JP6209130B2 - Optical film, composition, flat image display device, stereoscopic image display device, liquid crystal display device, organic EL display device, and method for producing optical film - Google Patents

Description

  The present invention relates to an optical film, a composition, in particular, a composition preferably used for producing an optical film, a method for producing an optical film, a flat image display device having an optical film, a stereoscopic image display device, a liquid crystal display device and an organic EL display. Relates to the device.

  Conventionally, as a method for producing an optical film, a solution in which a liquid crystal compound is dissolved in an organic solvent is prepared, and this solution is applied onto a transparent support, dried and cured to continuously produce an optical film. The method is used. By the way, in an optical film, it is calculated | required to orientate a liquid crystalline compound uniformly. In order to produce such an optical film continuously, a liquid crystal compound is applied on a transparent support coated with an alignment film, then dried at a high temperature, and polymerized and hardened by light or heat to achieve uniform alignment. We realize sex.

  Among them, a technique for curing a film by ultraviolet irradiation or the like is known as an efficient means from the viewpoint of productivity of an optical film. For example, in Patent Document 1, as a means for increasing the degree of hardening for the purpose of improving the durability and scratch resistance of an optical film, the optical film is irradiated with ultraviolet rays while being heated (100 ° C. or higher), whereby an alignment layer and a liquid crystal A method for hardening an optically anisotropic layer containing a functional compound is disclosed.

  Further, in Patent Document 2, an alignment film and an optically anisotropic layer containing a liquid crystal compound are laminated on a support in this order, and a photopolymerization initiator is included in the alignment film. An optical film is disclosed in which the maximum absorption wavelength is at least 20 nm longer than the maximum absorption wavelength of the liquid crystalline compound. In this document, wet heat durability is improved by adding an initiator to the alignment film.

  On the other hand, Patent Document 3 discloses the use of a polyfunctional (meth) acrylamide compound having a specific structure as a curing agent.

JP 2006-267628 A JP 2009-98664 A JP 2012-206992 A

  In recent years, thinning of liquid crystal display devices has progressed, and accordingly, an optical film as a constituent member is also required to be thinned. In reducing the thickness of the optical film, it has been studied to reduce the thickness of the support. However, in Patent Documents 1 and 2, when the thickness of the support of the optical film is reduced, UV irradiation is performed under heating conditions when hardening the alignment film layer and the optically anisotropic layer containing the liquid crystalline compound. It became clear that the thin support could not withstand the heat generated by the irradiation and deformed and wrinkled. Such wrinkles deteriorate the surface condition of the optical film, and when incorporated in an image display device, the display performance is degraded. On the other hand, when UV irradiation is performed under low-temperature heating conditions, the generation of wrinkles on the support can be suppressed, but sufficient alignment film cannot be hardened, and the wet heat durability of the optical film deteriorates. It has been found that the display performance is deteriorated when incorporated in the display.

  This invention is made | formed in view of such a situation, and it aims at providing the surface state of a support body favorable, and providing the optical film excellent in wet heat durability. Furthermore, it aims at providing the composition preferably used for manufacture of this optical film, the manufacturing method of an optical film, the flat image display apparatus using an optical film, a three-dimensional image display apparatus, a liquid crystal display device, and an organic EL display apparatus. To do.

  Under such circumstances, as a result of intensive studies by the present inventors, the use of a composition containing a polyvinyl alcohol having a polymerizable group and a polyfunctional (meth) acrylamide compound for the formation of an alignment film results in the above problem. It was found that can be solved. That is, the adhesion between the support or the optically anisotropic layer and the alignment film layer is improved by blending a polyfunctional (meth) acrylamide compound having an appropriate hydrophilicity with the polyvinyl alcohol having a polymerizable group. Can do. Further, by using a compound having a crosslinkable group, the film can be hardened even when polymerized at a low temperature. As a result, it was found that even if the support of the optical film is thin, wrinkles are not generated and the wet heat durability can be improved, and the present invention has been completed.

By the way, in a stereoscopic (3D) image display device that displays a stereoscopic image, in order to prevent deterioration of display performance with respect to rotation of the face of the viewer, or to separate a right eye image and a left eye image, As an optical member for obtaining a circularly polarized image in the opposite direction, a patterned optical anisotropic element is used in which regions having different slow axes and retardations are regularly arranged in a plane. In the so-called film pattern retarder (FPR) using a film as a support for the patterned optical anisotropic element, the present inventors find that the present invention is useful for enhancing the display performance of a stereoscopic image display device. It became clear by the study of.
Furthermore, in recent years, organic EL display devices used for portable terminals such as smartphones have become widespread, and display performance improvement accompanying use under external light has been demanded. As such an application, it is expected to be used for a λ / 4 plate applied to a circularly polarizing plate having antireflection performance, and the present invention is useful in enhancing the display performance of an organic EL display device. It became clear by research of inventors.

Specifically, the above problems have been solved by the following means <1> and <14>, preferably <2> to <13> and <11> to <28>.
<1> A support, an alignment film, and an optically anisotropic layer containing a liquid crystalline compound in this order, the alignment film having a polymerizable group, polyvinyl alcohol, a polyfunctional acrylamide compound, and a polyfunctional methacrylamide An optical film having a polyfunctional acrylamide compound selected from compounds.
<2> The optical film according to <1>, wherein the support has a thickness of 20 to 60 μm.
<3> The <1> or <2>, wherein the polyfunctional acrylamide compound includes two or more types in total of a structure represented by -L-acrylamide group and a structure represented by -L-methacrylamide group The described optical film; wherein L represents a single bond or a divalent linking group.
<4> The optical film according to any one of <1> to <3>, wherein the polyfunctional acrylamide compound includes 3 to 6 acrylamide groups and methacrylamide groups in total.
<5> The polyfunctional acrylamide-based compound has 4 to 40 atoms, respectively, that connect two groups selected from an acrylamide group and a methacrylamide group contained in the molecule. <1> to <4 > The optical film in any one of>.
<6> The optical film according to any one of <1> to <5>, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I):
Formula (I)
In general formula (I), Z represents an n-valent group, L represents a single bond or a divalent linking group, R represents a hydrogen atom or a methyl group, n represents an integer of 3 to 6, n Each L and R may be the same or different.
<7> Of the n —L—NH—C (═O) —CR═CH _{2 in} the general formula (I), (n−1) or (n−2) have the same L. The optical film according to <6>, which is the structure (A), and the remaining one or two are structures having L different from the structure (A).
<8> The optical film according to <6> or <7>, wherein Z in the general formula (I) has any one of the following structures;
In the formula, * represents a binding site with L in the general formula (I).
<9> The optical film according to any one of <1> to <5>, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I-1);
Formula (I-1)
In general formula (I-1), R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different.
<10> The optical film according to any one of <1> to <9>, in which the mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group in the alignment film is 1: 1 to 1:20. .
<11> The mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group in the alignment film is 1: 5 to 1:20, and the optical film is for a viewing angle widening film. <1> The optical film according to any one of to <10>.
<12> The mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group in the alignment film is 1: 1 to 1:20, and the optical film is for a patterned retarder film. <1> The optical film according to any one of to <10>.
<13> The mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group in the alignment film is 1: 1 to 1:20, and the optical film is for a circularly polarizing plate. <10> The optical film according to any one of the above.
<14> A composition comprising polyvinyl alcohol having a polymerizable group and a polyfunctional acrylamide compound selected from polyfunctional acrylamide compounds and polyfunctional methacrylamide compounds.
<15> The composition according to <14>, wherein the polyfunctional acrylamide compound includes a total of two or more types of structures represented by -L-acrylamide groups and -L-methacrylamide groups. ; However, L represents a single bond or a bivalent coupling group.
<16> The composition according to <14> or <15>, wherein the polyfunctional acrylamide compound includes 3 to 6 acrylamide groups and methacrylamide groups in total.
<17> The polyfunctional acrylamide compound has 4 to 40 atoms each connecting two groups selected from an acrylamide group and a methacrylamide group contained in the molecule. <14> to <16 > The composition in any one of>.
<18> The composition according to any one of <14> to <17>, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I):
Formula (I)
In general formula (I), Z represents an n-valent group, L represents a single bond or a divalent linking group, R represents a hydrogen atom or a methyl group, n represents an integer of 3 to 6, n Each L and R may be the same or different.
<19> Of the n —L—NH—C (═O) —CR═CH ₂ of the general formula (I), (n−1) or (n−2) have the same L The composition according to <18>, which is (A), and the remaining one or two are structures having L different from structure (A).
<20> The composition according to <18> or <19>, wherein Z in the general formula (I) is any one of the following structures;
In the formula, * represents a binding site with L in the general formula (I).
<21> The composition according to any one of <14> to <17>, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I-1);
Formula (I-1)
In general formula (I-1), R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different.
<22> The composition according to any one of <14> to <21>, wherein the polyvinyl alcohol having a polymerizable group is a polyvinyl alcohol having a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.
<23> The composition according to any one of <14> to <22>, wherein the mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group is 1: 1 to 1:20.
<24> The composition according to any one of <14> to <23>, which is for an optical film.
<25> A flat image display device or a stereoscopic image display device having the optical film according to any one of <1> to <13>.
<26> A liquid crystal display device or an organic EL display device having the optical film according to any one of <1> to <13>.
<27> Applying the composition according to any one of <14> to <24> in a layer form on a support, and applying a composition containing a liquid crystal compound on the surface of the layered composition in a layer form. A method for producing an optical film, comprising irradiating a composition containing a layered liquid crystal compound with ultraviolet rays at 40 to 90 ° C.
<28> The method for producing an optical film according to <27>, wherein the optical film is the optical film according to any one of <1> to <13>.

  It has become possible to provide an optical film having a favorable surface state of the support and excellent wet heat durability. Furthermore, the composition preferably used for manufacture of this optical film and the manufacturing method of an optical film can be provided. In addition, a flat image display device, a stereoscopic image display device, a liquid crystal display device, and an organic EL display device having an optical film can be provided.

It is a schematic diagram of a pattern optical anisotropic layer. It is a schematic diagram which shows an example of a pattern circularly-polarizing plate. It is typical sectional drawing which shows an example of the liquid crystal display device of this invention. It is typical sectional drawing which shows an example of the organic electroluminescent display apparatus of this invention. It is typical sectional drawing which shows an example of the stereo image display apparatus of this invention.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (λ) is measured with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments Co., Ltd.) by making light of wavelength λ nm incident in the normal direction of the film. In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like. When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method. This measuring method is also partially used for measuring the average tilt angle on the alignment film side of the discotic liquid crystal molecules in the optically anisotropic layer, which will be described later, and the average tilt angle on the opposite side.
Rth (λ) is Re (λ) with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (in the absence of the slow axis, in-film plane) Measure the light at a wavelength of λnm from each tilted direction in steps of 10 degrees from the normal direction to 50 ° on one side with respect to the film normal direction. KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value. In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative. The retardation value is measured from two inclined directions with the slow axis as the tilt axis (rotation axis) (if there is no slow axis, the arbitrary direction in the film plane is the rotation axis). Rth can also be calculated from the following formula (A) and formula (III) based on the value, the assumed value of the average refractive index, and the input film thickness value.
Formula (A):

Note that Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. In the formula (A), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz is the direction orthogonal to nx and ny. Represents the refractive index.
Rth = {(nx + ny) / 2−nz} × d Expression (III)

When the film to be measured is a film that cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film without a so-called optical axis, Rth (λ) is calculated by the following method. Rth (λ) is defined as Re (λ), an in-plane slow axis (determined by KOBRA 21ADH or WR) as an inclination axis (rotation axis), and −50 ° to +50 with respect to the film normal direction. Measured at 11 points by injecting light of wavelength λ nm from each inclined direction in 10 ° steps up to °°, and KOBRA based on the measured retardation value, assumed average refractive index value and input film thickness value. 21ADH or WR is calculated. In the above measurement, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. If the average refractive index is not known, it can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

  The “slow axis” means the direction in which the refractive index is maximized, and the measurement wavelength of the refractive index is a value in the visible light region (λ = 550 nm) unless otherwise specified.

  In the present specification, numerical values, numerical ranges, and qualitative expressions (for example, expressions such as “equivalent” and “equal”) indicating optical characteristics of each member such as an optical film and a liquid crystal layer, It shall be construed to indicate numerical values, numerical ranges and properties including generally acceptable errors for the members used therein.

