WO2015040959A1 - 長尺光学フィルム、該長尺光学フィルムを備える円偏光板ならびに有機エレクトロルミネッセンス表示装置 - Google Patents
長尺光学フィルム、該長尺光学フィルムを備える円偏光板ならびに有機エレクトロルミネッセンス表示装置 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
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- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
Definitions
- the present invention relates to a long optical film, a circularly polarizing plate provided with the long optical film, and an organic electroluminescence display device.
- organic EL display using organic electroluminescence (hereinafter abbreviated as organic EL) as a backlight is attracting attention as a new type of display device.
- organic EL organic electroluminescence
- an organic EL display in order to efficiently extract light from the light-emitting layer to the viewer side, a method using a highly light-reflective metal material as an electrode layer constituting the cathode or a metal plate as a separate reflecting member is provided.
- a reflection member having a mirror surface is provided on the surface opposite to the light extraction surface. For this reason, the organic EL display has a problem that external light is reflected on the reflecting member for extracting light and a reflection occurs, and the contrast is greatly reduced under an environment with high illuminance.
- Such a retardation plate has a problem in that a distribution occurs in the polarization state at each wavelength with respect to white light and the light is converted into colored polarized light. This originates in the material which comprises a phase difference plate having wavelength dispersion about a phase difference.
- a ⁇ / 4 wavelength plate in which the phase difference of birefringent light is 1 ⁇ 4 wavelength and a ⁇ / 2 wavelength plate in which the phase difference of birefringent light is 1 ⁇ 2 wavelength
- a phase difference plate in which the respective optical axes intersect with each other see, for example, Patent Document 2.
- a polymer monomer unit having positive refractive index anisotropy and a monomer unit having negative birefringence are copolymerized.
- a method of uniaxially stretching a polymer film made into a ⁇ / 4 retardation film has been studied (for example, see Patent Document 3).
- An optical film having both an optical compensation function and a function as a polarizing plate protective film has been studied (for example, see Patent Document 4).
- a cellulose ester resin is preferably used from the viewpoint of excellent production suitability of the polarizing plate.
- the retardation film obtained by the method described in Patent Document 3 has a problem that adhesiveness with a polarizer is not excellent when a polarizing plate is produced.
- cellulose ester resin is preferably used in the film obtained by the method described in Patent Documents 3 and 4.
- cellulose ester resin originally tends to cause phase difference fluctuations, and phase difference fluctuations due to humidity fluctuations.
- a matting agent is added from the viewpoint of suppressing an increase in haze.
- the additive described in Patent Document 5 is added to a cellulose ester film containing a matting agent, there is a problem that the matting agent aggregates and haze increases.
- the present invention has been made in view of the above-mentioned conventional problems, exhibits sufficient retardation, suppresses phase difference fluctuation due to humidity fluctuation, has excellent adhesiveness and brittleness with a polarizer, and increases haze. It is an object of the present invention to provide a long optical film in which the long optical film is suppressed, a circularly polarizing plate including the long optical film, and an organic electroluminescence display device.
- One aspect of the present invention includes a cellulose derivative and silica-based fine particles, the angle formed by the longitudinal direction and the slow axis is 40 to 50 °, and the in-plane retardation Ro 550 at a wavelength of 550 nm is 120 nm or more. It is a long optical film having a thickness of 160 nm or less and satisfying the following formulas (1) to (3).
- FIG. 1 is a schematic diagram for explaining the shrinkage ratio in oblique stretching.
- FIG. 2 is a schematic view showing an example of a rail pattern of an oblique stretching machine applicable to the production of the optical film of one embodiment of the present invention.
- FIG. 3 is a schematic view showing a method for producing an optical film according to an embodiment of the present invention (an example in which the optical film is drawn from a long film roll and then obliquely stretched).
- FIG. 4 is a schematic diagram illustrating a method for producing an optical film according to an embodiment of the present invention (an example in which a long film original is continuously stretched obliquely without being wound up).
- FIG. 5 is a schematic diagram showing an example of the configuration of an organic EL display according to an embodiment of the present invention.
- the present inventors solved the above problem by setting the ratio of the substituents of the cellulose derivative within a predetermined range in the long optical film containing the silica-based fine particles as the matting agent and the cellulose derivative. As a result, the present invention described later has been completed.
- the long optical film of the present embodiment (hereinafter also simply referred to as an optical film or a retardation film) is characterized in that the angle formed between the long direction and the slow axis is 40 to 50 °. That is, in the long optical film, the angle formed by the longitudinal direction and the in-plane slow axis is 40 to 50 °.
- the long optical film is characterized in that an in-plane retardation Ro 550 at a wavelength of 550 nm is 120 nm or more and 160 nm or less.
- the long optical film includes a cellulose derivative and silica-based fine particles, and the cellulose derivative satisfies the following formulas (1) to (3).
- the long optical film of the present embodiment has optical characteristics such that the slow axis and the in-plane retardation Ro 550 are within the above ranges, and therefore substantially ⁇ with respect to a wide band of visible light. A phase difference of / 4 can be imparted.
- the long optical film includes a cellulose derivative that is adjusted so that the ratio of substituents satisfies the following formulas (1) to (3) as a constituent component, the optical performance (color performance, reflection) Property) is suppressed, a haze increase suppressing effect is sufficiently obtained, and excellent brittleness is imparted to the film.
- the long optical film of the present embodiment will be described in the order of optical characteristics and constituent components.
- XES is the average ester substitution degree of the cellulose derivative
- XETH is the ether average substitution degree of the cellulose derivative
- Y is the total substitution degree of the cellulose derivative.
- optical film refers to a film having an optical function of imparting a desired phase difference to transmitted light. Examples of the optical function include a function of converting linearly polarized light having a specific wavelength into elliptically polarized light and circularly polarized light, or a function of converting elliptically polarized light and circularly polarized light into linearly polarized light.
- an optical film having a characteristic that the in-plane retardation of the film is about 1 ⁇ 4 with respect to a predetermined wavelength of light is referred to as a “ ⁇ / 4 retardation film”.
- the optical film of the present embodiment has a phase difference of approximately 1 ⁇ 4 of the wavelength in the visible light wavelength range in order to convert linearly polarized light into almost perfect circularly polarized light in a wide range of visible light wavelength.
- a broadband ⁇ / 4 retardation film is preferred.
- “a phase difference of approximately 1 ⁇ 4 in the wavelength range of visible light” means having an inverse wavelength dispersion characteristic in which the phase difference value increases in the longer wavelength range in the wavelength range of 400 nm to 700 nm.
- the in-plane retardation Ro in the optical film of the present embodiment is defined by the following formula.
- nx the refractive index in the slow axis direction x where the refractive index is maximum in the in-plane direction of the optical film
- ny is the direction y orthogonal to the slow axis direction x in the in-plane direction of the optical film.
- the refractive index in (d) represents the thickness of the optical film.
- Ro can be measured using an automatic birefringence meter in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH.
- Examples of the automatic birefringence meter include AxoScan manufactured by Axometrics, and KOBRA-21ADH manufactured by Oji Scientific Instruments.
- the optical film of the present embodiment is characterized in that Ro 550 is 120 nm or more and 160 nm or less.
- the in-plane retardation Ro 550 at a wavelength of 550 nm is an in-plane retardation measured with light having a wavelength of 550 nm.
- Ro 550 may be 120 nm or more and 160 nm or less, preferably 130 nm or more and 150 nm or less, and more preferably 135 nm or more and 148 nm or less.
- the phase difference at a wavelength of 550 nm is not approximately 1 ⁇ 4 wavelength, and such a film is formed.
- a circularly polarizing plate is produced and applied to an organic EL display, the reflection of indoor lighting becomes large, and black may not be expressed in a bright place.
- the in-plane retardation of the optical film at a wavelength of 450nm and Ro 450 when the in-plane retardation of the optical film at a wavelength of 550nm and Ro 550, the ratio of Ro 450 for Ro 550 (Ro 450 / Ro 550 ) is 0.70 or more and 0.98 or less, more preferably 0.75 or more and 0.92 or less, and further preferably 0.80 or more and 0.87 or less.
- the in-plane retardation Ro 450 at a wavelength of 450 nm is an in-plane retardation measured with light having a wavelength of 450 nm.
- the angle formed between the longitudinal direction and the slow axis is 40 to 50 °, preferably 42 to 48 °, more preferably 43 to 47 °. Since the optical film of the present embodiment has such a slow axis, a roll-shaped raw film and a roll-shaped polarizer film having a transmission axis parallel to the longitudinal direction are respectively unwound and long. A circularly polarizing plate can be easily manufactured by laminating with roll-to-roll so that the scale directions overlap each other. Thereby, the cut loss of a film can be reduced.
- a method of setting the range of the slow axis with respect to the longitudinal direction to such a range for example, there is a method of performing oblique stretching described later on the film before stretching formed into a film.
- An optical film is comprised from the resin component (resin composition containing a cellulose derivative) used as a main component, and an additive component (it contains components other than the said resin component, mat agents, such as a silica type microparticle).
- the optical film contains a cellulose derivative as a main component.
- the “main component” refers to a component contained in an amount of 55% by mass or more in the resin component constituting the optical film. Therefore, the optical film includes one in which a resin composition containing 55% by mass or more of a cellulose derivative is used as a constituent resin component.
- the cellulose derivative has a structure in which the hydroxyl group of cellulose is substituted with a substituent. Specifically, the cellulose derivative has a structure in which the substituent is bonded to the glucose skeleton by an ester bond or an ether bond described later.
- the optical film of this embodiment is characterized in that the degree of substitution of substituents of the glucose skeleton satisfies the following formulas (1) to (3). Examples of the “substituent that the glucose skeleton has” include “substituent that is ester-bonded to the glucose skeleton” and “substituent that is ether-bonded to the glucose skeleton” described later.
- the cellulose derivative has a glucose skeleton unit represented by the following general formula.
- R 2 is a substituent located at the 2-position of the glucose skeleton
- R 3 is a substituent located at the 3-position of the glucose skeleton
- R 6 is located at the 6-position of the glucose skeleton.
- R 2 , R 3 and R 6 may be selected so that the degree of substitution satisfies the above formulas (1) to (3), and each represents a hydrogen atom or a substituent.
- the total degree of substitution Y is 1.8 or more and 2.6 or less, preferably 1.9 or more and 2.4 or less, more preferably 2.0 or more and 2.3. It is as follows. When the total substitution degree Y is less than 1.8, the kind of solvent that can be dissolved alone is limited, and the water absorption of the film increases, and the phase difference tends to fluctuate due to humidity fluctuations. On the other hand, when the total substitution degree Y exceeds 2.6, not only sufficient retardation is not exhibited, but the resin tends to be expensive and expensive. In this embodiment, the total degree of substitution Y is represented by the sum of the ester average degree of substitution XES and the ether average degree of substitution XETH .
