Transmittance ⁇ (k1 + k2) / 2 ⁇ x 100 [%]
- k1 is the transmittance of the polarizer in the transmission axis direction
- k2 is the transmittance of the polarizer in the absorption axis direction.
- a polarizer containing a polyvinyl alcohol (PVA) -based resin containing a dichroic substance such as iodine or a dichroic dye as a main component can be used.
- the iodine content of the polarizer is preferably 1.8% by mass or more and 5.0% by mass or less, and more preferably 2.0% by mass or more and 4.0% by mass or less.
- the boric acid content of the polarizer is preferably 0.5% by mass or more and 3.0% by mass or less, more preferably 1.0% by mass or more and 2.8% by mass or less in terms of boron, and is particularly preferable. Is 1.5% by mass or more and 2.6% by mass or less. Thereby, a polarizer having excellent dimensional stability and optical durability in a humidified environment can be obtained without increasing the amount of boric acid.
- the polarizer may preferably further contain potassium.
- the potassium content is preferably 0.2% by mass or more and 1.0% by mass or less, more preferably 0.3% by mass or more and 0.9% by mass or less, and particularly preferably 0.4% by mass or more and 0. It is 0.8% by mass or less.
- the coefficient of linear expansion of the polarizer in the transmission axis direction is not particularly limited and may take any appropriate value.
- the coefficient of linear expansion of the polarizer in the transmission axis direction is 4.0 ⁇ 10 -5 / ° C or higher 5 It can be less than 0.0 ⁇ 10-5 / ° C.
- the thickness of the polarizer is not particularly limited, and is generally about 1 to 80 ⁇ m.
- At least one of the two protective films is the optical film of the present invention.
- the other may be the other optical film.
- optical films examples include commercially available cellulose ester films (eg, Konica Minolta Tuck KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR, KC8UY, KC6UY, KC4UY, KC6UY, KC4UY KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, manufactured by Konica Minolta Co., Ltd. Includes (manufactured by Film Co., Ltd.).
- cellulose ester films eg, Konica Minolta Tuck KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR, KC4KR,
- the thickness of the other optical film is not particularly limited, but is preferably 10 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and particularly preferably 20 to 60 ⁇ m.
- the protective film may further have other layers if necessary.
- other layers include an antireflection layer, an antistatic layer, a retardation layer, a brightness improving film layer, and the like.
- the adhesive layer may be a layer obtained by drying a completely saponified polyvinyl alcohol aqueous solution (water glue), or may be a cured product layer of an active energy ray-curable adhesive.
- the optical film and polarizing plate of the present invention can be used in various display devices such as a liquid crystal display device (LCD), an organic EL display device (OELD), and a touch panel.
- LCD liquid crystal display device
- OELD organic EL display device
- touch panel a touch panel
- the liquid crystal display device of the present invention has a liquid crystal cell, a first polarizing plate arranged on one surface of the liquid crystal cell (for example, a surface on the viewing side), and the other surface of the liquid crystal cell (for example, a surface on the backlight side). Includes a second polarizing plate arranged.
- One or both of the first and second polarizing plates are polarizing plates provided with the optical film of the present invention.
- the liquid crystal cell has two electrode substrates and a liquid crystal layer arranged between them.
- the liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.
- the rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °.
- the TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
- the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied.
- VA mode liquid crystal cell (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digist of Tech. Papers (proceedings) 28 (1997) 845 in which the VA mode is multi-domainized for expanding the viewing angle). ), (3) Liquid crystal cells in a mode (n-ASM mode) in which rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied and twisted and multi-domain oriented when a voltage is applied. (1998)) and (4) SURVAIVAL mode liquid crystal cells (announced at LCD International 98) are included.
- the OCB mode liquid crystal cell is a bend orientation mode liquid crystal cell in which rod-shaped liquid crystal molecules are oriented in substantially opposite directions (symmetrically) at the upper part and the lower part of the liquid crystal cell. It is disclosed in each specification of No. 5410422. Since the rod-shaped liquid crystal molecules are symmetrically oriented at the upper part and the lower part of the liquid crystal cell, the liquid crystal cell in the bend orientation mode has an adaptive optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Company Bend) liquid crystal mode.
- the liquid crystal display device in the bend orientation mode has an advantage of a high response speed.
- the IPS mode liquid crystal cell is a method of switching by applying a transverse electric field to the nematic liquid crystal.
- Proc. IDRC Alignment Citron Cell
- the ECB mode liquid crystal cell, rod-shaped liquid crystal molecules are substantially horizontally oriented when no voltage is applied.
- the ECB mode is one of the liquid crystal display modes having the simplest structure, and details are described in, for example, Japanese Patent Application Laid-Open No. 5-203946.
- the first polarizing plate includes a first polarizing element arranged on one surface of the liquid crystal cell (for example, a surface on the viewing side) and a protective film F1 arranged on the surface of the first polarizing element opposite to the liquid crystal cell. , Includes a protective film F2 arranged on the surface of the first polarizing element on the liquid crystal cell side.