  In this specification, in the description of the arrangement between the axes and directions and the angle of the crossing angle, in the case of simply “parallel”, “orthogonal”, “0 °”, “90 °”, “45 °”, etc. without indicating a range , “Approximately parallel”, “approximately orthogonal”, “approximately 0 °”, “approximately 90 °”, and “approximately 45 °”, and not strictly. Some deviation is allowed within the range to achieve each purpose. For example, “parallel” “0 °” means that the crossing angle is approximately 0 °, and is −10 ° to 10 °, preferably −5 ° to 5 °, more preferably −3 ° to 3 °. “Orthogonal” and “90 °” means that the crossing angle is approximately 90 °, and is 80 ° to 100 °, preferably 85 ° to 95 °, more preferably 87 ° to 93 °. “45 °” means that the crossing angle is approximately 45 °, and is 35 ° to 55 °, preferably 40 ° to 50 °, more preferably 42 ° to 48 °.

  In the present specification, the (meth) acrylamide compound means a compound containing an acrylamide group or a methacrylamide group in the molecule. That is, in this specification, a polyfunctional (meth) acrylamide compound means a polyfunctional acrylamide compound selected from a polyfunctional acrylamide compound and a polyfunctional methacrylamide compound. In the present specification, the polyfunctional (meth) acrylamide compound and the polyfunctional acrylamide compound are synonymous, and hereinafter, the polyfunctional acrylamide compound and the polyfunctional methacrylamide compound are also referred to as a polyfunctional (meth) acrylamide compound.

  In this specification, an acrylamide group and a methacrylamide group are collectively referred to as a (meth) acrylamide group. In the present specification, when the number of (meth) acrylamide groups is represented, it means the total number of acrylamide groups and methacrylamide groups.

<Composition>
The composition of the present invention comprises polyvinyl alcohol having a polymerizable group and a polyfunctional (meth) acrylamide compound.
When an alignment film, which will be described later, is formed using the composition of the present invention, an optical film having a good surface state and excellent wet heat durability can be provided.

<< Polyvinyl alcohol having a polymerizable group >>
The composition of the present invention has polyvinyl alcohol having a polymerizable group. Polyvinyl alcohol is not particularly defined, but for example, the one described in Example 1 described in Japanese Patent No. 3890368 can be used.
When the optical film is used as an optical compensation film or a viewing angle widening film, the saponification degree of polyvinyl alcohol is preferably 80 to 95 mol%, more preferably 83 to 90 mol%, and particularly preferably 85 to 89 mol%. Moreover, when using an optical film for a pattern retarder film (FPR), a circularly polarizing plate, etc., the saponification degree of polyvinyl alcohol is preferably 85 to 99 mol%, more preferably 88 to 98 mol%, most preferably 90 to 97 mol%. .

  The polymerizable group possessed by polyvinyl alcohol is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.
Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or a methyl group.
Among the formulas (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, and more preferably an epoxy group or an oxetanyl group.

  50-99.9 mass% is preferable in solid content of a composition, and, as for content of the polyvinyl alcohol which has a polymeric group, 60-99.9 mass% is more preferable.

<< Polyfunctional (meth) acrylamide compound >>
The composition of the present invention contains a polyfunctional (meth) acrylamide compound. Since the polyfunctional (meth) acrylamide compound has a function as a crosslinking agent, it is sufficiently hardened even under low-temperature heating conditions. In addition, when the composition of the present invention is used as an alignment film, it is possible to provide an optical film having a good surface state of the support and excellent wet heat durability.

The polyfunctional (meth) acrylamide compound used in the present invention is not particularly defined as long as it contains 3 or more (meth) acrylamide groups, but preferably contains 3 to 6 (meth) acrylamide groups.
The polyfunctional (meth) acrylamide compound used in the present invention includes a structure represented by two or more kinds of -L- (meth) acrylamide groups (where L is a single bond or a divalent linking group). Is preferred. Furthermore, among the structures represented by -L- (meth) acrylamide groups existing in two or more types in one molecule (where L is a single bond or a divalent linking group), The numbers are preferably different. By adopting such a configuration, the polyfunctional (meth) acrylamide compound has an asymmetric molecular structure, and as a result, the water solubility of the polyfunctional (meth) acrylamide compound is increased, thereby further improving the compatibility with polyvinyl alcohol. Can be made.
Here, L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, —O—, —S—, —CO—, —SO ₂ —, —NRa— (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. And a group selected from any one of an alkenylene group, an alkynylene group and an arylene group, or a group consisting of a combination of two or more of these groups is preferable. More preferably, it is a combination of an alkylene group, —O—, —CO—, —SO ₂ —, —NRa— (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom). Valent linking group. The number of atoms constituting the L chain portion is preferably 1-20. The chain here is a chain of atoms bonded to a (meth) acrylamide group, and is the longest chain. For example, when it is a —CH ₂ —CH ₂ — (meth) acrylamide group, the number of atoms constituting the chain portion of L is 2.
The alkylene group, alkenylene group, and alkynylene group may be linear, branched, and cyclic.

  In the polyfunctional (meth) acrylamide compound, the number of atoms connecting (meth) acrylamide groups contained in the molecule (that is, the number of atoms connecting two groups selected from acrylamide group and methacrylamide group) is respectively It is preferably 4 to 40, more preferably 4 to 30, and still more preferably 4 to 20. The number of atoms that link (meth) acrylamide groups refers to the number of atoms that form a chain portion that connects nitrogen atoms in two (meth) acrylamide groups in the molecule. Therefore, for example, in the case of a tetrafunctional (meth) acrylamide compound, there are six combinations of how to count the number of atoms of the chain portion in the (meth) acrylamide group, and it is preferable that each of them is within the above range. For example, in the case of the exemplary compound (1-a) described later, the numbers of atoms connecting the (meth) acrylamide groups are 6, 6, 6, 11, 11, and 11, respectively.

The polyfunctional (meth) acrylamide compound is preferably a compound represented by the following general formula (I).
Formula (I)
(In general formula (I), Z represents an n-valent group, L represents a single bond or a divalent linking group, R represents a hydrogen atom or a methyl group, and n represents an integer of 3 to 6. n L and R may be the same or different.)

  L is synonymous with L in the structure represented by the above-described two or more -L- (meth) acrylamide groups (where L is a single bond or a divalent linking group), and a preferred range is also synonymous. is there. In general formula (I), at least one of L is preferably a divalent linking group.

Z represents an n-valent group, preferably a 3-6 valent linking group, and more preferably a 3-4 valent linking group. As the n-valent group, a hydrocarbon group (preferably a hydrocarbon group having 1 to 10 carbon atoms) and the following Z-1, Z-2 or Z-3 are preferable. More preferably, it is an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms), Z-1, Z-2 or Z-3. More preferably, they are Z-1, Z-2, the following Z-5, or Z-6.
(In the formula, * represents a binding site with L.)

  n represents an integer of 3 to 6, an integer of 3 to 5 is preferable, and 3 or 4 is more preferable.

As the compound represented by the general formula (I), out of n -L-NH-C (= O) -CR = CH ₂ , (n-1) or (n-2) are the same. The structure (A) having L, and the remaining one or two are preferably structures having L different from the structure (A). With such a structure, when an alignment film is formed using the composition of the present invention and an optical film is produced, an optical film having a good surface condition of the support and excellent wet heat durability is obtained. It can be provided.

The compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-1).
Formula (I-1)
(In general formula (I-1), R represents a hydrogen atom or a methyl group. A plurality of R may be the same or different.)

  Although the preferable specific example of a polyfunctional (meth) acrylamide compound is shown below, this invention is not limited at all by the following specific examples.

  The polyfunctional (meth) acrylamide compound is preferably contained in an amount of 0.001 to 5 parts by mass, more preferably 0.01 to 4 parts by mass, with respect to 100 parts by mass of the polyvinyl alcohol having a polymerizable group. It is more preferable to contain ~ 3 parts by mass.

  When the composition of the present invention is used as an optical film, the mass ratio of the polyfunctional (meth) acrylamide compound and the polyvinyl alcohol having a polymerizable group is preferably 1: 1 to 1:20, and 1: 1 to The ratio is more preferably 1:15, and further preferably 1: 1 to 1:10.

  When the composition of the present invention is used as a viewing angle widening film which is one of optical films, the mass ratio of the polyfunctional (meth) acrylamide compound and the polyvinyl alcohol having a polymerizable group is 1: 5 to 1:20. It is preferably 1: 5 to 1:15, more preferably 1: 5 to 1:10.

  When the composition of the present invention is used as a patterned retarder film (FPR) which is one of optical films, the mass ratio of the polyfunctional (meth) acrylamide compound and the polyvinyl alcohol having a polymerizable group is from 1: 1 to 1: It is preferably 20, more preferably 1: 2 to 1:15, and still more preferably 1: 4 to 1:12.

  When the composition of the present invention is used as an optical film for a circularly polarizing plate, the mass ratio of the polyfunctional (meth) acrylamide compound and the polyvinyl alcohol having a polymerizable group is preferably 1: 1 to 1:20. 1: 2 to 1:15 is more preferable, and 1: 4 to 1:12 is even more preferable.

<< Other additives >>
The composition of the present invention may contain other additives in addition to the polyvinyl alcohol having a polymerizable group and the polyfunctional (meth) acrylamide compound.
Examples of other additives include surfactants, basic compounds (for example, sodium hydroxide, lithium hydroxide, triethylamine, etc.), acidic compounds (for example, hydrochloric acid, acetic acid, succinic acid, etc.) and the like. Specifically, bifunctional aldehydes and the like described in paragraph 0081 of Japanese Patent No. 3890368 can be referred to, and the contents thereof are incorporated herein.

<Optical film>
The optical film of the present invention has a support, an alignment film, and an optically anisotropic layer containing a liquid crystalline compound in this order, and the alignment film has a polymerizable group-containing polyvinyl alcohol and a polyfunctional (meth) acrylamide compound. It is characterized by having.
The optical film of the present invention has the composition of the present invention in the alignment film, so that even when it is thinned, the film surface state is good and the wet heat durability is excellent.
Hereinafter, each member will be described in detail.

<< Support >>
The thickness of the support used for the optical film of the present invention is preferably 20 to 60 μm, more preferably 25 to 60 μm, still more preferably 25 to 45 μm.
As a support, it is desirable to use a film having almost no in-plane and thickness direction retardation. The in-plane retardation Re (550) at a wavelength of 550 nm of the support is preferably 0 to 10 nm.

In the present specification, “MD” means a feeding direction of the support, and “TD” means a direction perpendicular to the support, and “MD” coincides with the longitudinal direction in the long support, and “TD”. Corresponds to the width direction. In some cases, it is difficult to specify “MD” and “TD”. In that case, one of the long and short sides of the rectangular support is set as MD, and the other is set as TD, and the tensile modulus is calculated. It shall be.
Moreover, as a support body used for the optical film of this invention, it is preferable that the tensile elasticity modulus of both MD and TD of a support body is 4.0 GPa or more. The higher the tensile modulus, the better. However, it is preferable that the tensile modulus is high enough not to be brittle. From these viewpoints, the average tensile elastic modulus of MD and TD is preferably 4.0 to 6.0 GPa.
As a result of intensive studies by the present inventors, in the present invention, by using a support having a tensile modulus having a high average value in the MD and TD directions, even when the support is thin, the surface shape such as wrinkles is obtained. The support can be transported and the optically anisotropic layer can be laminated without causing a failure. The tensile modulus can be measured with Strograph-R2 (manufactured by Toyo Seiki Co., Ltd.).

As a support used for the optical film of the present invention, a known transparent support for alignment films can be used without particular limitation.
As a material for forming the support, any material may be used as long as it is a polymer excellent in optical performance, transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like. Examples include polycarbonate polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin). Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfone polymers , Polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or a polymer obtained by mixing the aforementioned polymers Is also an example. In the present invention, the support may be formed as a cured layer of an acrylic, urethane, acrylurethane, epoxy, silicone, or other ultraviolet curable or thermosetting resin.

  As a material for forming the support, a thermoplastic norbornene resin can be preferably used. Examples of the thermoplastic norbornene-based resin include ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., and ARTON manufactured by JSR Corporation.