- the “total degree of substitution” refers to the average total degree of substitution, and among the three hydroxy groups (hydroxyl groups) of the glucose skeleton constituting cellulose, esterified or etherified hydroxy groups
- the average value of the number of 0 and 3.0 takes a value of 0 to 3.0. Therefore, when the total substitution degree Y is 1.8 or more and 2.6 or less, the ratio of a hydroxy group will be 0.4 or more and 1.2 or less.
- the ratio of the hydroxy group is within such a range, the hydrogen bonding property between the cellulose derivatives is increased, so that the brittleness of the obtained optical film is improved.
- the hydroxy group ratio is in such a range, the optical film easily exhibits a desired in-plane retardation value Ro when the film thickness is, for example, 20 to 60 ⁇ m.
- the average ester substitution degree XES is 0.3 or more and 1.5 or less, preferably 0.5 or more and 1.4 or less, more preferably 0.7 or more and 1 or less. .4 or less.
- the ester average substitution degree XES is less than 0.3, the transparency of the film tends to decrease.
- the ester average substitution degree XES exceeds 1.5, the water absorption of the film increases, and the phase difference tends to fluctuate due to humidity fluctuation.
- the average ether substitution degree X ETH is 0.3 or more and 2.3 or less, preferably 0.5 or more and 1.9 or less, more preferably 0.5 or more and 1 or less. .6 or less.
- the average ether substitution degree X ETH is less than 0.3
- the total substitution degree Y of the film substituted with an ester based on the range shown in the above formula (2) is less than the lower limit of 1.8
- the humidity tends to fluctuate due to fluctuations.
- the cellulose derivative of the present embodiment has a substituent ester-bonded to the glucose skeleton so as to satisfy the formula (2).
- Examples of the substituent ester-bonded to the glucose skeleton include an aliphatic acyl group and an aromatic group as R 2 , R 3 and R 6 in the general formula of the cellulose derivative.
- Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.
- the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and is preferably an aromatic hydrocarbon group.
- the aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12, and still more preferably 6 to 10.
- Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a terphenyl group.
- a phenyl group, a naphthyl group, and a biphenyl group are preferable, and a phenyl group is more preferable.
- aromatic heterocyclic group those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable.
- the heterocyclic ring include furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, Examples include phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, and tetrazaindene.
- aromatic heterocyclic group a
- aromatic group bonded to the glucose skeleton by an ether bond examples include benzyl ether, 4-phenylbenzyl ether, 4-thiomethylbenzyl ether, 4-methoxybenzyl ether, 2,4,5-trimethylbenzyl ether. 2,4,5-trimethoxybenzyl ether and the like.
- aromatic group bonded to the glucose skeleton through an ether bond examples include 2-thienyl ether, 3-thienyl ether, 4-thiazolyl ether, 2-thiazolyl ether, 2-furyl ether, 3 -Furyl ether, 4-oxazolyl ether, 2-oxazolyl ether, 2-pyrrolyl ether, 3-pyrrolyl ether, 3-imidazolyl ether, 2-triazolyl ether, 1-pyrrolyl ether, 1-imidazolyl ether, 1-pyrazolyl Ether, 2-pyridyl ether, 3-pyridyl ether, 4-pyridyl ether, 2-pyrazyl ether, 4-pyrimidyl ether, 2-pyrimidyl ether, 2-quinolyl ether, 2-quinoxalyl ether, 7- Quinolyl ether, 9-carbazolyl ether, 2-ben Thienylene ether, 2-benzo-furyl ether, 2-ind
- Preferred examples of the aromatic acyl group include benzoyl group, phenylbenzoyl group, 4-methylbenzoyl, 4-thiomethylbenzoyl group, 4-methoxybenzoyl group, 4-heptylbenzoyl group, 2,4,5-trimethoxybenzoyl Group, 2,4,5-trimethylbenzoyl group, 3,4,5-trimethoxybenzoyl group, naphthoyl group and the like.
- aromatic acyl group examples include 2-thiophene carboxylic acid ester, 3-thiophene carboxylic acid ester, 4-thiazole carboxylic acid ester, 2-thiazole carboxylic acid ester, 2-furan carboxylic acid ester, 3- Furan carboxylic acid ester, 4-oxazole carboxylic acid ester, 2-oxazole carboxylic acid ester, 2-pyrrole carboxylic acid ester, 3-pyrrole carboxylic acid ester, 3-imidazole carboxylic acid ester, 2-triazole carboxylic acid ester, 1-pyrrole Carboxylic acid ester, 1-imidazolecarboxylic acid ester, 1-pyrazolecarboxylic acid ester, 2-pyridinecarboxylic acid ester, 3-pyridinecarboxylic acid ester, 4-pyridinecarboxylic acid ester, 2-pyrazinecarboxylic acid ester 4-pyrimidine carboxylic acid ester, 2-pyrimidine carboxylic acid ester, 2-quinoline carboxylic acid
- aromatic groups may further have a substituent, but preferably do not have a substituent containing a carboxyl group (—C ( ⁇ O) O—).
- carboxyl group —C ( ⁇ O) O—
- the aromatic moiety is preferably unsubstituted or substituted with an alkyl group or an aryl group.
- An aliphatic acyl group refers to a group in which R of — (C ⁇ O) R is an aliphatic group.
- the aliphatic group site may be any of linear, branched and cyclic aliphatic groups.
- the carbon number of the aliphatic acyl group is preferably 1-20, more preferably 1-12, and even more preferably 1-6.
- the aliphatic acyl group may have a substituent at the aliphatic group site.
- the aliphatic acyl group is preferably unsubstituted, and more preferably an acetyl group, a propionyl group, or a butyryl group.
- the cellulose derivative of this embodiment has a substituent ether-bonded to the glucose skeleton so as to satisfy the formula (3). This is because, if most of the substituents bonded to the glucose skeleton of the cellulose derivative are ester groups, the resulting optical film is likely to cause a birefringence change due to the interaction between the ester groups and water. For this reason, a change in hue and a change in reflection performance with respect to a change in humidity are promoted. However, by introducing an ether group as a substituent, the hydrophobicity of the cellulose derivative is improved. Further, since the ether group has a small interaction with water and hardly causes a change in birefringence, it is considered that a change in hue and a change in reflection performance with respect to a change in humidity are improved.
- Examples of the substituent ether-bonded to the glucose skeleton include a case where R 2 , R 3 and R 6 in the general formula of the cellulose derivative are an aliphatic hydrocarbon group or an aromatic group.
- R 2 , R 3, and R 6 are aromatic groups, R 2 , R 3, and R 6 may be included in a substituent having a multiple bond (multiple bond group) described later.
- the substituent having an ether bond to the glucose skeleton is a substituent having an ether bond between the glucose skeleton and an aliphatic hydrocarbon group.
- the humidity changes This is preferable because a change in color tone and a change in reflection performance are suppressed.
- the aliphatic hydrocarbon groups an unsubstituted aliphatic hydrocarbon group is preferable.
- the unsubstituted aliphatic hydrocarbon group is an aliphatic group containing no atoms other than carbon atoms and hydrogen atoms, and may be any of linear, branched and cyclic groups.
- the aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a linear alkyl group.
- the carbon number of the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-12, and even more preferably 1-6. Of these, a methyl group and an ethyl group are particularly preferable.
- the aliphatic hydrocarbon group When the aliphatic hydrocarbon group has a substituent, it preferably has no substituent containing a carboxyl group (—C ( ⁇ O) O—). If it contains a carboxyl group, the hydrophilicity increases and the humidity dependence of the optical properties tends to deteriorate.
- the aliphatic hydrocarbon group having a substituent include a hydroxypropyl group.
- the cellulose derivative of the present embodiment has a substituent that is ester-bonded to the glucose skeleton so as to satisfy the range of the ester average substitution degree XES defined in the above formula (2), and the ether defined in the above formula (3). It has a substituent which is ether-bonded to the glucose skeleton so as to satisfy the range of the average substitution degree X ETH . Moreover, the cellulose derivative satisfies the range of the total substitution degree Y prescribed
- the cellulose derivative of this embodiment preferably has a multiple bond group.
- the multiple bond group is not particularly limited as long as it has at least one double bond or triple bond and has an absorption maximum at a wavelength of 220 nm to 350 nm.
- the average degree of substitution of the multiple bond group in the cellulose derivative is preferably 0.3 or more and 0.7 or less, more preferably 0.3 or more and 0.6 or less, and 0.3 or more and 0.00. More preferably, it is 5 or less.
- a cellulose derivative can further improve the reverse wavelength dispersion characteristic of the obtained optical film by having a multiple bond group exhibiting an absorption maximum and an average substitution degree in the above-mentioned range.
- Examples of such a multiple bond group include a substituent having an aromatic structure.
- Such an aromatic group may be a combination of a double bond and a triple bond.
- an electron-withdrawing or electron-donating functional group may be bonded to the aromatic group. From the viewpoint of improving the wavelength dispersibility of the obtained optical film, the electron-donating group is bonded to the aromatic group. It is preferable.
- the multiple bond group is such that R 2 , R 3 and R 6 in the general formula of the cellulose derivative are —R, —OC—R, —OCNH—R, —OC—O—R, etc. , R is an aromatic group).
- R 2 , R 3 and R 6 are aromatic groups
- the multiple bond group is ether-bonded to the glucose skeleton, and is included in the substituent having the above-described glucose skeleton and ether bond.
- the multiple bond group is bonded to the glucose skeleton through an ether bond, in the organic EL display produced using the obtained optical film, the color change and the reflection performance change are suppressed.
- the multiple bond group is an aromatic group
- excellent productivity is achieved.
- the multi-bonding group has an aromatic structure with a large change in birefringence with respect to the wavelength, so that the effect of adjusting the wavelength dispersion due to the multi-bonding group is easily exhibited. This is because an adjustment effect can be obtained. Therefore, the reaction time when introducing the multiple bond group into the glucose skeleton can be shortened, the influence of elimination of other substituents and the like can be suppressed, and the production stability is improved.
- the degree of substitution of multiple bond groups since it becomes possible to reduce the degree of substitution of multiple bond groups, the number of hydroxy groups per glucose skeleton unit can be increased, and as a result, film brittleness by increasing the hydrogen bond between resins It is also possible to improve.
- an aromatic means what was defined as an aromatic compound in the physics and chemistry dictionary (Iwanami Shoten) 4th edition 1208 pages.
- the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group.
- the aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a terphenyl group. Among them, a phenyl group, a naphthyl group, and a biphenyl group are preferable, and a phenyl group is preferable.
- aromatic heterocyclic group those containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom are preferable.
- heterocycles include furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline.
- aromatic group bonded to the glucose skeleton by an ether bond examples include benzyl ether, 4-phenylbenzyl ether, 4-thiomethylbenzyl ether, 4-methoxybenzyl ether, 2,4,5-trimethylbenzyl ether. 2,4,5-trimethoxybenzyl ether and the like.