- the second polarizing plate includes a second polarizing element arranged on the other surface of the liquid crystal cell (for example, a surface on the backlight side), a protective film F3 arranged on the surface of the second polarizing element on the liquid crystal cell side, and a second polarizing plate. Includes a protective film F4 arranged on the surface of the dipolarizer on the side opposite to the liquid crystal cell.
- the absorption axis of the first polarizer and the absorption axis of the second polarizer are orthogonal to each other (cross Nicol).
- At least one of the protective films F1, F2, F3 and F4 can be the optical film of the present invention.
- the optical film of the present invention is preferably used as the protective film F2 or F3.
- the liquid crystal display device including the optical film of the present invention as the protective film F2 or F3 is a liquid crystal display device that has been made thinner while maintaining high functionality.
- the polarizing plate of the present invention it is possible to obtain a liquid crystal display device having a thin screen while maintaining high functionality, even if the screen is a large-screen liquid crystal display device having a size of 30 inches or more.
- the optical film of the present invention can be used as a substrate (base film) for an organic EL element or the like or a protective film.
- the polarizing plate of the present invention can also be used as a circular polarizing plate of an organic EL display device.
- the organic EL display of the present invention may have an organic EL element having a light reflecting electrode, a light emitting layer, a transparent electrode layer, a transparent plastic film substrate, and a circularly polarizing plate.
- the circular polarizing plate has a polarizing element (linear polarizing film) and a ⁇ / 4 film provided between the transparent substrate and the polarizing element.
- the optical film of the present invention can be preferably used as a transparent plastic film substrate or a ⁇ / 4 film.
- the organic EL display device when the light reflecting electrode and the transparent electrode layer are energized, the light emitting layer emits light and an image can be displayed. Further, since all the light incident on the organic EL display device from the outside is absorbed by the polarizer, even if it is reflected by the light reflecting electrode of the organic EL display, it is not emitted to the outside, and the display characteristics are deteriorated due to the reflection of the background. Can be suppressed.
- the contents described in each publication of the above can be applied. Further, it is preferable to use it in combination with the contents described in JP-A-2001-148291, JP-A-2001-221916, and JP-A-2001-231443.
- the optical film of the present invention is suitable for touch panel applications, and for example, a touch panel can be produced according to the description in paragraphs [0073] to [0075] of JP2009-176608A.
- the touch panel can be used as an input device by incorporating it into a liquid crystal display device, a plasma display device, an organic EL display device, a CRT display device, a display device such as electronic paper, or the like.
- a liquid crystal display device a plasma display device, an organic EL display device, a CRT display device, a display device such as electronic paper, or the like.
- Capacitance type input devices have the advantage that a translucent conductive film may simply be formed on a single substrate. It is preferably a capacitance type.
- the electrode patterns are extended in the direction of intersecting each other as the transparent electrode layer, and it is detected that the capacitance between the electrodes changes when a finger or the like comes into contact with each other.
- a type that detects the input position can be preferably used.
- the configuration of such a touch panel for example, the descriptions of JP-A-2010-86684, JP-A-2010-152809, JP-A-2010-257492 and the like can be referred to.
- JP-A-2002-48913 can also be taken into consideration.
- Optical film 1. Optical film material
- a cycloolefin resin having a polar group a cycloolefin resin A consisting of a unit having a structure represented by the following formula (I) (in the formula (I), R is CH 3) . There is.) Was used.
- the cycloolefin resin having no polar group the cycloolefin resin B having a structure in which the group represented by COOR is replaced with a hydrogen atom in the following formula (I) was used.
- the obtained dope was kept at 40 ° C. and uniformly cast on a stainless belt, which is an endless metal support kept at 40 ° C.
- the cast dope was dried until the residual solvent amount became 80% by mass, and then peeled off from the stainless belt to obtain a film-like substance (unstretched film).
- the obtained film-like product was dried at 40 ° C. until the residual solvent amount became 5% by mass, and then stretched in the width direction at a stretching ratio of 1.5 times (stretching ratio: 50%).
- the obtained film-like material (stretched film) was further dried at 120 ° C. while being conveyed by a large number of rolls to obtain an optical film 1 having a thickness of 20 ⁇ m and a width of 1.3 m.
- Optical films 2 to 10 were obtained in the same manner as in the optical film 1 except that the type of the cycloolefin resin or the type of the compound was changed as shown in Table I.
- Table I were used for producing the optical film 1 to 10, (in Table I, "COP") a cycloolefin resin type, the type of compound, the angle of X 1 and X 2 with respect to the ring Y in said compound theta, and The content of the compound (% by mass with respect to 100% by mass of the cycloolefin resin) is shown.
- optical films 1 to 10 were evaluated for the retardation value Ro, the retardation value Rt, and the adhesiveness with the polarizer by the following methods. 3-1.