  As a material for forming the support, a cellulose polymer represented by triacetyl cellulose (hereinafter referred to as cellulose acylate), which has been used as a transparent protective film for polarizing plates, can be preferably used. Hereinafter, the cellulose ester film will be described in detail mainly as an example of the support, but it is obvious that the technical matters can be applied to other polymer films as well.

<<< Cellulose acylate >>>
The cellulose ester film preferably contains cellulose acylate as a main component. Cellulose acylate is not particularly limited. Among them, it is preferable to use cellulose acylate having an acetyl substitution degree of 2.70 or more and 2.95 or less. It is preferable that the degree of acetyl substitution is 2.70 or more because compatibility with a plasticizer that satisfies the conditions described later (for example, sucrose benzoate having a specific degree of substitution) is good, and haze of the film is suppressed. Furthermore, in addition to the transparency of the film, the moisture permeability and water content are good, which is preferable. Further, the polarizing plate durability and the wet heat durability of the film itself are also favorable, which is preferable. On the other hand, the degree of substitution is preferably 2.95 or less from the viewpoint of optical performance.

The degree of acetyl substitution of cellulose acylate is more preferably 2.75 or more and 2.90 or less, and particularly preferably 2.82 or more and 2.87 or less.
In addition, the preferable range of total acyl substitution degree is the same as the preferable range of acetyl substitution degree mentioned above.
In addition, the substitution degree of an acyl group can be measured according to the method prescribed | regulated to ASTM-D817-96. The portion not substituted with an acyl group is usually present as a hydroxyl group.

The acyl group substituted on the hydroxyl group of cellulose is preferably an acyl group having 2 to 22 carbon atoms. The acyl group having 2 to 22 carbon atoms may be an aliphatic group or an aryl group, and may be a single group or a mixture of two or more types. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. These preferred acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, Examples include oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl groups. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferable, and acetyl, propionyl and butanoyl are more preferable.
The cellulose acylate used in the present invention preferably has an acetyl group as a substituent.

  In addition, as the cellulose acylate, a mixed fatty acid cellulose acylate in which two or more kinds of acyl groups to be substituted with a hydroxyl group of cellulose may be used. Specific examples of the mixed fatty acid cellulose acylate include cellulose acetate propionate and cellulose acetate butyrate.

The basic principle of the cellulose acylate synthesis method is described in Mita et al., Wood Chemistry pages 180-190 (Kyoritsu Shuppan, 1968). A typical synthesis method is a liquid phase acetylation method using a carboxylic acid anhydride-acetic acid-sulfuric acid catalyst.
In order to obtain cellulose acylate, specifically, cellulose raw materials such as cotton linter and wood pulp are pretreated with an appropriate amount of acetic acid, and then put into a pre-cooled carboxylated mixture to be esterified, and complete cellulose acylate. (The total acyl substitution degree at the 2nd, 3rd and 6th positions is approximately 3.00). The carboxylated mixed solution generally contains acetic acid as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst. The carboxylic anhydride is usually used in a stoichiometric excess over the sum of the cellulose that reacts with it and the water present in the system. After completion of the esterification reaction, a neutralizing agent (for example, calcium, magnesium, iron, aluminum or zinc) is used for hydrolysis of excess carboxylic anhydride remaining in the system and neutralization of a part of the esterification catalyst. Of carbonate, acetate or oxide). Next, the obtained complete cellulose acylate is saponified and aged by maintaining it at 50 to 90 ° C. in the presence of a small amount of an acetylation reaction catalyst (generally, remaining sulfuric acid) to obtain a desired degree of acyl substitution and degree of polymerization. To a cellulose acylate having When the desired cellulose acylate is obtained, the catalyst remaining in the system is completely neutralized with a neutralizing agent as described above, or in water or dilute sulfuric acid without neutralization. The cellulose acylate solution is charged (or water or dilute sulfuric acid is charged into the cellulose acylate solution), the cellulose acylate is separated, washed and stabilized, and the like. Can be obtained.

The number average molecular weight (Mn) of the cellulose acylate is preferably 40,000 to 200,000, and more preferably 100,000 to 200,000. The cellulose acylate used in the present invention preferably has an Mw / Mn ratio of 4.0 or less, more preferably 1.4 to 2.3.
In the present invention, the average molecular weight and molecular weight distribution of cellulose acylate and the like are calculated by calculating the number average molecular weight (Mn) and the weight average molecular weight (Mw) using gel permeation chromatography (GPC). International Publication WO 2008-126535 The ratio can be calculated by the method described in the publication.

<<< Plasticizer >>>
The cellulose ester film may contain a plasticizer together with cellulose acylate as a main component. As the plasticizer, many compounds known as plasticizers for cellulose acylate can also be usefully used. For example, phosphoric acid ester, carboxylic acid ester, sugar ester, polycondensation ester and the like are used. These plasticizers may be used in combination of two or more.
The phosphoric acid ester or carboxylic acid ester that can be used in the present invention is described in, for example, paragraph 0078 of JP2013-032420A, and the contents thereof are incorporated herein.
Polycondensed esters that can be used in the present invention are described, for example, in paragraphs 0015 to 0030 of JP2011-012186A, the contents of which are incorporated herein.
Sugar esters that can be used in the present invention are described, for example, in paragraphs 0022 to 0050 of JP2012-215812A, the contents of which are incorporated herein. In the present invention, it is preferable to add the following sugar ester 1 or 2.
It is preferable that it is 1-40 mass parts with respect to 100 mass parts of polymer components containing a cellulose acylate, and, as for content of the plasticizer used for this invention, it is more preferable that it is 1-20 mass parts. By setting it as such a range, the cellulose-ester film excellent in transparency can be obtained.
When two or more kinds of plasticizers are used in combination, the total content is preferably within the above range.

<<<< UV absorber >>>>
The cellulose ester film may contain a UV (ultraviolet) absorber together with cellulose acylate as a main component. There is no restriction | limiting in particular about UV absorber which can be used for this invention. Any of the UV absorbers conventionally used for cellulose esters can be used. Examples of the UV absorber include compounds described in JP-A No. 2006-184874. Polymer ultraviolet absorbers can also be preferably used. In particular, polymer type ultraviolet absorbers described in JP-A-6-148430 are preferably used.
Although UV-1 to 3 are mentioned as an example, the UV absorber to be added is not limited thereto. The addition amount of the UV absorber is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate.

<<< Retardation expression agent >>>
The cellulose ester film preferably contains at least one retardation developer together with cellulose acylate as a main component. That is, in the present invention, a retardation developer may or may not be used, but it is preferable to use a retardation developer in order to develop a retardation value. Examples of the retardation enhancer that can be used in the present invention include those composed of rod-like or discotic compounds and positive birefringent compounds. As the rod-like or discotic compound, a compound having at least two aromatic rings can be preferably used as a retardation developer. The addition amount of the retardation developer composed of the rod-shaped compound is preferably 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate. Further preferred. The disk-shaped retardation developer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the cellulose acylate resin.
Since the discotic compound is superior to the rod-shaped compound in Rth retardation expression, it is preferably used when a particularly large Rth retardation is required. Two or more types of retardation developing agents may be used in combination, and the total content is preferably within the above range.
The retardation developer preferably has a maximum absorption in the wavelength region of 250 to 320 nm, and preferably has substantially no absorption in the visible region.

The discotic compound will be described. As the discotic compound, a compound having at least two aromatic rings can be used.
In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring. Examples of the discotic compound that can be used in the present invention include compounds described in paragraphs 0038 to 0046 of JP-A-2008-181105.

  In the present invention, rod-like compounds having a linear molecular structure can be preferably used in addition to the above-mentioned discotic compounds. Examples of the rod-like compound that can be used in the present invention include compounds described in paragraphs 0053 to 0095 of JP-A-2007-268898.

<< Method for producing cellulose ester film >>
There is no restriction | limiting in particular in the method of manufacturing a cellulose-ester film, It can form into a film using a well-known method. For example, the film may be formed using either a solution casting film forming method or a melt film forming method. From the viewpoint of improving the surface shape of the film, the cellulose ester film is preferably produced using a solution-flow casting method. A method for producing a cellulose ester film is described, for example, in paragraphs 0056 to 0083 of Japanese Patent Application Laid-Open No. 2012-215812, and the contents thereof are incorporated herein.

(Layer structure)
The cellulose ester film used in the present invention may be a single layer film or may have a laminated structure of two or more layers. For example, it is also preferable that it is a laminated structure composed of two layers of a core layer and a surface layer, and is formed by co-casting.

<< Physical properties of cellulose ester film >>

  The difference between the maximum film thickness and the minimum film thickness in the film width (TD) direction of the cellulose ester film is preferably 2 μm or more. The upper limit is preferably 5 μm or less. If it is 5 micrometers or less, a film physical property can be made uniform. In addition, stress concentration during roll storage can be suppressed. Moreover, since an optically anisotropic layer is laminated | stacked on the film width (TD) direction center part of a support body, as a width | variety (TD) direction position of the film thickness maximum part of a cellulose-ester film, it is a film width (TD) direction position. It is preferable that it exists 600 mm or more outside from the center.

The cellulose ester film preferably has a coefficient of dynamic friction on both surfaces of the film of 0.3 to 3.5, more preferably 0.3 to 3.0, and more preferably 0.3 to 2.0. Most preferably:
If the dynamic friction coefficient is 0.3 or more, the creaking at the time of film conveyance can be improved, and the handling ability can be improved. Moreover, if a dynamic friction coefficient is 3.5 or less, the slipperiness at the time of film conveyance can be improved, and handling aptitude can be improved. In particular, it is preferable that the coefficient of dynamic friction is 3.0 or less because handling aptitude is remarkably improved.
In this specification, the dynamic friction coefficient is calculated by the following method. First, film samples 100 mm × 200 mm and 75 mm × 100 mm were conditioned at 23 ° C. and relative humidity 65% for 2 hours, and a large film was placed on a Tensilon tensile tester (RTA-100, manufactured by Orientec Co., Ltd.). After fixing on top, place a small film with a weight of 200g. Pull the weight in the horizontal direction, measure the force F when moving, and calculate the dynamic friction coefficient μk from the following formula.
F = μk × W (W: weight of weight (Kgf))

  The absorbance at a wavelength of 200 to 450 nm is measured with a spectrophotometer (UV-3150, trade name, manufactured by Shimadzu Corporation) of a 40 mm × 40 mm cellulose ester film sample at 25 ° C. and 60% RH. Here, the minimum wavelength at which the absorbance is 0.1 or less is defined as the absorption edge absorbance, and is denoted as λaew. λaew is preferably 350 nm or less, and more preferably 330 nm or less.

<< Alignment film >>
The alignment film in the optical film of the present invention is formed on a support and has the composition of the present invention. The alignment film can be formed by applying a coating solution containing the composition of the present invention on a support and heating and drying.

  When forming the optical film, it is necessary to heat the optical film while irradiating ultraviolet rays in order to fix the alignment of the liquid crystal compound in the optically anisotropic layer and to harden the alignment film. It was found that when a thin support was used, the support was deformed by the heat generation temperature during heating, and the optical film was deformed. In addition, when the heating temperature is lowered, the alignment film layer is not sufficiently hardened to deteriorate the wet heat durability, and when the optical film is used in a liquid crystal display device, the display performance is impaired. It was. In the optical film of the present invention, these problems can be solved by using the alignment film having the composition of the present invention. That is, since the alignment film is hardened by the polyfunctional (meth) acrylamide compound in the composition of the present invention, the alignment film is sufficiently hardened even when the heating temperature is low, and the optical anisotropy is further improved. The orientation of the liquid crystal compound in the layer can be maintained. Moreover, since the polyfunctional (meth) acrylamide compound of this invention has moderate hydrophilicity, it is excellent in adhesiveness with a support body, and even if the thickness of a support body is made thin, an optical film does not deform | transform.

  The mass ratio of the polyfunctional (meth) acrylamide compound and the polyvinyl alcohol having a polymerizable group in the alignment film is preferably 1: 1 to 1:20, more preferably 1: 1 to 1:15. More preferably, the ratio is 1: 1 to 1:10.

  The thickness of the alignment film is not particularly defined, but can be, for example, 200 nm to 1 μm. In the case of the alignment film used in the present invention, sufficient alignment can be ensured even if the thickness is about 200 to 800 nm (preferably 200 to 600 nm).