- aromatic group bonded to the glucose skeleton through an ether bond examples include 2-thienyl ether, 3-thienyl ether, 4-thiazolyl ether, 2-thiazolyl ether, 2-furyl ether, 3 -Furyl ether, 4-oxazolyl ether, 2-oxazolyl ether, 2-pyrrolyl ether, 3-pyrrolyl ether, 3-imidazolyl ether, 2-triazolyl ether, 1-pyrrolyl ether, 1-imidazolyl ether, 1-pyrazolyl Ether, 2-pyridyl ether, 3-pyridyl ether, 4-pyridyl ether, 2-pyrazyl ether, 4-pyrimidyl ether, 2-pyrimidyl ether, 2-quinolyl ether, 2-quinoxalyl ether, 7- Quinolyl ether, 9-carbazolyl ether, 2-be Zone thienylene ether, 2-benzo-furyl ether, 2-in
- Preferred examples of the aromatic acyl group include benzoyl group, phenylbenzoyl group, 4-methylbenzoyl, 4-thiomethylbenzoyl group, 4-methoxybenzoyl group, 4-heptylbenzoyl group, 2,4,5-trimethoxybenzoyl Group, 2,4,5-trimethylbenzoyl group, 3,4,5-trimethoxybenzoyl group, naphthoyl group and the like.
- aromatic acyl group examples include 2-thiophene carboxylic acid ester, 3-thiophene carboxylic acid ester, 4-thiazole carboxylic acid ester, 2-thiazole carboxylic acid ester, 2-furan carboxylic acid ester, 3- Furan carboxylic acid ester, 4-oxazole carboxylic acid ester, 2-oxazole carboxylic acid ester, 2-pyrrole carboxylic acid ester, 3-pyrrole carboxylic acid ester, 3-imidazole carboxylic acid ester, 2-triazole carboxylic acid ester, 1-pyrrole Carboxylic acid ester, 1-imidazolecarboxylic acid ester, 1-pyrazolecarboxylic acid ester, 2-pyridinecarboxylic acid ester, 3-pyridinecarboxylic acid ester, 4-pyridinecarboxylic acid ester, 2-pyrazinecarboxylic acid ester Ter, 4-pyrimidine carboxylic acid ester, 2-pyrimidine carboxylic acid ester, 2-quinoline carb
- aromatic groups may further have a substituent, but preferably do not have a substituent containing a carboxyl group (—C ( ⁇ O) O—). If it contains a carboxyl group, the hydrophilicity increases and the humidity dependence of the optical properties tends to deteriorate.
- the aromatic moiety is preferably unsubstituted or substituted with an alkyl group or an aryl group.
- the cellulose derivative of the present embodiment can be produced by referring to a known method, for example, a method described in “Encyclopedia of Cellulose”, pages 131 to 164 (Asakura Shoten, 2000). Specifically, the cellulose derivative of the present embodiment uses, as a raw material, cellulose ether in which part of hydroxy groups at the 2-position, 3-position and 6-position are substituted with ether groups, and acid chloride in the presence of a base such as pyridine. Alternatively, it can be produced by introducing a desired substituent or an ester-bonded desired substituent by adding an acid anhydride.
- substitution degree of the substituent of the glucose skeleton can be determined by, for example, 1 H-NMR or 13 C using the method described in Cellulose Communication 6, 73-79 (1999) and Chality 12 (9), 670-674. -Determined by NMR.
- the weight average molecular weight of the cellulose ether derivative is preferably 100,000 to 400,000, more preferably 130,000 to 300,000, and further preferably 150,000 to 250,000.
- the molecular weight is larger than 400,000, not only the solubility in the solvent is lowered, but also the viscosity of the resulting solution becomes too high, not suitable for the solvent casting method, making thermoforming difficult, and the transparency of the film is lowered. Tend to cause such problems.
- the molecular weight is smaller than 100,000, the mechanical strength of the resulting film tends to decrease.
- cellulose ether derivative a cellulose ether derivative produced from a single raw material may be used, or two or more cellulose ether derivatives having different raw materials may be used in combination.
- the optical film of this embodiment includes silica-based fine particles that are matting agents.
- silica-based fine particles include silicon dioxide, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, and magnesium silicate.
- silicon dioxide is preferable from the viewpoint of suppressing an increase in haze of the obtained film.
- the fine particles of silicon dioxide preferably have an average primary particle diameter of 1 to 20 nm and an apparent specific gravity of 70 g / L or more. Among them, those having an average primary particle diameter of 5 to 16 nm are preferable because the haze of the obtained optical film can be satisfactorily lowered.
- the apparent specific gravity is preferably 90 to 200 g / L, more preferably 100 to 200 g / L. A larger apparent specific gravity is preferable because a high-concentration dispersion can be adjusted, and haze and aggregates are improved.
- silicon dioxide fine particles include commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (above, Nippon Aerosil Co., Ltd.).
- Aerosil 200V and Aerosil R972V are preferable because they have an average primary particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more, and have a large effect of reducing the friction coefficient while keeping the haze of the obtained film low.
- Silica-based fine particles usually form secondary particles having an average particle size of 0.05 to 2.0 ⁇ m. These secondary particles exist as aggregates of primary particles in the optical film, and form irregularities of 0.05 to 2.0 ⁇ m on the surface of the optical film.
- the average secondary particle diameter is preferably 0.05 to 1.0 ⁇ m, more preferably 0.1 to 0.7 ⁇ m, and further preferably 0.1 to 0.4 ⁇ m.
- the primary particle diameter and the secondary particle diameter can be calculated, for example, by observing fine particles in the optical film with a scanning electron microscope and setting the diameter of a circle circumscribing the particles as the particle size. At this time, it is possible to adopt a method of changing the place and observing 200 particles and setting the average value to the average particle size.
- the method for preparing silica-based fine particles is not particularly limited.
- a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared, and this fine particle dispersion is separately prepared using an in-line mixer.
- the method of mixing with can be adopted.
- the concentration of silicon dioxide is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20% by mass. More preferably.
- the final addition amount of the matting agent in the dope solution of the cellulose derivative is preferably in the range of 0.001 to 1.0% by mass, more preferably in the range of 0.005 to 0.5% by mass, The range of ⁇ 0.1% by mass is more preferable.
- the optical film of this embodiment can contain, for example, various additives listed below as other additives in addition to the silica-based fine particles described above.
- additives include deterioration inhibitors, ultraviolet absorbers, matting agents other than silica-based fine particles, and plasticizers.
- the optical film of the present embodiment may contain, for example, a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines.
- a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines.
- a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines.
- the deterioration inhibitor include those described in JP-A-3-199201, JP-A-5-97073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854.
- BHT butylated hydroxytoluene
- TAA tribenzylamine
- the content of the deterioration inhibitor is preferably within the range of 0.01 to 1% by mass of the cellulose solution (dope) from the viewpoint of suppressing bleed out (bleeding) to the film surface. More preferably, it is in the range of -0.2 mass%.
- the optical film of this embodiment can contain an ultraviolet absorber.
- the ultraviolet absorber include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Among these, a benzotriazole-based compound with little coloring is preferable. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used.
- an ultraviolet absorber having a wavelength of 370 nm or less is used from the viewpoint of preventing deterioration of a polarizer and an organic EL element. From the viewpoint of the display property of the organic EL element, it is preferable to have the characteristic that the absorption of visible light having a wavelength of 400 nm or more is small.
- benzotriazole compounds examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzo Triazole, 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1 , 1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-3'-t-butyl-5 '-Methylphenyl) -5-chlorobenzotriazole,
- the addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5.0% by mass and more preferably in the range of 0.5 to 5.0% by mass with respect to the cellulose derivative.
- the optical film of the present embodiment can contain a matting agent other than the silica-based fine particles described above.
- a matting agent include titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, and calcium phosphate. Since the particle size, apparent specific gravity, preparation method, and addition amount of these matting agents are the same as those of the silica-based fine particles, description thereof is omitted.
- plasticizer The optical film of the present embodiment can be used in combination with various plasticizers for the purpose of improving the fluidity and flexibility of the composition.
- plasticizers include polyhydric alcohol ester plasticizers, glycolate plasticizers, phthalate ester plasticizers, citrate ester plasticizers, fatty acid ester plasticizers, phosphate ester plasticizers, and polyvalent plasticizers.
- carboxylic acid ester plasticizers and acrylic plasticizers It can be applied to a wide range of uses by selecting or using these plasticizers according to the use.
- optical film of this embodiment can be formed according to a known method.
- typical solution casting methods and melt casting methods will be described.
- the optical film of this embodiment can be produced by a solution casting method.
- a step of preparing a dope by heating and dissolving a thermoplastic resin such as a cellulose derivative and additives (including silica-based fine particles) in an organic solvent, and supporting the prepared dope in a belt-shaped or drum-shaped metal support
- a thermoplastic resin such as a cellulose derivative and additives (including silica-based fine particles) in an organic solvent
- the cellulose derivative in the dope is preferably higher in concentration because the drying load after casting on the metal support can be reduced, but if the concentration of the cellulose derivative is too high, the load during filtration increases. , Filtration accuracy deteriorates. Therefore, the concentration for achieving both of these is preferably in the range of 10% by mass to 35% by mass, and more preferably in the range of 15% by mass to 30% by mass.
- the metal support used preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used.
- the cast width is preferably in the range of 1 m to 4 m.
- the surface temperature of the metal support in the casting step is ⁇ 50 ° C. or higher, and is set as appropriate within the temperature range where the solvent does not boil and foam. The higher the temperature, the faster the web can be dried. However, if the temperature is too high, the web may foam and flatness may deteriorate.
- the surface temperature of the metal support is preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 5 ° C. or higher and 30 ° C. or lower.
- the web can be gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
- the method for controlling the temperature of the metal support is not particularly limited, and a method of blowing warm air or cold air or a method of bringing hot water into contact with the back side of the metal support can be employed.
- the method using hot water is preferable because the heat transfer is efficiently performed, and the time until the temperature of the metal support becomes constant is short.
- warm air considering the decrease in the temperature of the web due to the latent heat of vaporization of the solvent, there are cases where warm air that is higher than the boiling point of the solvent is used and wind that is higher than the target temperature is used while preventing foaming. is there.
- the amount of residual solvent when peeling the web from the metal support is preferably in the range of 10% by weight to 150% by weight, and more preferably 20% by weight to 40%. More preferably, it is more preferably in the range of not more than mass% or in the range of not less than 60% by mass and not more than 130% by mass, more preferably in the range of not less than 20% by mass and not more than 30% by mass or in the range of not less than 70% by mass and not more than 120% by mass.
- the residual solvent amount is defined by the following formula.
- M the mass of the sample taken at any time during or after the web or film is produced
- N the sample taken at any time during or after the web or film is produced at 115 ° C. (Mass after heating for 1 hour)
- the web is peeled off from the metal support and further dried, and the residual solvent amount is preferably 1.0% by mass or less, more preferably 0.01% by mass or less.