- Optical film retardation value Ro and retardation value Rt The in-plane retardation value Ro and the thickness direction retardation value Rt of the optical films 1 to 10 were measured by the following methods.
- the optical film was humidity-controlled for 24 hours in an environment of 23 ° C. and 55% RH.
- the average refractive index of the obtained optical film was measured with an Abbe refractometer. Further, the thickness d of the optical film was measured using a commercially available micrometer.
- the retardation value Ro and the retardation value Rt of the optical film after humidity control at a measurement wavelength of 550 nm are measured in an environment of 23 ° C. and 55% RH using an automatic birefringence meter Axoscan (manufactured by Axometrics), respectively. Measured below. Specifically, the measurement was carried out by the following methods i) to iii).
- phase difference value Ro when light having a measurement wavelength of 550 nm was incident parallel to the normal direction of the surface of the sample piece was measured by Axoscan.
- the in-plane slow-phase axis of the sample piece is set as the tilt axis (rotation axis), and the measurement wavelength is 550 nm from the angle of ⁇ (incident angle ( ⁇ )) with respect to the normal of the surface of the sample piece.
- the phase difference value R ( ⁇ ) when light was incident was measured.
- the phase difference value R ( ⁇ ) was measured at 6 points every 10 ° in the range where ⁇ was 0 ° to 50 °.
- the in-plane slow-phase axis of the sample piece was confirmed by axoscan.
- iii) From the measured retardation value Ro and retardation value R ( ⁇ ), and the above-mentioned average refractive index and thickness, Axoscan calculated n x , n y, and n z , and the following formula (i) And (ii), the phase difference values Ro and Rt at the measurement wavelength of 550 nm were calculated.
- N x is the refractive index of the optical film in the slow axis direction in the film plane.
- n y is the refractive index in the direction (fast axis direction) perpendicular to the optical film, the slow axis in the film plane
- nz is the refractive index in the thickness direction of the optical film.
- d is the film thickness (nm) of the optical film.
- the refractive index is a refractive index measured at a wavelength of 550 nm in an environment of 23 ° C. and 55% RH.
- Ro was used to evaluate the phase difference of the optical film.
- the evaluation criteria for Ro are as follows. ⁇ : 145 nm or more ⁇ : 120 nm or more and less than 145 nm ⁇ : 80 nm or more and less than 120 nm ⁇ : less than 80 nm ⁇ or more, it was judged to be good.
- Polarizer Adhesion with polarizer
- a long roll polyvinyl alcohol film having a thickness of 120 ⁇ m is immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 5 times in the transport direction at 50 ° C. To prepare a polarizer.
- Optical films 1 to 10 are cut into widths of 40 to 50 mm and length of 120 mm, respectively, and obtained as described above using a water-based adhesive (water-based adhesive containing polyvinyl alcohol-based resin). It was affixed to one surface of the obtained polarizer and dried in an oven at 90 ° C. for 10 minutes to bond the two. After bonding, the polarizer with an optical film was cut into a width of 25 mm and a length of 120 mm to prepare a peeling test sample.
- a water-based adhesive water-based adhesive containing polyvinyl alcohol-based resin
- Peeling strength is 3.0 (N / 25 mm) or more ⁇ : Peeling strength is 1.0 (N / 25 mm) or more and less than 3.0 (N / 25 mm) ⁇ : Peeling strength is 0.5 (N / 25 mm) More than 1.0 (N / 25 mm) ⁇ : If the peel strength is 0 (N / 25 mm) or more and less than 0.5 (N / 25 mm) ⁇ or more, it is judged to be good.
- the film thickness is sufficiently thin, a desired optical compensation value can be obtained, and the adhesiveness to the polarizer is improved. It is good.
- a polarizing plate was prepared as follows using the optical film 2 and the polarizer obtained above.
- One surface of the optical film 2 was subjected to corona treatment (activation treatment) at an irradiation amount of 810 (W ⁇ min / m 2).
- the optical film 2 is applied to one surface of the polarizer via a water-based adhesive (water-based adhesive containing a polyvinyl alcohol-based resin), and the corona-treated surface is the polarizer. It was pasted so as to face each other.
- the obtained laminate was dried in an oven at 90 ° C. for 10 minutes to obtain a polarizing plate.
- the polarizing plate obtained above was attached to a commercially available liquid crystal display device as follows. Using a liquid crystal display device in VA mode, the polarizing plates on both sides that had been bonded in advance were peeled off, and the polarizing plates obtained above were respectively bonded to the glass surface of the liquid crystal cell. The prepared polarizing plates are bonded so that the optical film 2 is on the outside with respect to the glass surface of the liquid crystal cell and the absorption axis of the polarizer faces in the same direction as the previously bonded polarizing plate. , A liquid crystal display device was manufactured.
- the image quality of the liquid crystal display device obtained by this was as good as that before the polarizing plate was replaced, but the thickness was thinner than that before the polarizing plate was replaced.