<< Optically anisotropic layer >>
The optically anisotropic layer in the optical film of the present invention is formed on the alignment film. The optically anisotropic layer in the optical film of the present invention contains a liquid crystalline compound.

<<< Liquid crystal compound >>>
In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. In order to fix the liquid crystalline compound, it is more preferable to use a rod-like liquid crystalline compound having a polymerizable group or a discotic liquid crystalline compound, and the liquid crystalline compound has 2 polymerizable groups in one molecule. It is more preferable to have the above. In the case where the liquid crystal compound is a mixture of two or more, it is preferable that at least one liquid crystal compound has two or more polymerizable groups in one molecule.
Examples of the rod-like liquid crystal compound include those described in claim 1 of JP-T-11-53019, paragraphs 0026 to 0098 of JP-A-2005-289980, and paragraphs 0045 to 0066 of JP-A-2009-217256. Those can be preferably used.
As the discotic liquid crystalline compound, for example, those described in paragraphs 0020 to 0067 of JP-A-2007-108732 and paragraphs 0013 to 0108 of JP-A-2010-244038 can be preferably used, but are not limited thereto. Not.

  It is preferable that the molecules of the liquid crystal compound are fixed in any one of the vertical alignment, the horizontal alignment, the hybrid alignment, and the tilt alignment in the optically anisotropic layer.

Here, the hybrid alignment means that the angle between the disc plane of the discotic liquid crystal compound molecule or the molecular symmetry axis of the molecule of the rod-like liquid crystal compound and the layer plane is the depth direction of the optically anisotropic layer and the alignment film. Orientation that increases or decreases with increasing distance from the surface.
The angle preferably increases with increasing distance.
In addition, as the change of the angle, continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, or intermittent change including increase and decrease are possible. . The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction.
Furthermore, the angle may be increased or decreased as a whole even if it includes a region where the angle does not change, but it is preferable that the angle changes continuously. Of course, the orientation may be uniformly and uniformly inclined.
As an embodiment in which the liquid crystalline compound is fixed in such a hybrid alignment state, for example, an embodiment in which an optical film is used as a viewing angle widening film of a twisted alignment mode liquid crystal display device can be mentioned. Although what is described in Paragraphs 0123 to 0126 of 2012-3183 can be preferably used, the present invention is not limited thereto.

On the other hand, the alignment state of the liquid crystalline compound may be controlled in order to set the retardation in the optically anisotropic layer to about λ / 4. At this time, when the rod-like liquid crystalline compound is used, it is preferable to fix the rod-like liquid crystalline compound in a horizontally aligned state. When the discotic liquid crystalline compound is used, the discotic liquid crystalline compound is vertically aligned. It is preferable to fix in a state. In the present invention, “the rod-like liquid crystal compound is horizontally aligned” means that the director of the rod-like liquid crystal compound and the layer surface are parallel, and “the discotic liquid crystal compound is vertically aligned” means the discotic liquid crystal This means that the disk surface and layer surface of the active compound are perpendicular. It is not strictly required to be horizontal or vertical, but each means a range of ± 20 ° from an accurate angle. It is preferably within ± 5 °, more preferably within ± 3 °, even more preferably within ± 2 °, and most preferably within ± 1 °.
Moreover, in order to make a liquid crystalline compound into a horizontal alignment and a vertical alignment state, you may use the additive (alignment control agent) which accelerates a horizontal alignment and a vertical alignment. Various known additives can be used as the additive.
In the present invention, the optically anisotropic layer is formed by applying a coating solution containing a liquid crystalline compound and optionally other additives such as a polymerization initiator on the alignment film of the present invention. Is preferred. Hereinafter, materials other than the liquid crystalline compound that can be added to the coating solution will be described.

<<< Additives >>>
In the optically anisotropic layer, the liquid crystalline compound is preferably fixed while maintaining the alignment state. The alignment state of the liquid crystal compound is preferably fixed by a polymerization reaction of a polymerizable group introduced into the liquid crystal compound. For this purpose, it is preferable to contain a polymerization initiator in the coating solution. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and electron beam curing (EB curing) using an electron beam. Among these, photopolymerization (photocuring) and EB curing using a low energy electron beam are preferable. It is preferable to use ultraviolet rays for light irradiation for polymerization of the liquid crystalline compound. As an example of a polymerization initiator that generates radicals by the action of light, the description in paragraph No. 0069 of JP2013-007809A can be referred to, and the contents thereof are incorporated in the present specification. Among such photosensitive radical polymerization initiators composed of aromatic ketones, acetophenone compounds and benzyl compounds are particularly preferable in terms of curing characteristics, storage stability, odor, and the like. The photosensitive radical polymerization initiators composed of these aromatic ketones can be used alone or in combination of two or more according to the desired performance. In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity to light. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.

  Multiple photopolymerization initiators may be combined. The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating liquid for forming an optically anisotropic layer.

  In addition to the photopolymerization initiator, an additive may be appropriately added to the coating liquid for forming an optically anisotropic layer. For example, a plasticizer, a monomer, a surfactant, a cellulose ester, an alignment control agent, a chiral agent, and the like can be given. The orientation control agent will be described in detail below. The alignment control agent in the present invention is the alignment of the liquid crystal compound on the air interface side by being unevenly distributed on the surface of the liquid crystal compound layer after application of the coating liquid for forming an optically anisotropic layer, that is, on the air interface side. Represents a compound capable of controlling Depending on the structure of the alignment control agent, the liquid crystalline compound can be aligned substantially vertically on the air interface side, or conversely, can be aligned substantially horizontally. For example, in the case of a discotic liquid crystalline compound, a compound represented by the general formula (VI) described in JP-A Nos. 2000-344734 and 2002-129612 may be added.

  Further, the alignment controller may be a polymer compound as shown below. The alignment control agent to be added is not particularly limited as long as it is a polymer that can be dissolved in the coating solution. Preferred orientation control agents include, for example, polypropylene oxide, polytetramethylene oxide, poly-ε-caprolactone, poly-ε-caprolactone diol, poly-ε-caprolactone triol, polyvinyl acetate, polymelamine, poly (ethylene adipate), poly (1,4-butylene adipate), poly (1,4-butylene glutarate), poly (1,2-butylene glycol), poly (1,4-butylene succinate), poly (1,4-butylene terephthalate) , Poly (ethylene terephthalate), poly (2-methyl-1,3-propylene adipate), poly (2-methyl-1,3-propylene glutarate), poly (neopentyl glycol adipate), poly (neopentyl glycol sebacate) , Poly (1, 3-propylene adipate), poly (1,3-propylene glutarate), polyvinyl butyral, polyvinyl formal, polyvinyl acetal, polyvinyl propanal, polyvinyl hexanal, polyvinyl pyrrolidone, polyacrylic acid ester, polymethacrylic acid ester, poly (3- Hydroxybutyric acid) and the like.

  Moreover, the optically anisotropic layer in the present invention may contain a vertical alignment agent. As the vertical alignment agent, it is preferable to use a pyridinium compound or an onium compound. By containing these compounds, the vertical alignment agent acts as a vertical alignment agent that promotes homeotropic alignment at the alignment film interface of the liquid crystal compound. This also contributes to the improvement of the adhesion at the interface between the optically anisotropic layer (retardation layer) and the alignment film whose orientation state is fixed. The optically anisotropic layer in which the alignment state of the liquid crystal compound is fixed is, if necessary, an air interface side alignment control agent that controls the alignment on the air interface side (for example, a copolymer containing a repeating unit having a fluoroaliphatic group) ) May be contained. The pyridinium compound is described, for example, in paragraphs 0030 to 0052 of JP-A No. 2007-093864, and the onium compound is described in, for example, paragraphs 0027 to 0058 of JP-A No. 2012-208397. Captured in the book.

  From the viewpoint that the vertical alignment agent tends to be unevenly distributed to the alignment film side, the optically anisotropic layer preferably contains at least one selected from a boronic acid compound, boron fluoride, bromine, boron, and silicon. More preferably, at least one selected from boron fluoride is unevenly distributed on the side close to the alignment film.

  The addition amount of the alignment control agent is preferably 0.01% by mass to 10% by mass and more preferably 0.05% by mass to 5% by mass with respect to the liquid crystal compound.

  As a solvent used for preparation of a coating liquid, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, toluene, hexane) alkyl halides (eg, Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane), and the like . Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

  The solid content concentration of the liquid crystal compound and other additives in the coating solution is preferably 0.1% by mass to 60% by mass, more preferably 0.5% by mass to 50% by mass, and 2% by mass to 40% by mass. % Is more preferable. The viscosity of the coating solution is preferably 0.01 mPa · s to 100 mPa · s (0.01 cp to 100 cp), more preferably 0.1 mPa · s to 50 mPa · s (0.1 cp to 50 cp).

  Although the thickness of an optically anisotropic layer changes with uses, it is preferable that it is 0.1-10 micrometers, for example, and it is further more preferable that it is 0.5-5 micrometers.

The in-plane retardation Re (550) at a wavelength of 550 nm of the optically anisotropic layer is preferably 30 to 60 nm, more preferably 35 to 55 nm, and still more preferably 40 to 50 nm. The retardation Rth (550) in the thickness direction at a wavelength of 550 nm of the optically anisotropic layer is preferably 100 to 130 nm, more preferably 105 to 125 nm, and still more preferably 110 to 120 nm.
In the image display device, the optically anisotropic layer preferably has a phase difference region having a phase difference of about λ / 4 because it can be approximated to accurate circularly polarized light. Specifically, Re (550) ) Is preferably 10 to 200 nm, more preferably 110 to 165 nm, still more preferably 115 to 150 nm, and particularly preferably 120 to 145 nm.

<Method for producing optical film>
In the method for producing an optical film of the present invention, the composition of the present invention is applied in a layered manner on a support (Step 1), and the composition containing a liquid crystal compound is applied in a layered manner on the surface of the layered composition. (Step 2), the composition containing the layered liquid crystal compound is irradiated with ultraviolet rays at 60 to 90 ° C. (step 3).

<< Step 1 >>
In step 1, as a method of applying the composition of the present invention in a layered manner, a coating solution containing the composition of the present invention (also referred to as a coating solution for forming an alignment film) is formed on a support. Are preferably used. Examples of the coating method include known coating methods such as curtain coating, spin coating, printing coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, and wire bar method.
In step 1, it is preferable to perform drying after applying the composition of the present invention in layers. The drying temperature is 80 to 150 ° C., and preferably 30 to 180 seconds.

<< Step 2 >>
In step 2, the liquid crystal compound-containing composition is applied in a layered manner by applying a coating liquid (for forming an optically anisotropic layer) prepared by dissolving a discotic liquid crystalline compound or a rod-like liquid crystalline compound in a solvent that can be dissolved. The coating liquid) can be produced by coating on the composition (alignment film) of the present invention applied in layers. Further, if possible, formation by vapor deposition may be used, but formation by coating is preferably used. Examples of the coating method include known coating methods such as curtain coating, spin coating, printing coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, and wire bar method.

<< Step 3 >>
In step 3, the composition containing the layered liquid crystal compound is irradiated with ultraviolet rays at 40 to 90 ° C. Thereby, simultaneously with drying, the liquid crystalline compound is aligned, and further, the alignment of the liquid crystalline compound is fixed by ultraviolet irradiation or the like, thereby forming an optically anisotropic layer of the liquid crystalline compound. The heating temperature at this time is preferably 60 to 90 ° C, more preferably 70 to 90 ° C, and further preferably 75 to 90 ° C. The polymerization reaction for fixing the alignment of the liquid crystal compound is preferably a photopolymerization reaction, and ultraviolet light is preferably used for light irradiation during the reaction. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.

<< Application of optical film >>
The optical film of the present invention can be preferably used for an optical compensation film.
Moreover, since the optical film of this invention contributes to a viewing angle expansion, it is applicable as a viewing angle expansion film.
Further, the optically anisotropic layer has a pattern optical anisotropic having two retardation regions (first retardation region and second retardation region) having Re of about λ / 4 and different slow axis directions. It can also be used as a patterned retarder film (FPR) having a conductive layer.
Moreover, it is applicable as a λ / 4 plate.

<<< Viewing angle expansion film >>>
The optical film of the present invention can be used as a viewing angle widening film. Further, it can be used by being bonded to a polarizing plate described later. In particular, the viewing angle widening film is preferably used also as one of the transparent protective films of the polarizing plate described later from the viewpoint of thinning.