- a roller drying method for example, a method in which webs are alternately passed through a number of upper and lower rollers and a method in which a web is dried while being conveyed by a tenter method is employed.
- the optical film of this embodiment preferably has an in-plane retardation Ro 550 measured at a wavelength of 550 nm of 120 nm or more and 160 nm or less. Such retardation can be imparted by stretching the film.
- the stretching method is not particularly limited.
- a method of extending the distance between pins and pins in the direction of travel and extending in the vertical direction, a method of extending in the horizontal direction and extending in the horizontal direction, or a method of extending the length and width simultaneously and extending in both the vertical and horizontal directions are used alone or in combination.
- the film may be stretched in the transverse direction, longitudinally, or in both directions with respect to the film forming direction, and when stretched in both directions, simultaneous stretching or sequential stretching may be used. May be.
- driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.
- the film is usually stretched in the width direction (TD direction) and contracted in the transport direction (MD direction).
- TD direction width direction
- MD direction transport direction
- the shrinkage rate can be determined by the transport angle.
- FIG. 1 is a schematic diagram for explaining the shrinkage ratio in oblique stretching.
- Figure 1 when the oblique stretching the cellulose acylate film F in the direction of reference numeral 112, is the major axis M 1 in the conveying direction, contracts in M 2 by oblique bending.
- reference numeral 111 is an extending direction
- reference numeral 113 is a transport direction (MD direction)
- reference numeral 114 indicates a slow axis.
- the optical film of the present embodiment has an orientation angle of 45 ° ⁇ 2 ° with respect to the transport direction, and can be bonded to the polarizing film in a roll-to-roll manner. preferable.
- the orientation angle of the film can be freely set, and the orientation axis of the film can be set to the left and right with high precision across the film width direction.
- a film stretching apparatus that can be oriented and can control the film thickness and retardation with high accuracy is preferable.
- FIG. 2 is a schematic view showing an example of a rail pattern of an oblique stretching apparatus applicable to the production of the optical film of the present embodiment.
- the figure shown here is an example, Comprising: The extending
- the feeding direction D1 of the long film original is different from the winding direction D2 of the stretched film after stretching, and forms a feeding angle ⁇ i. is doing.
- the feeding angle ⁇ i can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the long film original is gripped by the right and left grippers (tenters) at the entrance of the oblique stretching apparatus (position A in the figure), and travels as the grippers travel.
- the left and right grippers Ci and Co facing the direction substantially perpendicular to the film traveling direction (feeding direction D1) at the oblique stretching apparatus entrance (position A in the figure) are the left and right asymmetric rails Ri and Ro. Run on the top and release the gripped film at the end of stretching (position B in the figure).
- the gripping tools Ci and Co that are opposed to the film feeding direction D1 at the oblique stretching apparatus entrance (the gripping start position by the film gripping tool) A are positions at the end of the film stretching.
- the straight line connecting the grippers Ci and Co is inclined by an angle ⁇ L with respect to the direction substantially perpendicular to the film winding direction D2.
- the original film is obliquely stretched so that the orientation angle is ⁇ L, and an optical film is obtained.
- substantially vertical indicates that the angle is in a range of 90 ⁇ 1 °.
- This stretching apparatus can heat a film original fabric to an arbitrary temperature at which it can be stretched and obliquely stretch the film.
- This stretching apparatus includes a heating zone, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails. Both ends of the film sequentially supplied to the inlet of the stretching apparatus are gripped by a gripping tool, the film is guided into the heating zone, and the film is released from the gripping tool at the outlet of the stretching apparatus. The film released from the gripping tool is wound around the core.
- Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the outlet portion of the stretching apparatus travels outside and is sequentially returned to the inlet portion.
- the rail pattern of the stretching apparatus has an asymmetric shape on the left and right, and the rail pattern can be adjusted manually or automatically depending on the orientation angle ⁇ , the stretching ratio, etc. given to the long stretched film to be manufactured.
- the position of each rail part and the rail connecting part can be freely set, and the rail pattern can be arbitrarily changed (circle part in FIG. 2 is an example of the connecting part) Is).
- the gripping tool of the stretching apparatus travels at a constant speed with a constant distance from the front and rear gripping tools.
- the traveling speed of the gripping tool can be selected as appropriate, but is usually 1 to 100 m / min.
- the difference in travel speed between the pair of left and right grippers is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. This is because if there is a difference in the traveling speed between the left and right sides of the film at the exit of the stretching device, wrinkles and shifts will occur at the exit of the stretching device, so the speed difference between the left and right gripping tools may be substantially the same speed. This is because it is required. In general stretching equipment, etc., there is a speed unevenness that occurs in the order of seconds or less depending on the period of the sprocket teeth driving the chain, the frequency of the drive motor, etc. This does not correspond to the speed difference described in the embodiment.
- a large bending rate is often required for the rail that regulates the locus of the gripping tool, particularly in a portion where the film is transported obliquely.
- the trajectory of the gripping tool draws a curve at the bent portion.
- the long film original fabric is gripped by the left and right grippers at the oblique stretching apparatus entrance (position A in the figure) in sequence, and travels as the grippers travel.
- the left and right gripping tools facing the direction substantially perpendicular to the film traveling direction (feeding direction D1) at the entrance of the oblique stretching apparatus (position A in the figure) run on a rail that is asymmetrical to the preheating zone. Through a heating zone having a stretching zone and a heat setting zone.
- the preheating zone refers to a section where the distance between the gripping tools gripping both ends is kept constant at the heating zone entrance.
- the stretching zone refers to the interval until the gap between the gripping tools that grips both ends starts to reach a predetermined interval.
- the above-described oblique stretching is performed, but longitudinal or lateral stretching may be performed before and after the oblique stretching as necessary.
- oblique stretching there is contraction in the MD direction (fast axis direction) which is a direction perpendicular to the slow axis during bending.
- the heat setting zone refers to the section in which the gripping tools at both ends run parallel to each other during the period when the spacing between the gripping tools after the stretching zone becomes constant again. You may pass through the area (cooling zone) by which the temperature in a zone is set to below the glass transition temperature Tg of the thermoplastic resin which comprises a film, after passing through a heat setting zone. At this time, in consideration of shrinkage of the film due to cooling, a rail pattern that narrows the gap between the opposing grippers in advance may be used.
- the temperature of each zone is within the range of Tg to Tg + 30 ° C. in the preheating zone, Tg to Tg + 30 ° C. in the stretching zone, and Tg ⁇ 30 ° C. to Tg in the cooling zone with respect to the glass transition temperature Tg of the cellulose derivative. It is preferable to set within the range.
- a temperature difference in the width direction may be applied in the stretching zone.
- a method of adjusting the opening degree of the nozzle for sending warm air into the temperature-controlled room so as to make a difference in the width direction, or controlling the heating by arranging the heaters in the width direction is known. Can be used.
- the lengths of the preheating zone, the stretching zone, and the heat setting zone can be appropriately selected.
- the length of the preheating zone is usually in the range of 100 to 150% with respect to the length of the stretching zone, and the length of the heat setting zone is Usually, it is in the range of 50 to 100%.
- the draw ratio (W / Wo) in the drawing step is preferably in the range of 1.3 to 3.0, more preferably in the range of 1.5 to 2.8. When the draw ratio is within this range, the thickness unevenness in the width direction can be reduced. In the stretching zone of the oblique stretching apparatus, the thickness direction unevenness can be further improved by making a difference in the stretching temperature in the width direction.
- Wo represents the width of the film before stretching
- W represents the width of the film after stretching.
- the oblique stretching method applicable in this embodiment includes the stretching methods shown in FIGS. 3 (a) to 3 (c) and FIGS. 4 (a) and 4 (b). Can be mentioned.
- FIG. 3 is a schematic view showing a method for producing the optical film of the present embodiment (an example in which the optical film is drawn from a long film roll and then obliquely stretched), and the long film roll once wound up in a roll shape. The pattern which extends
- FIG. 4 is a schematic view showing a method for producing the optical film of the present embodiment (an example of continuous oblique stretching without winding up the long film original fabric), and without winding up the long film original fabric. The pattern which performs a diagonal stretch process continuously is shown.
- reference numeral 15 indicates an oblique stretching apparatus
- reference numeral 16 indicates a film feeding apparatus
- reference numeral 17 indicates a transport direction changing apparatus
- reference numeral 18 indicates a winding apparatus
- Reference numeral 19 denotes a film forming apparatus. In each figure, reference numerals indicating the same components may be omitted.
- the film feeding device 16 is slidable and swivelable or slidable so that the film can be sent out at a predetermined angle with respect to the oblique stretching device inlet. It is preferable to be able to send FIGS. 3A to 3C show patterns in which the arrangement of the film feeding device 16 and the conveyance direction changing device 17 is changed. FIGS. 4A and 4B show a pattern in which the film formed by the film forming apparatus 19 is directly fed to a stretching apparatus.
- the width of the entire manufacturing apparatus can be further reduced, and the film feeding position and angle can be finely controlled.
- the film feeding device 16 and the transport direction changing device 17 it is possible to effectively prevent the left and right clips from being caught in the film.
- the winding device 18 can be finely controlled by taking up the film at a predetermined angle with respect to the outlet of the oblique stretching device so that the film can be taken up at a predetermined angle.
- a long stretched film having small variations in film thickness and optical value can be obtained. Therefore, the generation of wrinkles in the film can be effectively prevented, and the winding property of the film is improved, so that the film can be wound up in a long length.
- the take-up tension T (N / m) of the stretched film can be adjusted within a range of 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m. preferable.
- the above optical film may be formed by a melt film forming method.
- the melt film-forming method is a molding method in which a composition containing a cellulose derivative or the like is heated and melted to a temperature exhibiting fluidity, and then a melt containing the fluid cellulose derivative is cast.
- the molding method for heating and melting can be classified into, for example, a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretch molding method.
- the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy.
- the plurality of raw materials used in the melt extrusion method are usually preferably kneaded in advance and pelletized.
- Pelletization can be performed by a known method. For example, dry cellulose derivatives and additives are supplied to an extruder with a feeder, kneaded using a monoaxial or biaxial extruder, and formed into a strand from a die. It can be obtained by extrusion, water cooling or air cooling and cutting.
- the additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
- a small amount of additives such as fine particles and antioxidants are preferably mixed in advance in order to mix uniformly.
- the extruder used for pelletization preferably has a method of processing at as low a temperature as possible so that pelletization is possible so that the shearing force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
- a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
- Film formation is performed using the pellets obtained as described above.
- the raw material powder can be put into a feeder as it is, supplied to an extruder, heated and melted, and then directly formed into a film without being pelletized.
- the melting temperature when extruding is in the range of 200 ° C. or higher and 300 ° C. or lower, and removing foreign matter by filtering with a leaf disk type filter or the like.