- an optical film having a sufficiently thin film thickness, a desired optical compensation value (phase difference), and good adhesion to a polarizer, particularly an optical film mainly composed of a cycloolefin resin and The manufacturing method can be provided. Further, by using the optical film, it is possible to provide a polarizing plate and a display device in which the thickness is realized while maintaining the performance.
- Polarizing plate 1 Polarizer 2, 3 Protective film one is the optical film of the present invention
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Abstract
Description
すなわち、本発明に係る上記課題は、以下の手段により解決される。
Yは、員数5~20の芳香族複素環を表す。
X1及びX2は、それぞれ独立して、Yを構成する原子と単結合を形成する、置換又は非置換の芳香環基を表す。
Rは、それぞれ独立して、水素原子、シアノ基、ヒドロキシ基又は炭素数1~10のアルキル基を表す。Rが2個以上存在する場合、2個のRがこれらの基に代わってオキソ基(=O)として存在してもよい。
nは、Yの価数であり、2以上の整数である。
Yの中心とX1を構成する環のうち最もYから離れて位置する環の中心とを結ぶ直線L1と、Yの中心とX2を構成する環のうち最もYから離れて位置する環の中心とを結ぶ直線L2とがなす角が110°~145°の範囲内である。)
本発明の効果の発現機構ないし作用機構については、明確にはなっていないが、以下のように推察している。
この特徴は、下記各実施形態に共通する技術的特徴である。
本発明の光学フィルムは、シクロオレフィン樹脂と化合物(1)とを含有することを特徴とする。本発明の光学フィルムにおいて、化合物(1)は位相差上昇剤として作用する。本発明の光学フィルムは、化合物(1)以外の位相差上昇剤を含有してもよい。また、本発明の光学フィルムは、本発明の効果を損なわない範囲で、位相差上昇剤以外に、各種添加剤を含有してもよい。
化合物(1)は、下記一般式(1)で表される構造を有する化合物である。本明細書において、一般式(1)で表される構造を有する化合物を化合物(1)ともいう。同様に式(X1)で表される構造を有する基を基(X1)ともいう。他の化合物及び基においても同様である。また、Yで示される環を環Yということもある。
X1は、置換又は非置換の1価の芳香環基である。X1は少なくとも芳香環がYに単結合で結合する構造であればよく、該芳香環に結合する水素原子は置換基により置換されていてもよい。X1は、例えば、Yに結合するX11で示される芳香環基を有し、X11がX12で示される芳香環基又は脂環基で置換され、さらにX12がX13で示される芳香環基又は脂環基で置換されるというように、複数の環構造が単結合で結合された構造であってもよい。複数の環構造が単結合で結合された構造のX1は、例えば、以下の式(X)で表すことができる。
式(X)において、X11は環Yに結合する2価の芳香環基であり、X12及びX1L-1は2価の芳香環基又は脂環基であり、X1Lは1価の芳香環基又は脂環基である。Lは式(X)で示される基が有する環の数を示す。X1Lは末端の環でありYから最も離れて位置する環である。
本発明の光学フィルムは、該光学フィルムを主として構成する樹脂としてシクロオレフィン樹脂を含有する。本発明の光学フィルムは、後述のように本発明の効果を損なわない範囲でシクロオレフィン樹脂以外の樹脂を含有してもよいが、樹脂はシクロオレフィン樹脂のみでなることが好ましい。本発明で用いるシクロオレフィン樹脂としては、下記一般式(4)で表される構造を有する(共)重合体が挙げられる。
本発明の光学フィルムは、本発明の効果を損なわない範囲で、化合物(1)以外の従来公知の位相差上昇剤を含有してもよい。本発明の光学フィルムは、さらに、位相差上昇剤以外の各種添加剤を含有できる。該添加剤としては、可塑剤、紫外線吸収剤、酸化防止剤、帯電防止剤等が挙げられる。
本発明の光学フィルムにおいては、製造時における組成物の流動性や光学フィルムの柔軟性を向上するために、可塑剤を用いることも可能である。可塑剤としては、フタル酸エステル系、脂肪酸エステル系、トリメリット酸エステル系、リン酸エステル系、ポリエステル系、あるいはエポキシ系等が挙げられる。