<<< Pattern Retarder Film (FPR) >>>
The optical film of the present invention can be used as a pattern retarder film. Further, it can be used by being bonded to a polarizing plate described later. It is preferable from the viewpoint of thinning that the pattern retarder film is used also as one of the transparent protective films of the polarizing plate described later.
The patterned retarder film is laminated in the order of the support, the alignment film, and the patterned optically anisotropic layer. Since the patterned retarder film produced using the composition of the present invention can suppress the shift of the patterned optical anisotropic layer accompanying fine deformation of the support, the display performance when incorporated in a stereoscopic image display device Are better.
The patterned optically anisotropic layer formed on the alignment film has a first retardation region and a second retardation region on the alignment film, and has a boundary portion between the first and second retardation regions. In the pattern λ / 4 layer, the in-plane slow axes of the first and second retardation regions are orthogonal to each other and Re is λ / 4. When the patterned optically anisotropic layer of this aspect is combined with a polarizing film, the light that has passed through each of the first and second retardation regions becomes a circularly polarized state in opposite directions, and the right and left eye circles respectively. A polarized image is formed.

The pattern retarder film is useful as a member of a stereoscopic image display device, particularly a passive stereoscopic image display device. In this aspect, the polarized image that has passed through each of the first and second phase difference regions is recognized as an image for the right eye or the left eye through polarized glasses or the like. Therefore, it is preferable that the first and second phase difference regions have the same shape so that the left and right images do not become non-uniform, and that the respective arrangements are preferably uniform and symmetrical.
The patterned optical anisotropic layer will be described below.

1A to 1C are schematic front views of examples of patterned optically anisotropic layers.
For example, the optically anisotropic layer 12 shown in FIGS. 1A to 1C includes a first retardation region 12a and a second retardation region 12b that are different from each other in at least one of the in-plane slow axis directions, and The first retardation region 12a and the second retardation region 12b are patterned optically anisotropic layers arranged alternately in the plane. The first retardation region 12a and the second retardation region 12b have in-plane slow axes a and b that are orthogonal to each other.
Further, the first retardation region 12a and the second retardation region 12b in the optically anisotropic layer 12 are alternately arranged in stripes as shown in FIGS. 1A and 1B. The aspect arrange | positioned may be sufficient, and as shown in FIG.1 (C), the aspect which arrange | positioned the rectangular pattern in the grid | lattice form may be sufficient.
When a polarizing plate described later is used as a circular polarizing plate, the polarizing plate 20 (circular polarizing plate) includes a support 16, an alignment film 14, and an optically anisotropic layer 12, as shown in FIG. In the optical film 10 of the invention, the phase difference between the first retardation region 12a and the second retardation region 12b in the optical anisotropic layer 12 is about λ / 4, and the directions of the slow axes a and b are 90 °. For the different optical films 10, the slow axes a and b of the first retardation region 12a and the second retardation region 12b intersect with the absorption axis 23 of the polarizing film 22 at 45 ° (first retardation region 12a In addition, when the slow axes a and b of the second phase difference region 12b are set to 45 °, the absorption axis 23 of the polarizing film 22 is preferably arranged to be 0 °.

Although the following suitable aspects are illustrated as a formation method of the above-mentioned pattern optically anisotropic layer, it can form using various well-known methods, without being limited to these.
The first preferred embodiment utilizes a plurality of actions for controlling the alignment of the liquid crystal compound, and then eliminates any action by an external stimulus (heat treatment, etc.) to make the predetermined alignment control action dominant. Is the method. As the above method, for example, the liquid crystalline compound is brought into a predetermined alignment state by the combined action of the alignment control ability by the alignment film and the alignment control ability of the alignment controller added to the liquid crystalline compound, and then fixed. After forming one phase difference region, any action (for example, action by the alignment control agent) disappears by external stimulation (heat treatment, etc.), and the other orientation control action (action by the alignment film) dominates. Thus, another alignment state is realized and fixed to form the other retardation region. Details of this method are described in paragraphs 0017 to 0029 of JP2012-008170A, the contents of which are incorporated herein by reference.

  A 2nd suitable aspect is an aspect using a pattern orientation film. In this embodiment, pattern alignment films having different alignment control capabilities are formed, a liquid crystalline compound is disposed thereon, and the liquid crystalline compound is aligned. The liquid crystalline compounds achieve different alignment states depending on the alignment control ability of the pattern alignment film. By fixing each alignment state, the pattern of the 1st and 2nd phase difference area | region is formed according to the pattern of an alignment film. The pattern alignment film can be formed using a printing method, mask rubbing for the rubbing alignment film, mask exposure for the photo alignment film, or the like. A method using a printing method is preferable in that large-scale equipment is not required and manufacturing is easy. Details of this method are described in paragraphs 0166 to 0181 of JP2012-032661A, the contents of which are incorporated herein by reference.

  As a third preferred embodiment, for example, a photoacid generator is added to the alignment film. In this example, a photoacid generator is added to the alignment film, and pattern exposure exposes a region where the photoacid generator is decomposed to generate an acidic compound and a region where no acid compound is generated. The photoacid generator remains almost undecomposed in the non-irradiated portion, and the interaction between the alignment film material, the liquid crystal compound, and the alignment control agent added as necessary dominates the alignment state, and the liquid crystal compound Is oriented in a direction whose slow axis is perpendicular to the rubbing direction. When the alignment film is irradiated with light and an acidic compound is generated, the interaction is no longer dominant, the rubbing direction of the rubbing alignment film controls the alignment state, and the liquid crystalline compound has its slow axis parallel to the rubbing direction. To parallel orientation. As the photoacid generator used in the alignment film, a water-soluble compound is preferably used. Examples of photoacid generators that can be used include Prog. Polym. Sci. 23, page 1485 (1998). As the photoacid generator, pyridinium salts, iodonium salts and sulfonium salts are particularly preferably used. Details of this method are described in Japanese Patent Application No. 2010-289360, the contents of which are incorporated herein by reference.

  The patterned optically anisotropic layer is not limited to the above embodiment. A display pixel region in which one in-plane retardation of the first and second retardation regions is λ / 4 and the other in-plane retardation is 3λ / 4 can be used. Furthermore, a retardation region in which one in-plane retardation of the first and second retardation regions is λ / 2 and the other in-plane retardation is 0 may be used.

<< λ / 4 plate >>
The optical film of the present invention is applicable as a λ / 4 plate. Further, it may be used as a circularly polarizing plate by bonding with a polarizing plate described later. Thereby, it can be set as the circularly-polarizing plate which has antireflection performance. By incorporating this circularly polarizing plate into, for example, an organic EL display device, the display performance of the organic EL display device can be improved.
A λ / 4 plate (a plate having a λ / 4 function) is a plate having a function of converting linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). More specifically, the plate has an in-plane retardation value of λ / 4 (or an odd multiple thereof) at a predetermined wavelength λnm.
The in-plane retardation value (Re (550)) at a wavelength of 550 nm of the λ / 4 plate may have an error of about 25 nm around the ideal value (137.5 nm), for example, 110 to 160 nm. It is preferably 120 to 150 nm, more preferably 130 to 145 nm.

When the optically anisotropic layer of the optical film has a single-layer structure, the angle formed by the absorption axis of the polarizing plate and the in-plane slow axis of the optically anisotropic layer is preferably 45 °. In the case of a structure in which a plurality of optically anisotropic layers are laminated, a known configuration / axial relationship can be appropriately employed.
An example of an aspect in which the optically anisotropic layer has a multilayer structure is, for example, a laminated optically anisotropic layer formed by laminating a λ / 4 layer and a λ / 2 layer. In the laminated optically anisotropic layer, the angle between the in-plane slow axis of the λ / 4 layer plate and the in-plane slow axis of the λ / 2 layer is preferably 60 °.
Here, “λ / 4 layer” means in-plane retardation Re (λ) at a specific wavelength λnm,
Re (λ) = λ / 4
An optically anisotropic layer satisfying the above. The above equation may be achieved at any wavelength in the visible light range (for example, 550 nm), but the in-plane retardation Re (550) at a wavelength of 550 nm is preferably 100 nm to 180 nm, and 110 nm to 170 nm. It is more preferable that This range is preferable because the light leakage of reflected light can be further reduced when combined with a λ / 2 layer described later.
In addition, “λ / 2 layer” means in-plane retardation Re (λ) at a specific wavelength λnm,
Re (λ) = λ / 2
An optically anisotropic layer satisfying the above. The above equation may be achieved at any wavelength in the visible light range (for example, 550 nm). Further, the in-plane retardation Re1 of the λ / 2 layer is preferably set to be substantially twice the in-plane retardation Re2 of the λ / 4 layer. Here, “Retardation is substantially doubled”
Re1 = 2 × Re2 ± 50 nm
It means that. Above all,
Re1 = 2 × Re2 ± 20 nm
It is more preferable that The above equation may be achieved at any wavelength in the visible light range, but is preferably achieved at a wavelength of 550 nm. This range is preferable because the light leakage of reflected light can be further reduced when combined with the above-mentioned λ / 4 layer.

  In the laminated optically anisotropic layer, an alignment film may be disposed between the λ / 4 layer and the λ / 2 layer, but the λ / 4 layer and the λ / 2 layer are adjacent to each other, and λ / 4 It may be an embodiment having substantially no alignment film between the layer and the λ / 2 layer. When there is substantially no alignment film between the λ / 4 layer and the λ / 2 layer, a covalent bond between the compounds contained in the respective optically anisotropic layers can be used, and thus the adhesion is excellent. In this specification, “substantially no alignment film” means that a film formed only for functioning as an alignment film is not included. Even if the surface of the lower layer contributes to the alignment of the liquid crystal compound of the upper layer, as long as the lower layer is not formed only for use as an alignment film, this Included in the invention.

The material of the optically anisotropic layer constituting the λ / 4 plate is not particularly limited as long as it exhibits the above-mentioned characteristics. An optically anisotropic layer). More specifically, the optically anisotropic layer of the λ / 4 plate is a layer formed by fixing a liquid crystal compound having a polymerizable group (rod-like liquid crystal compound or disk-like liquid crystal compound) by polymerization or the like. Preferably, in this case, it is no longer necessary to exhibit liquid crystallinity after forming a layer.
Regarding the λ / 4 plate, the description in paragraphs 0022 to 0253 of JP-A-2003-262727 can be referred to, and the contents thereof are incorporated in the present specification.

<Polarizing plate>
The present invention relates to a polarizing plate having the optical film of the present invention and a polarizing film.
Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine-based polarizing film and the dye-based polarizing film can be generally produced using a polyvinyl alcohol film. The transmission axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film.
When the discotic liquid crystalline compound is used for the optically anisotropic layer, the transmission axis of the polarizing film is arranged so as to be substantially parallel to the surface of the discotic liquid crystalline molecule on the alignment film side. . When a rod-like liquid crystalline compound is used for the optically anisotropic layer, the transmission axis of the polarizing film is arranged so as to be substantially parallel to the major axis direction (slow axis) of the rod-like liquid crystalline molecule. Usually, it is preferably bonded to the support side of the retardation plate, but may be bonded to the optically anisotropic layer side if necessary.