- the film is cast from a T die into a film, and the film is nipped by a cooling roller and an elastic touch roller, and solidified on the cooling roller.
- the extrusion flow rate is preferably carried out stably by introducing a gear pump.
- a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
- Stainless steel fiber sintered filter is made by compressing the stainless steel fiber body in a complicatedly intertwined state, and sintering and integrating the contact points, changing the density depending on the thickness and compression amount of the fiber, Filtration accuracy can be adjusted.
- Additives such as plasticizers and fine particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
- the film temperature on the touch roller side when the film is nipped between the cooling roller and the elastic touch roller is preferably within the range of Tg or more (Tg + 110 ° C.) of the film.
- a known elastic touch roller can be used as the elastic touch roller having an elastic surface used for such a purpose.
- the elastic touch roller is also called a pinching rotary body, and a commercially available one can also be used.
- the film obtained as described above can be subjected to a stretching and shrinking treatment by a stretching operation after passing through a step of contacting a cooling roller.
- a known roller stretching device or oblique stretching device as described above can be preferably used as a method of stretching and shrinking. It is preferable that the stretching temperature is usually performed in a temperature range of Tg or more (Tg + 60 ° C.) of the resin constituting the film.
- the ends Before winding, the ends may be slit and trimmed to the width of the product, or knurled (embossed) may be applied to both ends to prevent sticking and scratching during winding.
- the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
- the holding part of the clip of both ends of a film is cut out and reused.
- the optical film described above can be formed into a circularly polarizing plate by laminating so that the angle between the slow axis and the transmission axis of the polarizer described later is substantially 45 °.
- substantially 45 ° means within a range of 40 ° to 50 °.
- the angle between the in-plane slow axis of the optical film and the transmission axis of the polarizer is preferably in the range of 41 ° to 49 °, and in the range of 42 ° to 48 °. Is more preferably in the range of 43 ° to 47 °, and particularly preferably in the range of 44 ° to 46 °.
- the circularly polarizing plate of this embodiment is produced by cutting a long roll having a long protective film, a long polarizer, and the above-described long optical film (retardation film) in this order. . Since the circularly polarizing plate is produced using the above optical film, it is effective for shielding the specular reflection of the metal electrode of the organic EL element at all wavelengths of visible light when applied to an organic EL display or the like described later. Can do. As a result, reflection during observation can be prevented and black expression can be improved.
- the circularly polarizing plate of this embodiment has an ultraviolet absorption function.
- the protective film on the viewing side has an ultraviolet absorbing function, a protective effect against ultraviolet rays can be exhibited in both the polarizer and the organic EL element.
- the retardation film on the light emitter side also has an ultraviolet absorbing function, when used in an organic EL display described later, deterioration of the organic EL element can be further suppressed.
- the circularly polarizing plate of the present embodiment uses the retardation film in which the angle of the slow axis (that is, the orientation angle ⁇ ) is adjusted to be “substantially 45 °” with respect to the longitudinal direction,
- a consistent production line enables formation of an adhesive layer and bonding of a polarizer and a retardation film.
- the step of bonding the polarizer and the retardation film is incorporated during the subsequent drying step or after the drying step.
- Each of them can be continuously supplied, and can be connected in a production line that is consistent with the next process by winding in a roll state even after bonding.
- a protective film when bonding a polarizer and retardation film, a protective film can be simultaneously supplied in a roll state and can be bonded continuously. From the viewpoint of performance and production efficiency, it is preferable to simultaneously bond a retardation film and a protective film to a polarizer. That is, after finishing the process of drawing a polarizer by stretching a polarizing film, the protective film and the retardation film are bonded to both sides with an adhesive during the subsequent drying process or after the drying process. It is possible to obtain a rolled circularly polarizing plate.
- the polarizer is preferably sandwiched between the retardation film and the protective film, and a cured layer is preferably laminated on the viewing side of the protective film.
- a cellulose ester-containing film is preferably used as the protective film used for the circularly polarizing plate.
- a cellulose ester-containing film is preferably used.
- the thickness of the protective film is not particularly limited and can be about 10 to 200 ⁇ m, preferably 10 to 100 ⁇ m, and more preferably 10 to 70 ⁇ m.
- a polarizer is an element that passes only light having a plane of polarization in a certain direction, such as a polyvinyl alcohol polarizing film.
- the polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
- the polarizer can be produced by uniaxially stretching a polyvinyl alcohol film or by dyeing the polyvinyl alcohol film and then uniaxially stretching, preferably by further performing a durability treatment with a boron compound.
- the film thickness of the polarizer is preferably in the range of 5 to 30 ⁇ m, and more preferably in the range of 5 to 15 ⁇ m.
- the polyvinyl alcohol film has an ethylene unit content of 1 to 4 mol% described in JP-A Nos. 2003-248123 and 2003-342322, and has a degree of polymerization of 2000 to 4000 and a degree of saponification of 99.000.
- Ethylene-modified polyvinyl alcohol having a content of 0 to 99.99 mol% is preferably used. Further, it can be produced by the methods described in JP 2011-1000016 A, JP 4691205 A, and JP 4804589 A.
- Organic EL display of this embodiment is produced using the circularly polarizing plate. More specifically, the organic EL display of the present embodiment includes a circularly polarizing plate using the retardation film and an organic EL element.
- the screen size of the organic EL display is not particularly limited, and can be 20 inches or more.
- FIG. 5 is a schematic diagram of the configuration of the organic EL display of the present embodiment. Note that the configuration of the organic EL display 100 shown in FIG. 5 is an example, and the configuration of the organic EL display of the present embodiment is not limited at all.
- the organic EL element 200 having the layer 6, the sealing layer 7 and the film 8 (optional) the above-described circularly polarizing plate 300 in which the polarizer 10 is sandwiched between the above-described retardation film 9 and the protective film 11 is provided.
- the organic EL display 100 is configured.
- the protective film 11 is preferably laminated with a cured layer 12.
- the cured layer 12 not only prevents scratches on the surface of the organic EL display but also has an effect of preventing warpage due to the circularly polarizing plate. Further, an antireflection layer 13 may be provided on the cured layer.
- the thickness of the organic EL element itself is about 1 ⁇ m.
- the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Or a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a stack of these hole injection layer, light-emitting layer, and electron injection layer.
- a laminate of various organic thin films for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Or a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a stack of these hole injection layer, light-emitting layer, and electron injection layer.
- holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the fluorescent material. It emits light on the principle that it emits light when the excited fluorescent material returns to the ground state.
- the mechanism of recombination is the same as that of a general diode, and current and light emission intensity show strong nonlinearity with rectification with respect to applied voltage.
- a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO) is used. It is preferably used as an anode.
- ITO indium tin oxide
- a metal electrode such as Mg—Ag or Al—Li is used as a cathode.
- the circularly polarizing plate having the above retardation film can be applied to an organic EL display having a large screen having a screen size of 20 inches or more, that is, a diagonal distance of 50.8 cm or more.
- the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. Therefore, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate.
- the display surface of the organic EL display looks like a mirror surface.
- an organic EL display including an organic EL element having a transparent electrode on the surface side of an organic light emitting layer that emits light by applying a voltage and a metal electrode on the back side of the organic light emitting layer, the surface side (viewing side) of the transparent electrode ), And a retardation plate between the transparent electrode and the polarizing plate.
- the retardation film and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action.
- the retardation film is composed of a quarter retardation film and the angle formed by the polarization direction of the polarizing plate and the retardation film is adjusted to ⁇ / 4, the mirror surface of the metal electrode can be completely shielded. it can.
- the linearly polarized light component of the external light incident on the organic EL display is transmitted by the polarizing plate, and this linearly polarized light is generally elliptically polarized light by the retardation plate.
- the retardation film is a ⁇ / 4 retardation film and the angle formed by the polarization direction of the polarizing plate and the retardation film is ⁇ / 4, it becomes circularly polarized light.
- This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again in the retardation film.
- this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate
- the mirror surface of the metal electrode can be completely shielded. Therefore, according to the organic EL display of this embodiment, external light reflection is suppressed and the bright place contrast and black reproducibility are excellent.
- One aspect of the present invention includes a cellulose derivative and silica-based fine particles, the angle between the long direction and the slow axis is 40 to 50 °, and the in-plane retardation Ro 550 at a wavelength of 550 nm is 120 nm.
- This is a long optical film having a thickness of 160 nm or less and satisfying the following formulas (1) to (3).
- XES is the average ester substitution degree of the cellulose derivative
- XETH is the ether average substitution degree of the cellulose derivative
- Y is the total substitution degree of the cellulose derivative.
- the ratio of the substituent of the cellulose derivative to be used is not suppressed by adding an additive to the retardation fluctuation caused by water coordination to the cellulose derivative. It is suppressed by adjusting.
- changes in optical performance (color performance, reflection characteristics) with respect to humidity fluctuations are suppressed.
- the added matting agent silicone-based fine particles
- the long optical film of the present invention can give a phase difference of ⁇ / 4 to light in a wide band of visible light and exhibits excellent brittleness.
- the ratio of the in-plane retardation Ro 450 at a wavelength of 450 nm to Ro 550 is preferably 0.70 or more and 0.98 or less. This shows excellent reverse wavelength dispersion characteristics.
- the cellulose derivative has a multiple bond group having an absorption maximum at a wavelength of 220 nm to 350 nm, and the average degree of substitution of the multiple bond group in the cellulose derivative is 0.3. It is preferable that it is 0.7 or more. Thereby, the reverse wavelength dispersion characteristic can be further improved.
- the film thickness is preferably in the range of 20 to 60 ⁇ m. This makes it easy to express a desired in-plane retardation value Ro.
- another aspect of the present invention is a circularly polarizing plate in which the long optical film and a polarizer are bonded.
- the effect of shielding the specular reflection of the metal electrode of the organic EL element can be exhibited at all wavelengths of visible light. As a result, reflection during observation can be prevented and black expression can be improved.
- Another aspect of the present invention is an organic electroluminescence display device provided with the circularly polarizing plate.
- a long optical film which exhibits sufficient retardation development, suppresses phase difference fluctuation due to humidity fluctuation, is excellent in adhesiveness and brittleness with a polarizer, and haze increase is suppressed,
- a circularly polarizing plate provided with an optical film and an organic electroluminescence display device can be provided.
- the retardation film 1 was produced by the following method.
- the obtained white solid was dried at 60 ° C. overnight and then vacuum-dried at 90 ° C. for 6 hours to obtain cellulose derivative 1.
- degree of substitution of the substituent of the glucose skeleton of the obtained cellulose derivative according to the method described in Cellulose Communication 6, 73-79 (1999) and Chality 12 (9), 670-674, 1 H-NMR and The average value was determined by 13 C-NMR.
- the number of substituents of the butoxy group which is a substituent having an ether bond was 2.1
- the number of substituents of the acetyl group was 0.3
- the total degree of substitution was 2.4.