本発明の光学フィルムは紫外線吸収剤を含有することも好ましく、用いられる紫外線吸収剤としては、ベンゾトリアゾール系、2-ヒドロキシベンゾフェノン系又はサリチル酸フェニルエステル系のもの等が挙げられる。例えば、2-(5-メチル-2-ヒドロキシフェニル)ベンゾトリアゾール、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール、2-(3,5-ジ-t-ブチル-2-ヒドロキシフェニル)ベンゾトリアゾール等のトリアゾール類、2-ヒドロキシ-4-メトキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノン、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン等のベンゾフェノン類を例示することができる。
本発明では、酸化防止剤としては、通常知られているものを光学フィルムに使用することができる。特に、ラクトン系、イオウ系、フェノール系、二重結合系、ヒンダードアミン系、リン系化合物のものを好ましく用いることができる。例えば、BASFジャパン株式会社から、IrgafosXP40、IrgafosXP60という商品名で市販されているものを含むものが好ましい。
本発明の光学フィルムの物性は、膜厚について、薄膜化の観点から30μm以下が好ましい。さらに、強度、均一性及び生産性の観点から、光学フィルム膜厚は、5~30μmであることがより好ましい。
本発明の光学フィルムの、下記式(i)で定義される面内方向の位相差値Ro(nm)は30nm以上が好ましく、下記式(ii)で定義される厚さ方向の位相差値Rt(nm)は100nm以上が好ましい。
式(ii) Rt={(nx+ny)/2-nz}×d (nxは、光学フィルムの、フィルム面内の遅相軸方向での屈折率であり、
nyは、光学フィルムの、フィルム面内の遅相軸に直交する方向(進相軸方向)での屈折率であり、
nzは、光学フィルムの厚さ方向の屈折率であり、
dは、光学フィルムの膜厚(nm)である。)
なお、屈折率は23℃、55%RHの環境下、波長550nmで測定した屈折率である。
2)調湿後の光学フィルムの、測定波長550nmにおける位相差値Ro及び位相差値Rtを、それぞれ自動複屈折計アクソスキャン(アクソメトリックス社製)を用いて、23℃、55%RHの環境下で測定する。具体的には、以下のi)~iii)の方法で測定する。
ii)さらに、アクソスキャンにより、試料片の面内遅相軸を傾斜軸(回転軸)として、試料片の表面の法線に対してθの角度(入射角(θ))から測定波長550nmの光を入射させたときの位相差値R(θ)を測定する。位相差値R(θ)の測定は、θが0°~50°の範囲で10°毎に6点行う。試料片の面内遅相軸は、アクソスキャンにより確認できる。
iii)測定された位相差値Ro及び位相差値R(θ)と、前述の平均屈折率と厚さとから、アクソスキャンがnx、ny及びnzを算出し、上記式(ii)に基づいて測定波長550nmでの位相差値Rtを算出する。
本発明の光学フィルムは、透明性が高いことが好ましい。光学フィルムのヘイズは、4.0%以下であることが好ましく、2.0%以下であることがより好ましく、1.0%以下であることがさらに好ましい。ヘイズは、試料40mm×80mmを25℃、60%RHでヘイズメーター(HGM-2DP、スガ試験機)により、JIS K-6714に従って測定することができる。
本発明の光学フィルムの成形方法としては、溶融流延法、溶液流延法、カレンダー成形法等の公知の延伸工程を含む成形方法が挙げられる。溶融流延法、溶液流延法に用いることが好ましく、溶液流延法が特に好ましい。
(1)上記一般式(1)で表される構造を有する化合物及びシクロオレフィン樹脂と溶媒を含有するドープを調製する工程(以下、「ドープ調製工程」という。)
(2)(1)で得られたドープを支持体上に流延し未延伸フィルムを得る工程(以下、「流延工程」という。)
(3)(2)で得られた未延伸フィルムを延伸する工程(以下、「延伸工程」という。)
以下、各工程について説明する。
本発明に係るシクロオレフィン樹脂に対する良溶媒を主とする有機溶媒に、溶解釜中で当該シクロオレフィン樹脂及び本発明に係る化合物(1)、場合によって、その他の樹脂又は添加剤を撹拌しながら溶解しドープを調製する工程、又は当該シクロオレフィン樹脂溶液(場合によって、その他の樹脂を含んでいてもよい)に、上記化合物(1)、場合によって、その他の添加剤を含む溶液を混合して主溶解液であるドープを調製する工程である。
(2-1)ドープの流延
ドープを、送液ポンプ(例えば、加圧型定量ギヤポンプ)を通して加圧ダイに送液し、無限に移送する無端の支持体、例えば、ステンレスベルト、又は回転する金属ドラム等の金属支持体上の流延位置に、加圧ダイスリットからドープを流延する工程である。
ウェブを流延用支持体上で加熱し、溶媒を蒸発させる工程であり、後述する剥離時の残留溶媒量を制御する工程である。
金属支持体上で溶媒が蒸発したウェブを、剥離位置で剥離する工程である。剥離されたウェブは未延伸フィルムとして次工程に送られる。