In the polarizing plate, the surface of the optical film on the support side may be bonded to the polarizing film, or the surface of the optical film on the optical anisotropic layer side may be bonded to the polarizing film. An adhesive layer may be disposed between the optical film and the polarizing film. As the pressure-sensitive adhesive layer, for example, the ratio (tan δ = G ″ / G ′) between the storage elastic modulus G ′ and the loss elastic modulus G ″ measured by a dynamic viscoelasticity measuring device is 0.001 to 1.5. Represents a substance, and includes so-called adhesives and substances that are easy to creep. For example, although a polyvinyl alcohol-type adhesive is mentioned, it is not limited to this.
Moreover, you may bond a transparent protective film on the surface on the opposite side to the surface where the optical film of a polarizing film is arrange | positioned, and / or the optical film side. As the transparent protective film, a transparent polymer film is preferable. That the protective film is transparent means that the light transmittance is 80% or more. As the transparent protective film, generally a cellulose ester film, preferably a triacetyl cellulose film is used. The cellulose ester film is preferably formed by a solvent cast method. The thickness of the transparent protective film is preferably 20 to 500 μm, and more preferably 20 to 100 μm.
The polarizing plate may further include a functional layer. Examples of the functional layer include at least one selected from the group consisting of an antireflection layer, an antiglare layer, and a hard coat layer. A known layer material is used for these. Note that a plurality of these layers may be stacked.
For example, the antireflection layer has a simplest configuration in which only the low refractive index layer is coated on the outermost surface of the film. In order to further reduce the reflectivity, it is preferable to configure the antireflection layer by combining a high refractive index layer having a high refractive index and a low refractive index layer having a low refractive index. As a configuration example, two layers of a high refractive index layer / low refractive index layer or three layers having different refractive indexes are arranged in order from the bottom, and a medium refractive index layer (having a higher refractive index than the lower layer and a high refractive index). In some cases, a layer having a lower refractive index than a layer) / a layer having a higher refractive index / a layer having a lower refractive index are stacked in this order. Among them, from the viewpoint of durability, optical characteristics, cost, productivity, etc., it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer in this order on the hard coat layer. Examples include the configurations described in JP-A-8-110401, JP-A-10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like. Japanese Patent Application Laid-Open No. 2008-262187 discloses an antireflection film having a three-layer structure that is excellent in robustness to film thickness fluctuations. When the antireflection film having the above three-layer structure is installed on the surface of an image display device, the average value of reflectance can be reduced to 0.5% or less, reflection can be remarkably reduced, and a three-dimensional effect can be achieved. An excellent image can be obtained. Further, each layer may be provided with other functions, for example, an antifouling low refractive index layer, an antistatic high refractive index layer, an antistatic hard coat layer, an antiglare hard coat layer, and the like. (For example, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.) and the like.

<Circularly polarizing plate>
The present invention relates to a circularly polarizing plate. The circularly polarizing plate includes a λ / 4 plate using the optical film of the present invention and a polarizing film. More specifically, the circularly polarizing plate has a λ / 4 plate and a polarizing film.
The λ / 4 plate is mainly composed of a support, an alignment film formed using the composition of the present invention, and an optically anisotropic layer.
The circularly polarizing plate having the above configuration is suitable for antireflection applications of image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). It is used to improve the contrast ratio of the display light.
For example, the aspect which used the circularly-polarizing plate of this invention for the light extraction surface side of an organic electroluminescence display is mentioned. In this case, external light becomes linearly polarized light by the polarizing film and then becomes circularly polarized light by passing through the retardation plate. When this is reflected by the metal electrode, the circularly polarized state is reversed, and when it passes through the phase difference plate again, it becomes linearly polarized light inclined by 90 ° from the incident time and reaches the polarizing film and is absorbed. As a result, the influence of external light can be suppressed.

When the optically anisotropic layer of the λ / 4 plate is a laminated optically anisotropic layer including the first optically anisotropic layer (H) and the second optically anisotropic layer (Q), the first optical anisotropic layer There are no particular restrictions on the angle formed between the slow axis of the crystalline layer (H) and the second optically anisotropic layer (Q) and the absorption axis of the polarizing film, and the first and second optically anisotropic layers (H) and 2nd The optimum angle is appropriately adjusted according to the properties of the optically anisotropic layer (Q).
For example, the first optical anisotropic layer (H) is a λ / 2 layer, the second optical anisotropic layer (Q) is a λ / 4 layer, and the wavelength of the first optical anisotropic layer (H) is 550 nm. When Rth in is negative, the angle formed by the slow axis direction of the first optical anisotropic layer (H) and the absorption axis direction of the polarizing film is preferably in the range of 75 ° ± 10 °, A range of 75 ° ± 8 ° is more preferable, and a range of 75 ° ± 5 ° is more preferable. Further, at this time, the angle formed by the slow axis direction of the second optically anisotropic layer (Q) and the absorption axis direction of the polarizing film is preferably in the range of 15 ° ± 10 °, and is preferably 15 ° ± 8 °. The range is more preferable, and the range of 15 ° ± 5 ° is more preferable. The above range is preferable because light leakage of reflected light can be reduced to a level where it is not visually recognized.

  The first optical anisotropic layer (H) is a λ / 2 layer, the second optical anisotropic layer (Q) is a λ / 4 layer, and the wavelength of the first optical anisotropic layer (H) is 550 nm. When Rth in is positive, the angle formed by the slow axis direction of the first optical anisotropic layer (H) and the absorption axis direction of the polarizing film is preferably in the range of 15 ° ± 10 °, The range of 15 ° ± 8 ° is more preferable, and the range of 15 ° ± 5 ° is more preferable. Further, at this time, the angle formed between the slow axis direction of the second optically anisotropic layer (Q) and the absorption axis direction of the polarizing film is preferably in the range of 75 ° ± 10 °, and is 75 ° ± 8 °. The range is more preferable, and the range of 75 ° ± 5 ° is more preferable. The above range is preferable because light leakage of reflected light can be reduced to a level where it is not visually recognized.

  The polarizing film may be a member having a function of converting natural light into specific linearly polarized light, and an absorbing polarizing film can be used. There is no restriction | limiting in particular in the kind of polarizing film, The polarizing film used normally can be utilized, For example, what was mentioned above can be used. In addition, it is common that a polarizing film is used as a polarizing plate by which the protective film was bonded on both surfaces.

  Although the manufacturing method of a circularly-polarizing plate is not specifically limited, For example, it is preferable to include the process of laminating | stacking a (lambda) / 4 board (optical film of this invention) and a polarizing film continuously in a respectively elongate state. The long circularly polarizing plate is cut according to the size of the screen of the image display device used.

The circularly polarizing plate may further include another layer. For example, the circularly polarizing plate includes a circularly polarizing plate including a λ / 4 plate, a polarizing film, and a protective film. As the protective film, it is preferable to use a cellulose ester film having high optical isotropy.
Moreover, the circularly-polarizing plate which has (lambda) / 4 board, a polarizing film, a protective film, and a functional layer is mentioned. Examples of the functional layer include at least one selected from the group consisting of an antireflection layer, an antiglare layer, and a hard coat layer. For these, known layer materials as described above are used. Note that a plurality of these layers may be stacked.

<Plane image display device>
The present invention also relates to a flat image display device having the polarizing plate of the present invention.
Examples of the flat image display device include a liquid crystal display device and an organic EL display device.

<< Liquid Crystal Display >>
In the present invention, any known mode such as a TN mode, a VA mode, a transverse electric field mode including an IPS mode, an OCB mode, and an ECB mode can be used as a driving mode of the liquid crystal display device. Especially, as a liquid crystal display device, it is suitable for a TN type liquid crystal display device. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known. The Δn · d of the liquid crystal cell is about 300 to 500 nm.

FIG. 3 shows a schematic cross-sectional view of a liquid crystal display device which is an example of the flat image display device of the present invention.
In the liquid crystal display device 100 shown in FIG. 3, a polarizing plate 104 including the optical film 102 of the present invention and a polarizing film 103 is laminated on the viewing side of the liquid crystal cell 101.
The optical film 102 functions as an optical compensation film and is preferably a viewing angle widening film.
A protective film, a functional layer, or the like may be formed on the polarizing film 103.
A polarizing film (backlight side) 105 is disposed on the backlight side of the liquid crystal cell 101. A protective film may be disposed on the front and back surfaces of the polarizing film (backlight side) 105. As the protective film, the optical film of the present invention may be used, or a cellulose ester film such as a cellulose acylate film may be used.
About each layer, you may adhere together through the adhesive and adhesive agent which are not shown in figure.

  In addition, a liquid crystal display device is not limited to the aspect of FIG. For example, in FIG. 3, the optical film of the present invention is disposed only on the viewing side of the liquid crystal cell 101, but the optical film of the present invention may be disposed only on the backlight side of the liquid crystal cell 101. The optical film of the present invention may be disposed on both the viewing side and the backlight side. In FIG. 3, the surface on the optical film 102 side of the polarizing plate 104 is laminated on the liquid crystal cell 101 on the viewing side of the liquid crystal cell 101, but the surface on the opposite side of the optical film 102 of the polarizing plate 104 is The liquid crystal cell 101 may be laminated. That is, on the viewing side, the polarizing plate 104 may be arranged so that the optical film 102 is the outermost surface.

<< Organic EL display device >>
The organic EL display device is a display device configured using an organic EL element in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode).
The organic EL display device of the present invention has a λ / 4 plate (or a circularly polarizing plate) using the above-described optical film of the present invention. Usually, a circularly-polarizing plate is provided on the organic EL panel of an organic EL display device.

FIG. 4 shows a schematic cross-sectional view of an organic EL display device which is an example of the flat image display device of the present invention.
In the organic EL display device 200 shown in FIG. 4, a circularly polarizing plate 204 including a λ / 4 plate 202 and a polarizing film 203 is disposed on the viewing side of the organic EL panel 201. The λ / 4 plate 202 is formed using the optical film of the present invention. The polarizing film 203 may be formed with a protective film, a functional layer, and the like.
About each layer, you may adhere together through the adhesive and adhesive agent which are not shown in figure.

  The organic EL panel 201 is a member in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes of an anode and a cathode. In addition to the light emitting layer, a hole injection layer, a hole transport layer, an electron injection It may have a layer, an electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used for forming each layer.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

  The organic EL display device is not limited to the embodiment shown in FIG. For example, in FIG. 4, the surface on the λ / 4 plate 202 side of the circularly polarizing plate 204 is laminated on the organic EL panel 201, but the surface on the opposite side of the λ / 4 plate 202 of the circularly polarizing plate 204 is It may be laminated on the organic EL panel 201. That is, the circularly polarizing plate 204 may be disposed so that the λ / 4 plate 202 is the outermost surface.

<Stereoscopic image display device>
The present invention also relates to a stereoscopic image display device having the polarizing plate of the present invention. The stereoscopic image display device of the present invention includes at least a third polarizing plate disposed outside the polarizing plate of the stereoscopic image display device of the present invention, and allows a stereoscopic image to be visually recognized through the third polarizing plate. Are preferably used. In the present invention, it is preferable to recognize an image through a glasses-shaped polarizing plate as the third polarizing plate in order to make the viewer recognize a stereoscopic image called a stereoscopic image.

A schematic cross-sectional view of the stereoscopic image display apparatus of the present invention is shown in FIG.
In the stereoscopic image display device 300 illustrated in FIG. 5, a polarizing plate 704 including a pattern retarder film 302 and a polarizing film 303 is disposed on a liquid crystal cell 301. The pattern retarder film 302 is formed using the optical film of the present invention. A protective film, a functional layer, or the like may be formed on the polarizing film 303.
A polarizing film (backlight side) 305 is disposed on the backlight side of the liquid crystal cell 301. A protective film may be disposed on the front and back surfaces of the polarizing film (backlight side) 305.
About each layer, you may adhere together through the adhesive and adhesive agent which are not shown in figure.
The stereoscopic image display device shown in FIG. 5 is a liquid crystal display device, but may be an organic EL display device.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

<Example 101>
Preparation of optical film (KH-1) << Preparation of cellulose acetate solution >>
The composition shown in the following table was put into a mixing tank and stirred while heating to 30 ° C. to dissolve each component to prepare a cellulose acetate solution.

<< Production of Cellulose Acetate Film (Support) >>
The obtained inner layer dope and outer layer dope were cast on a drum cooled to 0 ° C. using a three-layer co-casting die.
The film having a residual solvent amount of 70% by mass was peeled off from the drum, both ends were fixed with a pin tenter, and the film was dried at 80 ° C. while being conveyed with a draw ratio in the MD direction of 110%, and the residual solvent amount was 10%. By the way, it was dried at 110 ° C.
Thereafter, it was dried at a temperature of 140 ° C. for 30 minutes to prepare a cellulose acetate film (outer layer: 3 μm, inner layer: 34 μm, outer layer: 3 μm) having a residual solvent of 0.3% by mass. The optical properties of the produced cellulose acetate film (support (PK-1)) were measured. The thickness of the obtained cellulose acetate film (support (PK-1)) was 40 μm. Re was 5 nm and Rth was 40 nm. The tensile elastic modulus was 4.0 GPa.

  The support (PK-1) thus produced was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried. It was 63 mN / m when the surface energy of this support body (PK-1) was calculated | required by the contact angle method by JIS-3527.