- Fine particle additive solution 1 50 parts by mass of dimethyl chloride was placed in the dissolution tank, and 50 parts by mass of the fine particle dispersion prepared above was slowly added while sufficiently stirring the dimethyl chloride. Further, the secondary particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
- the prepared dope was cast on a stainless steel belt support, and then the film was peeled from the stainless steel belt support.
- the peeled original film was uniaxially stretched only in the width direction (TD direction) using a stretching apparatus while being heated, and the transport tension was adjusted so as not to shrink in the transport direction (MD direction).
- drying was terminated while the drying zone was conveyed through many rollers, and a roll-shaped raw film was produced.
- the above-mentioned Ro 550 and Ro 450 / Ro 550 measure the in-plane retardation Ro 450 and Ro 550 at wavelengths of 450 nm and 550 nm using Axometrics manufactured by Axometrics in an environment of 23 ° C. and 55% RH. In addition, Ro 450 / Ro 550 was calculated.
- Example 2 (Synthesis of cellulose derivatives 2-8) In the synthesis of the cellulose derivative 1, the ratio of each constituent material and the reaction conditions in the first step to the second step are appropriately selected and synthesized so as to have the substituent structure of the glucose skeleton shown in Table 1. 1-8 were obtained.
- retardation films 2 to 8 were produced in the same manner except that cellulose derivatives 2 to 8 were used in place of the cellulose derivative 1, respectively.
- the original film is adjusted so that the in-plane retardation value Ro 550 measured at a light wavelength of 550 nm is 140 nm, the film thickness is 50 ⁇ m, and Ro 450 / Ro 550 is the value described in Table 1.
- the film thickness, stretching temperature, width direction (TD direction) and stretching ratio in the transport direction (MD direction) were appropriately adjusted.
- the degree of substitution of the substituent of the glucose skeleton of the cellulose derivative 10 prepared above according to the method described in Cellulose Communication 6, 73-79 (1999) and Chality 12 (9), 670-674, 1 H-NMR and The average value was determined by 13 C-NMR.
- the number of substituents of the butoxy group which is a substituent having an ether bond is 0.7
- the number of substituents of the acetyl group is 1.4
- the acetyl group substitution degree includes the acetyl group and includes multiple bonds.
- haze evaluation The haze was measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) in an environment of 23 ° C. and 55% RH.
- Haze was less than 0.1.
- ⁇ Haze was 0.1 or more and less than 0.5.
- X Haze was 0.5 or more.
- a circularly polarizing plate was prepared by the following method, and the prepared circularly polarizing plate was cut into a 5 cm square, immersed in water for 30 minutes, and then the film was peeled from the circularly polarizing plate to evaluate brittleness.
- a 120 ⁇ m-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.
- the retardation films 1 to 11 are bonded using an adhesive so that the slow axis of the retardation films 1 to 11 and the absorption axis of the polarizer are 45 °, and a protective film (Konica Minoltack KC4UY, 40 ⁇ m thick, manufactured by Konica Minolta Co., Ltd.) were pasted together with water paste to prepare circularly polarizing plates, respectively.
- a protective film Konica Minoltack KC4UY, 40 ⁇ m thick, manufactured by Konica Minolta Co., Ltd.
- an organic EL display for evaluation was produced in the same manner except that, when the organic EL cell was produced, red, blue and green lines were given to the surface on the viewing side with magic ink.
- red, blue, and green lines were given to the surface on the viewing side with magic ink.
- the visibility (reflection performance) of the line of the magic ink attached to the organic EL display was evaluated.
- the visibility (reflection performance) of the magic ink line was similarly evaluated by 10 general monitors according to the following criteria under a high humidity environment of 23 ° C. and 80% RH. In addition, if it was more than (circle), it was judged practically possible as humidity stability of reflective performance.
- the reflection performance here means not the reflection of the surface of a circularly-polarizing plate but the reflection in the organic EL cell which entered the inside of the circularly-polarizing plate.
- the optical films of Examples 1 to 4 (retardation films 1 and 8 to 10) satisfying the numerical range of the formulas (1) to (3) have small haze. Excellent brittleness. Moreover, these optical films were excellent also in the adhesiveness with a polarizer, and the organic electroluminescent display produced using this was excellent also in the black color and antireflection performance.
- the optical film of Comparative Example 1 (retardation film 2) having an ester average substitution degree less than the lower limit of the formula (2) had a large haze.
- the optical film (retardation film 5) of Comparative Example 4 in which the average ether substitution degree exceeds the upper limit of the formula (3) and the total substitution degree exceeds the upper limit of the formula (1) is not excellent in brittleness. The anti-reflective performance of the organic EL display produced using this was not excellent.
- the optical film of the comparative example 5 (retardation film 6) in which the total degree of substitution was less than the lower limit of the formula (1) has a large haze, and the black color and reflection of the organic EL display produced using the optical film. The prevention performance was not excellent.
- the present invention it is possible to obtain a long optical film that exhibits sufficient retardation, suppresses retardation fluctuation due to humidity fluctuation, has excellent adhesion to a polarizer and brittleness, and suppresses haze increase. Therefore, the present invention can be suitably used, for example, in the field of image display devices and the like that are required to obtain good contrast and color tone balance with a wide viewing angle. Moreover, according to this invention, the circularly-polarizing plate provided with the said elongate optical film and an organic electroluminescent display apparatus are provided.