残留溶媒量(%)=(ウェブ又は未延伸フィルムの加熱処理前質量-ウェブ又は未延伸フィルムの加熱処理後質量)/(ウェブ又は未延伸フィルムの加熱処理後質量)×100
なお、残留溶媒量を測定する際の加熱処理とは、115℃で1時間の加熱処理を行うことを表す。
乾燥工程は予備乾燥工程(第1乾燥工程)、本乾燥工程(第2乾燥工程)に分けて行うこともできる。
金属支持体からウェブ剥離して得られた未延伸フィルムは第1乾燥装置にて予備乾燥させる。フィルムの予備乾燥は、フィルムを、上下に配置した多数のローラーにより搬送しながら乾燥させてもよいし、テンター乾燥機のようにフィルムの両端部をクリップで固定して搬送しながら乾燥させてもよい。
本発明の光学フィルムの製造方法においては、延伸装置にて特定の残留溶媒量の未延伸フィルムに対して低延伸率の延伸処理を行うことで、フィルム表面近傍の微小なクレーズの発生を抑制することができる。さらに、該延伸時に、化合物(1)自体が配向するとともに、化合物(1)が上記のように作用してフィルム内のシクロオレフィン樹脂の配向を制御することで、低延伸率においても目標とする位相差値Ro及び位相差値Rtを得ることができる。
・長手方向に延伸→幅手方向に延伸→長手方向に延伸→長手方向に延伸
・幅手方向に延伸→幅手方向に延伸→長手方向に延伸→長手方向に延伸
また、同時二軸延伸には、一方向に延伸し、もう一方を、張力を緩和して収縮させる場合も含まれる。
(式1において、d1は延伸後の本発明の光学フィルムの前記延伸方向の幅寸法であり、d2は延伸前の未延伸フィルムの前記延伸方向の幅寸法であり、tは延伸に要する時間(min)である。)
本発明の光学フィルムの製造方法においては、本乾燥工程で、第2乾燥装置によって延伸後の延伸フィルムを加熱して乾燥させる。熱風等により延伸フィルムを加熱する場合、使用済みの熱風(溶媒を含んだエアーや濡れ込みエアー)を排気できるノズルを設置して、使用済み熱風の混入を防ぐ手段も好ましく用いられる。熱風温度は、40~350℃の範囲がより好ましい。また、乾燥時間は5秒~60分程度が好ましく、10秒~30分がより好ましい。
(4-1)ナーリング加工
所定の熱処理又は冷却処理の後、光学フィルムは、巻取り前にスリッターを設けて端部を切り落とすことが良好な巻姿を得るために好ましい。更に、幅手両端部にはナーリング加工をすることが好ましい。
フィルム中の残留溶媒量が2質量%以下となってから光学フィルムとして巻取る工程であり、残留溶媒量を好ましくは0.4質量%以下にすることにより寸法安定性の良好な光学フィルムを得ることができる。
本発明の偏光板は、偏光子と、偏光子の少なくとも一方の面に配置された本発明の光学フィルムとを具備することを特徴とする。偏光板は、例えば、偏光子と、該偏光子の両面に配置された2つの保護フィルムとを有するものであって、2つの保護フィルムの少なくとも一方が本発明の光学フィルムである。
偏光子としては、任意の適切な偏光子を用いることができる。例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等のポリエン系配向フィルム等が挙げられる。これらのなかでも、ポリビニルアルコール系フィルムにヨウ素などの二色性物質を吸着させて一軸延伸した偏光子が、偏光二色比が高く特に好ましい。
二色比DR=log(0.919/k2)/log(0.919/k1)
ここで、k1は偏光子の透過軸方向の透過率であり、k2は偏光子の吸収軸方向の透過率であり、定数0.919は界面反射率である。
透過率={(k1+k2)/2}×100 [%]
ここで、k1は、偏光子の透過軸方向の透過率であり、k2は、偏光子の吸収軸方向の透過率である。
2つの保護フィルムのうち少なくとも一方は、本発明の光学フィルムである。2つの保護フィルムのうち一方が本発明の光学フィルムである場合、他方は、他の光学フィルムであってもよい。
接着層は、完全ケン化型ポリビニルアルコール水溶液(水糊)を乾燥させて得られる層であってもよいし、活性エネルギー線硬化性接着剤の硬化物層であってもよい。
本発明の光学フィルムや偏光板は、液晶表示装置(LCD)、有機EL表示装置(OELD)やタッチパネル等の各種表示装置に用いることができる。
本発明の液晶表示装置は、液晶セルと、液晶セルの一方の面(例えば視認側の面)に配置された第1偏光板と、液晶セルの他方の面(例えばバックライト側の面)に配置された第2偏光板とを含む。第1及び第2偏光板のうち一方または両方が、本発明の光学フィルムを具備する偏光板である。
本発明の光学フィルムは、有機EL素子等の基板(基材フィルム)や保護フィルムとして用いることができる。本発明の偏光板は、有機EL表示装置の円偏光板として用いることもできる。
本発明の光学フィルムは、タッチパネル用途に好適であり、例えば、特開2009-176608号公報の段落[0073]~[0075]の記載に従い、タッチパネルを作製することができる。
1.光学フィルムの材料
(1)シクロオレフィン樹脂