<< Preparation of alignment film >>
On this support (PK-1) (alkali-treated surface), an alignment film coating solution (composition for forming an alignment film) having the following composition was applied at 28 mL / m ² with a # 16 wire bar coater.
Thereafter, the film was dried with warm air of 60 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds to produce an alignment film.

<<< Alignment film coating solution composition >>>
Modified polyvinyl alcohol represented by the following general formula (VI): 10 parts by mass of water ... ········ 371 parts by mass Methanol ··············································································・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5 mass part citrate ester (AS3 manufactured by Sankyo Chemical Co., Ltd.) ・ ・ ・ ・ 0.175 mass part light Polymerization initiator (Irgacure 2959, manufactured by Ciba Geigy Co., Ltd.) ... 2.0 parts by mass of the compound represented by the general formula (I) (1-a) ... 0.5 Parts by mass

Formula (VI)
Compound (1-a) represented by general formula (I)

  Subsequently, the alignment film was rubbed in a direction parallel to the slow axis (measured at a wavelength of 632.8 nm) of the support (PK-1).

<< Formation of optically anisotropic layer >>
<<< Coating liquid composition of optically anisotropic layer >>>
The following composition was dissolved in 107 parts by mass of methyl ethyl ketone to prepare a coating solution.
The following discotic liquid crystalline compound (1) 41.01 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 2.25 parts by mass Cellulose acetate butyrate (CAB551-0. 2, manufactured by Eastman Chemical Co., Ltd. 0.02 parts by mass Cellulose acetate butyrate The following fluoroaliphatic group-containing polymer 1 0.11 parts by mass The following fluoroaliphatic group-containing polymer 2 0.04 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Corp.) 1.35 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.45 parts by mass

Discotic liquid crystalline compounds (1)
Fluoroaliphatic group-containing polymer 1
Fluoroaliphatic group-containing polymer 2 (a / b = 90/10% by mass)

In the step of continuously heating from room temperature to 100 ° C., the solvent is dried, and then the film surface wind speed of the discotic liquid crystalline compound layer is 2.5 m / sec with a dry zone of 130 ° C. For about 90 seconds to align the discotic liquid crystalline compound.
Next, in the ultraviolet irradiation step, the film was transported at a surface temperature (UV temperature) of 90 ° C., and irradiated with ultraviolet rays having an illuminance of 800 mW by an ultraviolet irradiation device (air-cooled metal halide lamp (manufactured by Eye Graphics)).
Then, it was allowed to cool to room temperature and wound into a cylindrical shape to form a roll. Thus, the roll-shaped optical film (KH-1) was produced.

<< Preparation of Polarizing Plate (HB-1) >>
(Preparation of polarizing film)
Polyvinyl alcohol (PVA) having an average polymerization degree of 4,000 and a saponification degree of 99.8 mol% was dissolved in water to obtain a 4.0% aqueous solution. This solution was band-cast using a die having a taper and dried to form a film so that the width before stretching was 110 mm, the thickness was 120 μm at the left end, and 135 μm at the right end.
The film was peeled off from the band, obliquely stretched in the 45 ° direction in a dry state, and immersed in an aqueous solution of iodine 0.5 g / L and potassium iodide 50 g / L for 1 minute at 30 ° C., and then boric acid 100 g / L. L, immersed in an aqueous solution of 60 g / L of potassium iodide at 70 ° C. for 5 minutes, further washed with water at 20 ° C. for 10 seconds, dried at 80 ° C. for 5 minutes, and then iodine-based polarizing film (HF-01 ) The obtained polarizing film (HF-01) had a width of 660 mm and a thickness of 20 μm on both the left and right sides.

<< Attaching optical film >>
The support (PK-1) surface of the optical film (KH-1) is attached to the polarizing film (HF-01) using a polyvinyl alcohol-based adhesive to the produced polarizing film (HF-01). It was.
In addition, a saponified 40 μm thick triacetylcellulose film (TDP40: manufactured by Fuji Film Co., Ltd.) is used to form a polarizing film (HF-01) optical film (KH-1) using a polyvinyl alcohol adhesive. Affixed to the side opposite to the side where the is pasted.
In addition, it arrange | positions so that MD direction of a polarizing film (HF-01), MD direction of a support body (PK-1), and MD direction of a commercially available triacetyl cellulose film (TDP40) may all become parallel. did. In this way, a polarizing plate (HB-1) was produced.

<Example 102>
In Example 101, an optical film (KH-) was prepared in the same manner as in Example 101 except that the amount of the compound (1-a) represented by formula (I) was changed from 0.5 mass to 1.0 mass. 2) and a polarizing plate (HB-2) were produced.

<Example 103>
In Example 101, the optical film (KH- 3) and a polarizing plate (HB-3) were produced.

<Example 104>
In Example 101, an optical film (KH-4) and a polarizing plate (HB-4) were produced in the same manner as in Example 101 except that a cellulose acetate film was produced as follows.

<< Preparation of Cellulose Ester Solution A >>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose ester solution A. The degree of acetyl substitution was measured according to ASTM D-817-91. The viscosity average degree of polymerization was measured by Uda et al.'S intrinsic viscosity method {Kazuo Uda, Hideo Saito, "Journal of the Textile Society", Vol. 18, No. 1, 105-120 (1962)}.

Composition of cellulose ester solution A ―――――――――――――――――――――――――――――――――――
Cellulose acetate (acetyl substitution degree 2.86) 100 parts by weight sugar ester 1 6 parts by weight sugar ester 2 2 parts by weight methylene chloride 365.8 parts by weight methanol 92.6 parts by weight butanol 4.6 parts by weight ―――――――――――――――――――――――――――――

Sugar ester 1 is a compound or mixture of the following structure: In addition, the measuring method of the average ester substitution degree of sugar ester 1 was measured with the following method.
By measurement under the following HPLC conditions, the peak having a retention time of about 31.5 min is 8 substituted, the peak group of 27 to 29 min is 7 substituted, the peak group of 22 to 25 min is 6 substituted, The peak group in the vicinity of 15 to 20 min is 5 substitutions, the peak group in the vicinity of 8.5 to 13 min is 4 substitutions, the peak group in the vicinity of 3 to 6 min is 3 substitutions, and the total area ratio is relative to the total The average degree of substitution was calculated.
<< HPLC measurement conditions >>
Column: TSK-gel ODS-100Z (Tosoh), 4.6 * 150 mm, lot number (P0014)
Eluent A: H ₂ O = 100, Eluent B: AR = 100. A and B both in acetic acid and triethylamine 0.1% (volume ratio) flow rate: 1 ml / min, column temperature: 40 ° C., wavelength: 254 nm, sensitivity: AUX2, injection volume: 10 μl, rinse solution: THF / H ₂ O = 9/1 (volume ratio)
Sample concentration: 5 mg / 10 ml (THF)
In addition, although average ester substitution degree can be measured similarly about sugar ester 2 used in another Example, the following sugar ester 2 was a single compound with ester substitution degree of almost 100%.
Moreover, the sucrose benzoate used in all the examples used what was less than 100 ppm after carrying out the vacuum drying (10 mmHg or less) of toluene which is a reaction solvent.

Sugar ester 1: 71% average ester substitution degree

Sugar ester 2: Average ester substitution degree 100% (single compound)
R = acetyl group / i-butyryl group (2/6)

<<< Preparation of Matting Agent Dispersion B >>>
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent dispersion B.

<<< Preparation of UV absorber solution C-1 >>>
The following composition was put into another mixing tank and stirred while heating to dissolve each component to prepare an ultraviolet absorber solution C-1.

<<< Preparation of UV absorber solution C-2 >>>
The following composition was put into another mixing tank and stirred while heating to dissolve each component to prepare an ultraviolet absorber solution C-2.

<< Production of cellulose ester film >>
The matting agent dispersion B was added to the cellulose ester solution A so that the sugar ester 1 would be in the above-mentioned amount added per 100 parts by mass of the cellulose ester. To the obtained solution, UV absorber solution C-1 or C-2 was added so that the UV absorber (UV-1) and the UV absorber (UV-2) were added in the amounts described above. The dope was prepared by sufficiently stirring while heating to dissolve each component. The obtained dope was heated to 30 ° C., and cast on a mirror surface stainless steel support, which was a drum having a diameter of 3 m, through a casting Giuser. The surface temperature of the support was set to −5 ° C., and the coating width was 1470 mm. The space temperature of the entire casting part was set to 15 ° C. The cellulose ester film cast and rotated 50 cm before the end point of the casting part was peeled off from the drum, and then both ends were clipped with a pin tenter. The residual solvent amount of the cellulose ester film immediately after peeling was 70%, and the film surface temperature of the cellulose ester film was 5 ° C.

The cellulose ester film held by the pin tenter was transported to the drying zone. In the initial drying, a drying air of 45 ° C. was blown. Next, it was dried at 110 ° C. for 5 minutes and further at 140 ° C. for 10 minutes.
The film thickness of the cellulose ester film was 40 μm. Furthermore, the film thickness distribution in the width direction was 2 μm. The tensile elastic modulus was 4.8 GPa.

<Example 105>
In Example 101, an optical film (KH-5) and a polarizing plate (HB-5) were produced in the same manner as in Example 101 except that 0.05 part by mass of the following boronic acid compound was added to the optically anisotropic layer. did.
Boronic acid compounds

<Example 106>
In Example 101, an optical film (KH-6) and a polarizing plate (HB) were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to (3-a). -6) was produced.

<Example 107>
In Example 101, an optical film (KH-7) and a polarizing plate (HB) were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to (3-j). -7) was produced.

<Example 108>
In Example 101, an optical film (KH-8) and a polarizing plate (HB) were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to (4-a). -8) was produced.

<Example 109>
In Example 101, an optical film (KH-9) and a polarizing plate (HB) were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to (4-m). -9) was produced.

<Example 110>
In Example 101, an optical film (KH-10) and a polarizing plate (HB) were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to (4-n). -10) was produced.

<Comparative Example 101>
In Example 101, an optical film (CKH-1) and a polarizing plate (CHB-1) were produced in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was not added. .

<Comparative Example 102>
In Example 104, an optical film (CKH-2) and a polarizing plate (CHB-2) were produced in the same manner as in Example 104 except that the compound (1-a) represented by the general formula (I) was not added. .

<Comparative Example 103>
In Example 105, an optical film (CKH-3) and a polarizing plate (CHB-3) were produced in the same manner as in Example 105 except that the compound (1-a) represented by the general formula (I) was not added. .

<Comparative Example 104>
Example 101 is the same as Example 101 except that the compound (1-a) represented by the general formula (I) is not added and the surface temperature of the film in the ultraviolet irradiation step is 110 ° C. An optical film (CKH-4) and a polarizing plate (CHB-4) were produced.

<Comparative Example 105>
In Example 101, an optical film (CKH-5) and a polarizing plate were obtained in the same manner as in Example 101 except that the compound (1-a) represented by the general formula (I) was changed to the following compound (2-a). (CHB-5) was produced.

<Evaluation of optical film, polarizing plate, and liquid crystal display device>

<< Evaluation of surface condition >>
The polarizing plates produced in Examples 101 to 110 and Comparative Examples 101 to 105 were evaluated at room temperature (25 ° C.) based on the following evaluation criteria. The results are shown in Table 5.
-Evaluation criteria-
A: Wrinkles cannot be observed visually in a 10 cm square, and there is no problem as a product.
B: Although slight wrinkles are generated in 10 cm square, it does not cause a problem as a product.
C: Wrinkles that can be visually observed are generated on the entire surface of the 10 cm square and cannot be used as a product.

<< Evaluation of wet heat durability >>
Each polarizing plate produced in each example and comparative example was affixed to glass as a sample, left for 24 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, and then returned to room temperature (25 ° C.). The state of cracks generated in the sample was observed visually or with a stereomicroscope (SMZ1500, manufactured by Nikon Corporation) and evaluated based on the following evaluation criteria. The results are shown in Table 5.
-Evaluation criteria-
A: A crack cannot be observed visually in a 10 cm square, and does not cause a problem as a product.
B: Although one crack is generated in 10 cm square, it does not cause a problem as a product.
C: One or more cracks that can be observed visually in a 10 cm square, and cannot be used as a product.