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Abstract
Description
0.3≦XES≦1.5 ・・・ (2)
0.3≦XETH≦2.3 ・・・ (3)
(式中、XESは、セルロース誘導体のエステル平均置換度であり、XETHは、セルロース誘導体のエーテル平均置換度であり、Yは、セルロース誘導体の総置換度である。)
本実施形態の長尺光学フィルム(以下、単に光学フィルムや位相差フィルムともいう)は、長尺方向と遅相軸とのなす角が、40~50°であることを特徴とする。すなわち、長尺光学フィルムは、その長手方向と面内の遅相軸とのなす角が、40~50°である。また、長尺光学フィルムは、波長550nmにおける面内位相差Ro550が120nm以上160nm以下であることを特徴とする。また、長尺光学フィルムは、セルロース誘導体とシリカ系微粒子とを含み、セルロース誘導体が、以下の式(1)~(3)を満たすことを特徴とする。本実施形態の長尺光学フィルムは、遅相軸や面内位相差Ro550が上記範囲内となる光学特性を有しているため、可視光の広い帯域の光に対して、実質的にλ/4の位相差を付与することができる。また、長尺光学フィルムは、構成成分として、置換基の割合が以下の式(1)~(3)を満たすよう調整されたセルロース誘導体を含むため、湿度変動に対する光学性能(色味性能、反射特性)の変化が抑制されるとともに、ヘイズ上昇の抑制効果も充分に得られ、かつ、フィルムに優れた脆性が付与される。以下、本実施形態の長尺光学フィルムについて、光学特性、構成成分の順に説明する。
0.3≦XES≦1.5 ・・・ (2)
0.3≦XETH≦2.3 ・・・ (3)
式中、XESは、セルロース誘導体のエステル平均置換度であり、XETHは、セルロース誘導体のエーテル平均置換度であり、Yは、セルロース誘導体の総置換度である。
本実施形態の光学フィルムにおける面内位相差Roは、以下の式で定義される。
(式中、nxは光学フィルムの面内方向において屈折率が最大になる遅相軸方向xにおける屈折率を表し、nyは光学フィルムの面内方向において前記遅相軸方向xと直交する方向yにおける屈折率を表し、d(nm)は、光学フィルムの厚みを表す。)
次に、本実施形態の光学フィルムの構成成分について説明する。光学フィルムは、主たる成分となる樹脂成分(セルロース誘導体を含む樹脂組成物)と、添加剤成分(上記樹脂成分以外の成分、シリカ系微粒子等のマット剤を含む)とから構成される。
光学フィルムは、主たる成分として、セルロース誘導体を含む。なお、本明細書において、「主たる成分」とは、光学フィルムを構成する樹脂成分において55質量%以上含まれる成分をいう。よって、光学フィルムは、構成する樹脂成分として、セルロース誘導体を55質量%以上含む樹脂組成物が用いられたものが挙げられる。
0.3≦XES≦1.5 ・・・ (2)
0.3≦XETH≦2.3 ・・・ (3)
(式中、XESは、セルロース誘導体のエステル平均置換度であり、XETHは、セルロース誘導体のエーテル平均置換度であり、Yは、セルロース誘導体の総置換度である。)
本実施形態のセルロース誘導体は、式(2)を満たすよう、グルコース骨格にエステル結合した置換基を有する。
本実施形態のセルロース誘導体は、式(3)を満たすよう、グルコース骨格にエーテル結合した置換基を有する。これは、仮にセルロース誘導体のグルコース骨格と結合する置換基の大部分がエステル基である場合、得られる光学フィルムはエステル基と水との相互作用により複屈折変化を引き起こしやすくなる。そのため、湿度変化に対する色味変化や反射性能変化が助長されるが、置換基としてエーテル基を導入することにより、セルロース誘導体の疎水性が向上する。また、エーテル基は、水との相互作用が小さく、複屈折変化を引き起こしにくいため、湿度変化に対する色味変化や反射性能変化が改良されると考えられる。
本実施形態のセルロース誘導体は、多重結合性基を有することが好ましい。多重結合性基としては、少なくとも1つの二重結合または三重結合を有し、波長220nm以上350nm以下において吸収極大を有するものであれば特に限定されない。また、セルロース誘導体における多重結合性基の平均置換度は、0.3以上0.7以下であることが好ましく、0.3以上0.6以下であることがより好ましく、0.3以上0.5以下であることがさらに好ましい。セルロース誘導体は、上記範囲の吸収極大および平均置換度を示す多重結合性基を有することにより、得られる光学フィルムの逆波長分散特性をより向上させることができる。
本実施形態の光学フィルムは、マット剤であるシリカ系微粒子を含む。このようなシリカ系微粒子としては、二酸化ケイ素、タルク、クレイ、焼成カオリン、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム等を挙げることができる。これらの中でも、得られるフィルムのヘイズ上昇を抑制する観点から、二酸化ケイ素が好ましい。二酸化ケイ素の微粒子は、平均一次粒子径が1~20nmであり、かつ見かけ比重が70g/L以上であるものが好ましい。中でも、平均一次粒子径が5~16nmであるものが、得られる光学フィルムのヘイズを良好に下げることができるため好ましい。また、見かけ比重は、90~200g/Lであることが好ましく、100~200g/Lであることがより好ましい。見かけ比重は、値が大きいほど、高濃度の分散液を調整でき、ヘイズ、凝集物が改良されるため好ましい。
本実施形態の光学フィルムは、上記したシリカ系微粒子以外に、その他の添加剤として、たとえば、以下に挙げられる各種添加剤を含有することができる。このような添加剤としては、たとえば、劣化抑制剤、紫外線吸収剤、シリカ系微粒子以外のマット剤、可塑剤等が挙げられる。
本実施形態の光学フィルムには、たとえば、酸化防止剤、過酸化物分解剤、ラジカル重合禁止剤、金属不活性化剤、酸捕獲剤、アミン類等の劣化抑制剤を含有することができる。劣化抑制剤としては、たとえば、特開平3-199201号公報、特開平5-197073号公報、特開平5-194789号公報、特開平5-271471号公報、特開平6-107854号公報に記載のものを使用することができ、具体的には、ブチル化ヒドロキシトルエン(BHT)、トリベンジルアミン(TBA)を使用することができる。劣化抑制剤の含有量としては、フィルム表面へのブリードアウト(滲み出し)を抑制する観点から、セルロース溶液(ドープ)の0.01~1質量%の範囲内であることが好ましく、0.01~0.2質量%の範囲内であることがより好ましい。
本実施形態の光学フィルムは、紫外線吸収剤を含有することができる。紫外線吸収剤としては、たとえば、オキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、ニッケル錯塩系化合物等が挙げられる。これらの中でも、着色が少ないベンゾトリアゾール系化合物が好ましい。また、特開平10-182621号公報、特開平8-337574号公報に記載の紫外線吸収剤、特開平6-148430号公報に記載の高分子紫外線吸収剤も好ましく用いられる。本実施形態の光学フィルムを、位相差フィルムのほかに、偏光板の保護フィルムとして使用する場合、紫外線吸収剤としては、偏光子や有機EL素子の劣化を防止する観点から、波長370nm以下の紫外線の吸収能に優れ、かつ有機EL素子の表示性の観点から、波長400nm以上の可視光の吸収が少ない特性を備えていることが好ましい。
本実施形態の光学フィルムは、上記したシリカ系微粒子以外のマット剤を含有することができる。このようなマット剤としては、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、炭酸カルシウムおよびリン酸カルシウム等が挙げられる。これらマット剤の粒子サイズ、見かけ比重、調製方法および添加量は、シリカ系微粒子と同様であるため、説明は省略する。
本実施形態の光学フィルムは、組成物の流動性や柔軟性を向上する目的で、各種可塑剤を併用することができる。可塑剤としては、たとえば、多価アルコールエステル系可塑剤、グリコレート系可塑剤、フタル酸エステル系可塑剤、クエン酸エステル系可塑剤、脂肪酸エステル系可塑剤、リン酸エステル系可塑剤、多価カルボン酸エステル系可塑剤、アクリル系可塑剤等が挙げられる。用途に応じてこれらの可塑剤を選択、あるいは併用することによって、広範囲の用途に適用できる。
次に、上記した光学フィルムの製造方法を説明する。本実施形態の光学フィルムは、公知の方法に従って製膜することができる。以下、代表的な溶液流延法および溶融流延法について説明する。
本実施形態の光学フィルムは、溶液流延法によって製造することができる。溶液流延法では、セルロース誘導体等の熱可塑性樹脂および添加剤等(シリカ系微粒子を含む)を有機溶媒に加熱溶解させてドープを調製する工程、調製したドープをベルト状またはドラム状の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、剥離したウェブを延伸または収縮する工程、さらに乾燥する工程、仕上がったフィルムを巻き取る工程等が含まれる。
ドープ調整工程において、ドープ中のセルロース誘導体は、濃度が高い方が金属支持体に流延した後の乾燥負荷は低減できて好ましいが、セルロース誘導体の濃度が高過ぎると濾過時の負荷が増大し、濾過精度が悪くなる。そのため、これらを両立する濃度としては、10質量%以上35質量%以下の範囲内であることが好ましく、15質量%以上30質量%以下の範囲内であることがより好ましい。
流延(キャスト)工程において、使用する金属支持体は、表面を鏡面仕上げしたものが好ましく、ステンレススティールベルト、または鋳物で表面をメッキ仕上げしたドラムが好ましく用いられる。
(式中、Mはウェブまたはフィルムを製造中または製造後の任意の時点で採取した試料の質量で、Nはウェブまたはフィルムを製造中または製造後の任意の時点で採取した試料を115℃で1時間の加熱した後の質量である)
乾燥工程において採用される乾燥方法としては、米国特許第2,336,310号、同第2,367,603号、同第2,492,078号、同第2,492,977号、同第2,492,978号、同第2,607,704号、同第2,739,069号および同第2,739,070号の各明細書、英国特許第640,731号および同第736,892号の各明細書、ならびに特公昭45-4554号公報、同49-5614号公報、特開昭60-176834号公報、同60-203430号公報および同62-115035号公報に記載の方法がある。ドラムまたはバンド上での乾燥は、ウェブに対し空気、窒素などの不活性ガスを送風することにより行うことができる。
本実施形態の光学フィルムは、上記のとおり、波長550nmで測定した面内位相差Ro550が、120nm以上160nm以下であることが好ましい。このような位相差は、フィルムを延伸することによって付与し得る。
収縮率(%)=((M1-M2)/M1)×100
で表される。屈曲角度をθとすると、
M2=M1×sin(π-θ)
となり、収縮率は、
収縮率(%)=(1-sin(π-θ))×100
で表される。
次いで、45°の方向に延伸する斜め延伸方法について、さらに説明する。本実施形態の光学フィルムの製造方法において、延伸する光学フィルムに斜め方向の配向を付与する方法として、斜め延伸装置を用いることが好ましい。
上記した光学フィルムは、溶融製膜法によって製膜してもよい。溶融製膜法は、セルロース誘導体等を含む組成物を、流動性を呈する温度まで加熱溶融し、その後、流動性のセルロース誘導体を含む溶融物を流延する成形方法である。
本実施形態の円偏光板は、長尺状の保護フィルム、長尺状の偏光子および上記した長尺状の光学フィルム(位相差フィルム)をこの順に有する長尺ロールを断裁して作製される。円偏光板は、上記光学フィルムを用いて作製されるため、後述する有機ELディスプレイ等に適用することにより、可視光の全波長において、有機EL素子の金属電極の鏡面反射を遮蔽する効果を発現し得る。その結果、観察時の映り込みを防止することができるとともに、黒色表現を向上させることができる。
円偏光板に使用される保護フィルムとしては、セルロースエステル含有フィルムが好適に用いられ、たとえば、市販のセルロースエステルフィルム(たとえば、コニカミノルタタックKC8UX、KC5UX、KC4UX、KC8UCR3、KC4SR、KC4BR、KC4CR、KC4DR、KC4FR、KC4KR、KC8UY、KC6UY、KC4UY、KC4UE、KC8UE、KC8UY-HA、KC2UA、KC4UA、KC6UAKC、2UAH、KC4UAH、KC6UAH、以上、コニカミノルタ(株)製、フジタックT40UZ、フジタックT60UZ、フジタックT80UZ、フジタックTD80UL、フジタックTD60UL、フジタックTD40UL、フジタックR02、フジタックR06、以上、富士フイルム(株)製)が好ましく用いられる。保護フィルムの厚さは、特に限定されず、10~200μm程度とすることができ、好ましくは10~100μmであり、より好ましくは10~70μmである。
偏光子は、一定方向の偏波面の光だけを通す素子であり、たとえば、ポリビニルアルコール系偏光フィルムがある。ポリビニルアルコール系偏光フィルムには、ポリビニルアルコール系フィルムにヨウ素を染色させたものと、二色性染料を染色させたものとがある。
本実施形態の有機ELディスプレイは、上記円偏光板を用いて作製される。より詳細には、本実施形態の有機ELディスプレイは、上記位相差フィルムを用いた円偏光板と、有機EL素子とを備える。有機ELディスプレイの画面サイズは、特に限定されず、20インチ以上とすることができる。
0.3≦XES≦1.5 ・・・ (2)
0.3≦XETH≦2.3 ・・・ (3)