極性基を有するシクロオレフィン樹脂として、下記式(I)で表される構造を有する単位からなるシクロオレフィン樹脂A(式(I)中、RはCH3である。)を用いた。また、極性基を有しないシクロオレフィン樹脂として、下記式(I)において、COORで表される基が水素原子に置き換わった構造を有する単位からなる、シクロオレフィン樹脂Bを用いた。
(2-1)化合物(1)
化合物(1)として、化合物1-1~1-6を用いた。
比較例用に下記式Cf-1~Cf-3で表される構造を有する化合物Cf-1~Cf-3を準備した。化合物Cf-1~Cf-3において、化合物(1)の環Yに対するX1とX2のなす角θに相当する角度は、それぞれ128°、150°及び75°である。
<光学フィルム1の作製>
(ドープの調製)
下記成分を密閉容器に投入し、加熱し、撹拌しながら、完全に溶解し、安積濾紙(株)製の安積濾紙No.24を使用して濾過し、ドープを調製した。
シクロオレフィン樹脂A: 228質量部
化合物1-1: 12質量部
ジクロロメタン: 659質量部
エタノール: 42質量部
得られたドープを40℃に保ち、40℃に保温された無端の金属支持体であるステンレスベルト上に均一に流延した。流延したドープを、残留溶媒量が80質量%となるまで乾燥させた後、ステンレスベルト上から剥離して膜状物(未延伸フィルム)を得た。得られた膜状物を、残留溶媒量が5質量%となるまで40℃で乾燥させた後、幅方向に延伸倍率1.5倍(延伸率50%)で延伸した。得られた膜状物(延伸フィルム)を、多数のロールで搬送させながら120℃でさらに乾燥させて、厚さ20μm、幅1.3mの光学フィルム1を得た。
シクロオレフィン樹脂の種類又は化合物の種類を表Iに示されるように変更した以外は光学フィルム1と同様にして光学フィルム2~10を得た。
表Iに光学フィルム1~10の作製に用いた、シクロオレフィン樹脂(表I中、「COP」)の種類、化合物の種類、該化合物における環Yに対するX1とX2のなす角θ、及び化合物の含有量(シクロオレフィン樹脂100質量%に対する質量%)を示す。
作製した光学フィルム1~10について、以下の方法で位相差値Ro及び位相差値Rt並びに偏光子との接着性の評価を実施した。
3-1.光学フィルムの位相差値Ro及び位相差値Rt
光学フィルム1~10の面内方向の位相差値Ro及び厚さ方向の位相差値Rtを、以下の方法で測定した。
2)調湿後の光学フィルムの、測定波長550nmにおける位相差値Ro及び位相差値Rtを、それぞれ自動複屈折計アクソスキャン(アクソメトリックス社製)を用いて、23℃、55%RHの環境下で測定した。具体的には、以下のi)~iii)の方法で測定した。
ii)さらに、アクソスキャンにより、試料片の面内遅相軸を傾斜軸(回転軸)として、試料片の表面の法線に対してθの角度(入射角(θ))から測定波長550nmの光を入射させたときの位相差値R(θ)を測定した。位相差値R(θ)の測定は、θが0°~50°の範囲で10°毎に6点行った。試料片の面内遅相軸は、アクソスキャンにより確認した。
iii)測定された位相差値Ro及び位相差値R(θ)と、前述の平均屈折率と厚さとから、アクソスキャンがnx、ny及びnzを算出し、以下の式(i)及び(ii)に基づいて測定波長550nmでの位相差値Ro及びRtを算出した。
式(ii) Rt={(nx+ny)/2-nz}×d
(nxは、光学フィルムの、フィルム面内の遅相軸方向での屈折率であり、
nyは、光学フィルムの、フィルム面内の遅相軸に直交する方向(進相軸方向)での屈折率であり、
nzは、光学フィルムの厚さ方向の屈折率であり、
dは、光学フィルムの膜厚(nm)である。)
なお、屈折率は23℃、55%RHの環境下、波長550nmで測定した屈折率である。
◎:145nm以上
○:120nm以上145nm未満
△:80nm以上120nm未満
×:80nm未満
△以上であれば、良好と判断した。
(1)偏光子の作製
厚さ120μmの長尺ロールポリビニルアルコールフィルムを、ヨウ素1質量部、ホウ酸4質量部を含む水溶液100質量部に浸漬し、50℃で5倍に搬送方向に延伸して、偏光子を作製した。
光学フィルム1~10を、それぞれ幅40~50mm×長さ120mmにカットして、水系接着剤(ポリビニルアルコール系樹脂を含む水系接着剤)を用いて、上記で得られた偏光子の一方の面に貼合し、90℃のオーブンで10分間乾燥して両者を接着させた。接着後、光学膜付き偏光子を幅25mm×長さ120mmにカットして剥離試験サンプルとした。
剥離試験サンプルにおいて、光学フィルムを偏光子から長さ120mm方向の20mmだけ剥がして、クリップの掴み代としてテンシロン(オリエンテック社製)に設置し剥離強度(接着性)を測定した。評価基準は以下のとおりとした。
◎:剥離強度が3.0(N/25mm)以上
○:剥離強度が1.0(N/25mm)以上3.0(N/25mm)未満
△:剥離強度が0.5(N/25mm)以上1.0(N/25mm)未満
×:剥離強度が0(N/25mm)以上0.5(N/25mm)未満
△以上であれば、良好と判断した。