式中、XESは、セルロース誘導体のエステル平均置換度であり、XETHは、セルロース誘導体のエーテル平均置換度であり、Yは、セルロース誘導体の総置換度である。
以下の方法により位相差フィルム1を作製した。
(第1工程:セルロースエーテルの合成)
まず、広葉樹前加水分解クラフト法パルプ(αセルロース含量98.4%)の100gに、60%の水酸化ナトリウム溶液140gを加え混合した。次に、ブロモブタンの400gを加え、撹拌しながら0~5℃の温度範囲に約1時間保った後、30~40℃の温度範囲に加温して6時間反応させた。内容物を濾別して、沈殿物を取除いた後、これに温水を加えた。1%のリン酸水溶液で中和した後、アセトン中に滴下して反応生成物を析出させた。濾別により分離し、アセトン/水(9:1)溶液で数回洗浄を繰り返し、60℃で真空乾燥を行い、ブチルセルロースを得た。生成物のブロモブタンによる置換度(MS)は、NMRによる測定の結果、1.1であり、これをセルロースエーテルとした。
メカニカルスターラー、温度計、冷却管および滴下ロートを装着した3Lの三ツ口フラスコに、第1工程で得られたセルロースエーテルを200g、アセトンを2000mL添加し、室温で撹拌した。ここに350gのアセチルクロリドをゆっくりと滴下し、添加後さらに50℃にて8時間撹拌した。反応後、室温に戻るまで放冷し、反応溶液をメタノール20Lへ激しく撹拌しながら投入すると、白色固体が析出した。白色固体を吸引濾過により濾別し、大量のメタノールで3回洗浄を行った。得られた白色固体を60℃で終夜乾燥した後、90℃で6時間真空乾燥することによりセルロース誘導体1を得た。得られたセルロース誘導体1のグルコース骨格の置換基の置換度について、Cellulose Communication 6,73-79(1999)およびChrality 12(9),670-674に記載の方法に準じて、1H-NMRおよび13C-NMRにより測定し、その平均値を求めた。その結果、エーテル結合を有する置換基であるブトキシ基の置換基数は2.1であり、アセチル基の置換基数は0.3であり、総置換度は2.4であった。
(微粒子分散液の調製)
微粒子(アエロジル R812 日本アエロジル(株)製) 11質量部
エタノール 89質量部
溶解タンクにジメチルクロライドを50質量部入れ、ジメチルクロライドを充分に撹拌しながら、上記調製した微粒子分散液の50質量部をゆっくりと添加した。さらに、二次粒子の粒径が、所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過して、微粒子添加液1を調製した。
はじめに、加圧溶解タンクに下記に示すジメチルクロライドとエタノールを添加した。有機溶媒の入った加圧溶解タンクに、上記合成したセルロース誘導体1を撹拌しながら投入した。これを加熱し、撹拌しながら、完全に溶解した。次いで、微粒子添加液1を添加した後、安積濾紙(株)製の安積濾紙No.244を使用して濾過し、ドープを調製した。
ジメチルクロライド 340質量部
エタノール 64質量部
セルロース誘導体1 100質量部
微粒子添加液1 2質量部
上記調製したドープを、ステンレスベルト支持体上で、流延(キャスト)した後、ステンレスベルト支持体上からフィルムを剥離した。剥離した原反フィルムを、加熱しながら延伸装置を用いて、幅手方向(TD方向)にのみ一軸延伸し、搬送方向(MD方向)には収縮しないように搬送張力を調整した。次いで、乾燥ゾーンを多数のローラーを介して搬送させながら乾燥を終了させ、ロール状の原反フィルムを作製した。
この原反フィルムを、図2に記載の構成からなる斜め延伸装置を用いて、搬送方向に対して、フィルムの光学遅相軸が45°となるよう斜め方向に延伸することでロール状の位相差フィルム1を作製した。なお、延伸条件としては、光波長550nmで測定したフィルム面内位相差Ro550が138nm、膜厚が50μm、Ro450/Ro550が0.9となるように、原反フィルムの膜厚、延伸温度、幅手方向(TD方向)および搬送方向(MD方向)の延伸倍率を適宜調整した。
(セルロース誘導体2~8の合成)
上記セルロース誘導体1の合成において、第1工程~第2工程における各構成材料の比率および反応条件を適宜選択して、表1に記載のグルコース骨格の置換基構成となるように合成し、セルロース誘導体1~8を得た。
上記位相差フィルム1の作製において、セルロース誘導体1に代えて、それぞれセルロース誘導体2~8を用いた以外は同様にして、位相差フィルム2~8を作製した。なお、延伸条件としては、光波長550nmで測定したフィルム面内の位相差値Ro550が140nm、膜厚が50μm、Ro450/Ro550が表1に記載の値となるように、原反フィルムの膜厚、延伸温度、幅手方向(TD方向)および搬送方向(MD方向)の延伸倍率を適宜調整した。
(セルロース誘導体9の合成)
(第1工程)
実施例1と同様の方法により、セルロースエーテルを作製した。
メカニカルスターラー、温度計、冷却管および滴下ロートを装着した3Lの三ツ口フラスコに、第1工程で得られたセルロースエーテルを200g、ピリジンを120mL、アセトンを2000mL添加し、室温で撹拌した。ここに1650gのアセチルクロリドをゆっくりと滴下し、添加後さらに50℃にて8時間撹拌した。反応後、室温に戻るまで放冷し、反応溶液をメタノール20Lへ激しく撹拌しながら投入すると、白色固体が析出した。白色固体を吸引濾過により濾別し、大量のメタノールで3回洗浄を行った。得られた白色固体を60℃で終夜乾燥した後、90℃で6時間真空乾燥することによりセルロース誘導体9を得た。
上記位相差フィルム1の作製において、セルロース誘導体1に代えて、セルロース誘導体9を用いた以外は同様にして、位相差フィルム9を作製した。
(セルロース誘導体10の合成)
(第1工程)
実施例1と同様の方法により、セルロースエーテルを作製した。
メカニカルスターラー、温度計、冷却管及び滴下ロートを装着した3Lの三ツ口フラスコに、第1工程で得られたセルロースエーテルを200g、ピリジンを120mL、アセトンを2000mL添加し、室温で撹拌した。42gのチオフェン-2-カルボニルクロリドをゆっくりと滴下した後、さらに50℃にて8時間撹拌した。反応後、室温に戻るまで放冷し、反応溶液をメタノール20Lへ激しく撹拌しながら投入すると、白色固体が析出した。白色固体を吸引濾過により濾別し、大量のメタノールで3回洗浄を行った。得られた白色固体を60℃で終夜乾燥した後、90℃で6時間真空乾燥することによりセルロース誘導体10を得た。
上記位相差フィルム1の作製において、セルロース誘導体1に代えて、セルロース誘導体10を用いた以外は同様にして、位相差フィルム10を作製した。
帝人化成(株)製の「ピュアエース」WR-W142を用い、位相差フィルム11とした。
ヘイズは23℃、55%RH環境下で、ヘイズメータ(日本電色工業(株)製のNDH2000)を用いて測定した。
◎:ヘイズが0.1未満であった。
○:ヘイズが0.1以上0.5未満であった。
×:ヘイズが0.5以上であった。
以下の方法により円偏光板を作製し、作製した円偏光板を5cm四方に切り取り、水に30分間浸漬させた後、円偏光板からフィルムを剥離することにより脆性を評価した。
厚さ120μmのポリビニルアルコールフィルムを、一軸延伸(温度110℃、延伸倍率5倍)した。これをヨウ素0.075g、ヨウ化カリウム5g、水100gからなる水溶液に60秒間浸漬し、次いでヨウ化カリウム6g、ホウ酸7.5g、水100gからなる68℃の水溶液に浸漬した。これを水洗、乾燥して偏光子を得た。位相差フィルム1~11の遅相軸と、偏光子の吸収軸とが45°となるように、粘着剤を用いて貼合し、偏光子の裏面側には保護フィルム(コニカミノルタタックKC4UY、厚さ40μm、コニカミノルタ(株)製)を水糊によって貼り合せ、それぞれ円偏光板を作製した。
○:剥離する際にフィルムが全く裂けることがなかった。
×:剥離する際にフィルムが裂けた。
上記作製した各偏光板を、23℃80%RHの雰囲気下で24時間保存し、その後、同雰囲気下において、手で剥離性を測定し剥離できたかどうかで確認した。
○:手で剥がせなかった。または端部のみが剥がれ、それ以上剥がすと部材が破壊された。
×:手で端部以外の部分も剥がせた。
3mm厚の50インチ(127cm)用無アルカリガラスを用いて、特開2010-20925号公報の実施例に記載されている方法に準じて、特開2010-20925号公報の図8に記載された構成からなる有機ELセルを作製した。
上記作製した各円偏光板の位相差フィルム1~11の表面に接着剤を塗工した後、有機ELセルの視認側に貼合することでそれぞれ有機ELディスプレイを作製した。
上記作製した各有機ELディスプレイについて、以下の評価を行った。
23℃、20%RHの低湿環境下で、各有機ELディスプレイの最表面から5cm高い位置での照度が1000Lxとなる条件下で、有機ELディスプレイに黒画像を表示した。次いで、23℃、80%RHの高湿環境下で、同様に黒画像を表示した。上記二つの環境下で、各有機ELディスプレイの正面位置(面法線に対し0°)と、面法線に対し40°の斜め角度からの黒画像の色味を比較観察し、湿度による黒味への影響の有無を一般モニター10人により以下の基準に従って評価した。なお、○以上であれば、黒味の湿度安定性としては実用上可と判断した。
◎:9人以上のモニターが、表示された黒の湿度影響はなしと判定した。
○:5~8人のモニターが、表示された黒の湿度影響はなしと判定した。
×:表示された黒の湿度影響はなしと判定したモニターが、4人以下であった。
上記有機ELディスプレイの作製において、有機ELセルを作製した段階で、視認側表面にマジックインキで赤、青、緑の線を付与した以外は同様にして、評価用の有機ELディスプレイを作製した。作製した赤、青、緑の線を有する有機ELディスプレイについて、23℃、20%RHの低湿環境下で、各有機ELディスプレイの最表面から5cm高い位置での照度が1000Lxとなる条件下で、有機ELディスプレイに付したマジックインキの線の視認性(反射性能)を評価した。次いで、23℃、80%RHの高湿環境下で、同様にマジックインキの線の視認性(反射性能)を、一般モニター10人により以下の基準に従って評価した。なお、○以上であれば、反射性能の湿度安定性としては実用上可と判断した。なお、ここでいう反射性能とは、円偏光板の表面の反射でなく、円偏光板の内部に入った有機ELセルにおける反射をいう。
◎:9人以上のモニターが、湿度によるマジックインキの線の視認性影響はなしと判定した。
○:5~8人のモニターが、湿度によるマジックインキの線の視認性影響はなしと判定した。
×:湿度によるマジックインキの線の視認性影響はなしと判定したモニターが、4人以下であった。
B 延伸終了時の位置
Ci、Co 把持具
D1 繰出方向
D2 巻取方向
F セルロースアシレートフィルム
Ri、Ro レール
100 有機ELディスプレイ
200 有機EL素子
300 円偏光板
1 透明基板
2 金属電極
3 TFT
4 有機発光層
5 透明電極
6 絶縁層
7 封止層
8 フィルム
9 位相差フィルム
10 偏光子
11 保護フィルム
12 硬化層
13 反射防止層
15 斜め延伸装置
16 フィルム繰り出し装置
17 搬送方向変更装置
18 巻き取り装置
19 製膜装置
111、112 延伸方向
113 搬送方向
114 遅相軸
Claims (6)
- セルロース誘導体と、シリカ系微粒子とを含み、
長尺方向と遅相軸とのなす角が、40~50°であり、
波長550nmにおける面内位相差Ro550が、120nm以上160nm以下であり、
以下の式(1)~(3)を満たす、長尺光学フィルム。
1.8≦Y≦2.6 ・・・ (1)
0.3≦XES≦1.5 ・・・ (2)
0.3≦XETH≦2.3 ・・・ (3)
(式中、XESは、セルロース誘導体のエステル平均置換度であり、XETHは、セルロース誘導体のエーテル平均置換度であり、Yは、セルロース誘導体の総置換度である) - Ro550に対する波長450nmにおける面内位相差Ro450の比率(Ro450/Ro550)が、0.70以上0.98以下である、請求項1記載の長尺光学フィルム。
- 前記セルロース誘導体は、波長220nm以上350nm以下において吸収極大を有する多重結合性基を有し、
前記セルロース誘導体における前記多重結合性基の平均置換度は、0.3以上0.7以下である、請求項1または2記載の長尺光学フィルム。 - 膜厚が、20~60μmの範囲内である、請求項1~3のいずれか1項に記載の長尺光学フィルム。
- 請求項1~4のいずれか1項に記載の長尺光学フィルムと、偏光子とが貼合されている、円偏光板。
- 請求項5記載の円偏光板が具備されている、有機エレクトロルミネッセンス表示装置。
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WO2012133003A1 (ja) * | 2011-03-30 | 2012-10-04 | 独立行政法人理化学研究所 | セルロース誘導体のエステル化物およびその製造方法 |
WO2013031364A1 (ja) * | 2011-08-31 | 2013-03-07 | コニカミノルタアドバンストレイヤー株式会社 | 有機エレクトロルミネッセンス画像表示装置 |
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WO2012133003A1 (ja) * | 2011-03-30 | 2012-10-04 | 独立行政法人理化学研究所 | セルロース誘導体のエステル化物およびその製造方法 |
WO2013031364A1 (ja) * | 2011-08-31 | 2013-03-07 | コニカミノルタアドバンストレイヤー株式会社 | 有機エレクトロルミネッセンス画像表示装置 |
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CN108752643A (zh) * | 2018-04-10 | 2018-11-06 | 哈尔滨工程大学 | 基于纤维素衍生物纳米二氧化硅杂化材料的制备方法 |
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