(1)偏光板の作製
上記で得られた光学フィルム2と偏光子を用いて以下のとおり偏光板を作製した。
光学フィルム2の一方の面に、810(W・min/m2)の照射量でコロナ処理(活性化処理)を施した。次いで、コロナ処理から、所定の時間経過後、偏光子の一方の面に、水系接着剤(ポリビニルアルコール系樹脂を含む水系接着剤)を介して、光学フィルム2を、そのコロナ処理面が偏光子と対向するように貼り合わせた。また、偏光子の他方の面(光学フィルムと対向していない面)に、前述と同様の水系接着剤を介して、アルカリけん化処理したコニカミノルタ社製のTACフィルム6UAを貼り合わせた。得られた積層物を、90℃のオーブンで10分間乾燥させて、偏光板を得た。
上記で得られた偏光板を以下のとおり市販の液晶表示装置に取り付けた。
VAモードの液晶表示装置を用いて、あらかじめ貼合されていた両面の偏光板を剥がして、上記で得られた偏光板をそれぞれ液晶セルのガラス面に貼合した。作製した偏光板をそれぞれ光学フィルム2が液晶セルのガラス面に対して外側になるように、かつあらかじめ貼合されていた偏光板と同一の方向に偏光子の吸収軸が向くように貼合し、液晶表示装置を作製した。
1 偏光子
2、3 保護フィルム(一方が本発明の光学フィルム)
Claims (8)
- シクロオレフィン樹脂と下記一般式(1)で表される構造を有する化合物とを含有する光学フィルム。
Yは、員数5~20の芳香族複素環を表す。
X1及びX2は、それぞれ独立して、Yを構成する原子と単結合を形成する、置換又は非置換の芳香環基を表す。
Rは、それぞれ独立して、水素原子、シアノ基、ヒドロキシ基又は炭素数1~10のアルキル基を表す。Rが2個以上存在する場合、2個のRがこれらの基に代わってオキソ基(=O)として存在してもよい。
nは、Yの価数であり、2以上の整数である。
Yの中心とX1を構成する環のうち最もYから離れて位置する環の中心とを結ぶ直線L1と、Yの中心とX2を構成する環のうち最もYから離れて位置する環の中心とを結ぶ直線L2とがなす角が110°~145°の範囲内である。) - 前記X1及びX2の少なくとも一方が、芳香族複素環を有する請求項1に記載の光学フィルム。
- 前記X1及びX2の少なくとも一方が、芳香族縮合環を有する請求項1又は請求項2に記載の光学フィルム。
- 前記Yが、員数が6であり、ヘテロ原子の数が1個の単環であり、かつ前記X1及びX2がそれぞれ前記ヘテロ原子の両側の炭素原子に結合している請求項1から請求項3までのいずれか一項に記載の光学フィルム。
- 前記シクロオレフィン樹脂が、極性基を有する請求項1から請求項4までのいずれか一項に記載の光学フィルム。
- 請求項1から請求項5までのいずれか一項に記載の光学フィルムを製造する光学フィルムの製造方法であって、前記一般式(1)で表される構造を有する化合物及び前記シクロオレフィン樹脂と溶媒を含有するドープを調製し、前記ドープを支持体上に流延して未延伸フィルムを得、前記未延伸フィルムを延伸することを含む光学フィルムの製造方法。
- 偏光子と、前記偏光子の少なくとも一方の面に配置された請求項1から請求項5までのいずれか一項に記載の光学フィルムとを具備する偏光板。
- 請求項1から請求項5までのいずれか一項に記載の光学フィルムを具備する表示装置。
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JP2002022942A (ja) * | 2000-07-04 | 2002-01-23 | Fuji Photo Film Co Ltd | 光学補償シート、偏光板および液晶表示装置 |
JP2012208173A (ja) * | 2011-03-29 | 2012-10-25 | Konica Minolta Advanced Layers Inc | 光学フィルム、及びそれを用いた偏光板、液晶表示装置 |
JP2014148496A (ja) * | 2013-01-10 | 2014-08-21 | Konica Minolta Inc | トリアゾール化合物の製造方法及び光学フィルム |
JP2014178518A (ja) * | 2013-03-15 | 2014-09-25 | Fujifilm Corp | セルロースアセテートブチレートフィルム、偏光板および液晶表示装置 |
WO2016181756A1 (ja) * | 2015-05-13 | 2016-11-17 | コニカミノルタ株式会社 | タッチパネル付き液晶表示装置及びその製造方法 |
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KR20220092919A (ko) | 2022-07-04 |
CN114746782A (zh) | 2022-07-12 |
JPWO2021111721A1 (ja) | 2021-06-10 |
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