  From the said table | surface, it turns out that polarizing plate HB-1-10 of Examples 101-110 is excellent in wet heat durability compared with polarizing plate CHB-1-5 of Comparative Examples 101-105. This is considered to be because the curing of the alignment film layer proceeds sufficiently even when the surface temperature of the film is set to a low temperature in the ultraviolet irradiation step during the production of the optical film. From Comparative Example 104, it can be seen that the surface condition deteriorates when the surface temperature of the film in the ultraviolet irradiation process is set to a high temperature in order to improve the wet heat durability. The deterioration of the surface state is caused by the thin support deformed by heat. On the other hand, the optical film of the present invention can lower the temperature in the same process, so that the wet heat durability is improved. It can be seen that a good surface state can be maintained.

<< Production of Liquid Crystal Display >>
The polarizing plate of a commercially available liquid crystal television (BRAVIA J5000 from Sony Corporation) is peeled off from both sides of the liquid crystal cell, and the polarizing plates HB-1 to 10 prepared in the above examples are optical films in the polarizing plates of the above examples. A liquid crystal display device was obtained by being attached to a liquid crystal cell via an adhesive so that KH-1 to 10 were disposed on the liquid crystal cell side.
The liquid crystal display device incorporating the polarizing plates HB-1 to 10 of the above examples was adjusted to a halftone on the entire surface, and display unevenness was evaluated. In any liquid crystal display device, display unevenness was not observed from any direction, and good display performance was shown.

<Example 201>
<< Preparation of pattern retarder film >>
In Example 104, an optical film (FPR-1) was produced in the same manner as in Example 104 except that a patterned optically anisotropic layer was produced as follows.
(Preparation of coating solution for antiglare layer)
Each component was mixed with a mixed solvent (89 to 11 (mass ratio)) of MIBK (methyl isobutyl ketone) and MEK (methyl ethyl ketone) so as to have the following composition. It filtered with the polypropylene filter with the hole diameter of 30 micrometers, and prepared the coating liquid 1 for glare-proof layers. The solid concentration of each coating solution is 40% by mass. In preparing the coating solution, the resin particles and smectite were added in the state of a dispersion described later.
――――――――――――――――――――――――――――――――――――――――
Antiglare layer coating solution 1
――――――――――――――――――――――――――――――――――――――――
Smectite (Lucentite STN, manufactured by Co-op Chemical) 1.00% by mass
Resin particles (Techpolymer SSX, manufactured by Sekisui Plastics Co., Ltd.) 8.00% by mass
Acrylate monomer (NK ester A9550, manufactured by Shin-Nakamura Chemical Co., Ltd.)
87.79% by mass
Polymerization initiator (Irgacure 907, manufactured by BASF) 3.00% by mass
Leveling agent (P-4) 0.15% by mass
Dispersant (DISPERBYK-2164, manufactured by Big Chemie Japan)
0.06 mass%
――――――――――――――――――――――――――――――――――――――――

(Preparation of resin particle dispersion)
The dispersion of the translucent resin particles is gradually added to the stirred MIBK solution until the translucent resin particles (Techpolymer SSX, manufactured by Sekisui Kasei Co., Ltd.) reach a solid content concentration of 30% by mass. For 30 minutes.

(Preparation of smectite dispersion)
As the smectite dispersion, all MEKs used in the coating solution for the antiglare layer are finally added, and smectite (Lucentite STN, manufactured by Corp Chemical Co.) is gradually added to the MEK while stirring, followed by stirring for 30 minutes. Prepared.

(Coating of antiglare layer)
A 60 μm-thick triacetyl cellulose film containing an ultraviolet absorber was unwound in a roll form, and the antiglare layer was applied so as to have a film thickness of 4 μm using the coating solution 1 for the antiglare layer.
Specifically, in the die coating method using the slot die described in JP-A-2006-122889, Example 1, each coating solution was applied under the condition of a conveyance speed of 30 m / min, and after drying at 80 ° C. for 150 seconds, Further, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of about 0.1% under a nitrogen purge, the coating layer was irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 180 mJ / cm ^2. Was cured to form an antiglare layer, and then wound up to prepare a support 1 with an antireflection layer.

(Preparation of alkali saponified support 1)
The prepared anti-reflective layered support 1 is passed through a dielectric heating roll having a temperature of 60 ° C., and after the film surface temperature is raised to 40 ° C., it is opposite to the surface on which the antiglare layer of the film is formed. An alkaline solution having the composition shown below is continuously applied to the side surface with a # 6 wire bar, heated to 110 ° C., and conveyed for 10 seconds under a steam far-infrared heater manufactured by Noritake Company Limited. did. Subsequently, 3 ml / m ^{2 of} pure water was applied using the same bar coater. Next, washing with a fountain coater and draining with an air knife were repeated three times, and then transported to a drying zone at 70 ° C. for 10 seconds and dried to prepare an alkali saponified support 1.
────────────────────────────────────
Composition of alkaline solution ────────────────────────────────────
Potassium hydroxide 2.0 parts by weight Water 6.5 parts by weight Isopropanol 85.0 parts by weight Surfactant SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H 0.035 parts by weight Propylene glycol 6. 5 parts by mass ─────────────────────────────────────

(Preparation of support 1 with alignment film before exposure)
An alignment film coating solution 1 having the following composition was continuously applied with a # 14 wire bar to the alkali saponified surface of the prepared support 1 subjected to the alkali saponification treatment. Drying with warm air of 60 ° C. for 60 seconds, and further with warm air of 100 ° C. for 120 seconds, the support 1 with an alignment film before exposure was formed. The film thickness of the alignment film before exposure was 0.45 μm.
────────────────────────────────────
Composition of coating liquid 1 for alignment film formation ────────────────────────────────────
Polymer material for alignment film (P-1) 2.4 parts by mass of compound (1-a) represented by general formula (I) 0.2 parts by mass of photoacid generator (S-1) 0.17 parts by mass of radical Polymerization initiator (Irgacure 2959, manufactured by Ciba Specialty Chemicals)
0.18 parts by weight Methanol 16.5 parts by weight IPA (isopropanol) 7.2 parts by weight water 73.55 parts by weight ──────────────────────── ────────────

(UV exposure)
Next, a stripe mask having a lateral stripe width of 363 μm in the transmissive part and a lateral stripe width of 363 μm in the shielding part is placed on the prepared support 1 with an alignment film before exposure, and a wavelength region of 200 nm to 400 nm under room temperature air. A pattern alignment film is formed by irradiating ultraviolet rays for 0.06 seconds (30 mJ / cm ² ) using a UV light irradiation device (Light Hammer 10, 240 W / cm, manufactured by Fusion UV Systems) with a illuminance of 500 mW / cm ^{2 as} a light source unit. did.

(Formation of patterned optical anisotropic layer)
The pattern alignment film after the ultraviolet exposure was rubbed once in one direction at 500 rpm while maintaining an angle of 45 ° with respect to the stripe of the stripe mask. Next, the following coating solution for optically anisotropic layer was applied with a wire bar # 3.2. Furthermore, after aging by heating at a film surface temperature of 110 ° C. for 2 minutes, the film was cooled to 80 ° C. and irradiated with ultraviolet rays for 20 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm ^{2 in} the air. A patterned optically anisotropic layer was formed by fixing the orientation state. In the mask exposure portion (first retardation region), the discotic liquid crystal compound is vertically aligned with the slow axis direction parallel to the rubbing direction, and the unexposed portion (second retardation region) is vertically aligned perpendicularly. Was. The film thickness of the optically anisotropic layer was 1.15 μm.

────────────────────────────────────
Composition of optically anisotropic layer coating solution────────────────────────────────────
Discotic liquid crystalline compound E-2 80 parts by mass Discotic liquid crystalline compound E-3 20 parts by mass alignment film interface alignment agent (II-1) 0.9 parts by mass alignment film interface alignment agent (III-1) 0.08 0.2 parts by mass air interface aligning agent (P-3) 0.6 parts by mass photopolymerization initiator (Irgacure 907, manufactured by BASF) 3.0 parts by mass other functional monomer (Ethylene oxide modified trimethylolpropane triacrylate (Biscoat 360, manufactured by Osaka Organic Chemical Co., Ltd.)) 10 parts by mass Methyl ethyl ketone 268 parts by mass ─────────────────────── ─────────────

As described above, an optical film (FPR-1) in which an antiglare layer and a patterned optically anisotropic layer were formed on both surfaces of a support was produced.
As shown in the table below, the thickness of the support, the addition amount of the compound represented by the general formula (I), the surface temperature (UV temperature) of the film in the ultraviolet irradiation step during the production of the optically anisotropic layer were changed. Except for the above, optical films FPR-2 to 4 of Examples 202 to 204 were produced in the same manner as in the production method of the optical film (FPR-1). Moreover, about the comparative example, except not adding the compound represented by general formula (I), the optical films CFPR-1 to CFPR-1 to Comparative examples 201 to 204 were respectively produced as shown in the following table.

<Preparation of Polarizing Plate FHB-1>
1) Saponification of film Optical anisotropy of commercially available cellulose acylate film (Fujitack ZRD40, manufactured by Fuji Film Co., Ltd.), commercially available cellulose acylate film (Fujitac TD60, manufactured by Fuji Film Co., Ltd.) and optical film FPR-1 The surface of the conductive layer was immersed in a 1.5 mol / L NaOH aqueous solution (saponification solution) maintained at 55 ° C. for 2 minutes, and then the film was washed with water, and then washed in a 0.05 mol / L sulfuric acid aqueous solution at 25 ° C. for 30 seconds. After dipping, the film was neutralized by passing a washing bath under running water for 30 seconds. Then, draining with an air knife was repeated three times, and after dropping the water, the film was retained in a drying zone at 70 ° C. for 15 seconds and dried to produce saponified films.

2) Production of Polarizing Film According to Example 1 of Japanese Patent Application Laid-Open No. 2001-141926, iodine was adsorbed to a stretched polyvinyl alcohol film to produce a polarizing film having a thickness of 20 μm.

3) Bonding (production of front-side polarizing plate F-1)
The cellulose acylate film ZRD40 after saponification, the polarizing film prepared by the above-described method, and the optical film FPR-1 with an antiglare hard coat layer after saponification are bonded in this order with a PVA adhesive and thermally dried. Front side polarizing plate F-1 was produced. At this time, the saponified surface of the cellulose acylate film ZRD40 and the surface side of the saponified optically anisotropic layer of the optical film FPR-1 were set to the polarizing film side.
Under the present circumstances, it arrange | positioned so that MD direction of the roll of the produced polarizing film and MD direction of the optical film FPR-1 with an anti-glare hard-coat layer may become parallel. Moreover, it arrange | positioned so that MD direction of the roll of the polarizing film and MD direction of the roll of the said cellulose acylate film ZRD40 may become parallel.
Except having changed optical film FPR-1 into FPR-2-4 and CFPR-1-4, it carried out similarly to the preparation methods of polarizing plate FHB-1, and polarizing plate FHB-2-4 of Examples 202-204, Polarizing plates CFHB-1 to Comparative example 201 to 204 were prepared.

(Preparation of rear-side polarizing plate)
The cellulose acylate film TD60 after saponification prepared above, the stretched iodine-based PVA polarizing film, and the cellulose acylate film ZRD40 after saponification are bonded together in this order with a PVA-based adhesive, heat-dried, and the rear-side polarizing plate Got.
Under the present circumstances, it arrange | positioned so that MD direction of the roll of the produced polarizing film and MD direction of the cellulose acylate film TD60 may become parallel. Moreover, it arrange | positioned so that MD direction of the roll of the polarizing film and MD direction of the roll of the said cellulose acylate film ZRD40 may become parallel.

<Production of Liquid Crystal Display Device G1-a>
The polarizing plates on both sides of the IPS mode liquid crystal cell (LGS 42LS5600) are peeled off, the front side polarizing plate F-1 is placed on the front side (the viewing side of the liquid crystal display device), and the rear side (the back side of the liquid crystal display device) is placed on the rear side. The side polarizing plates were attached to the front side and the rear side one by one through an adhesive so that the cellulose acylate film ZRD40 was on the liquid crystal cell side. The crossed Nicols were arranged so that the absorption axis of the front-side polarizing plate was in the MD direction (left-right direction) and the transmission axis of the rear-side polarizing plate was in the MD direction (left-right direction). The thickness of the glass used for the liquid crystal cell was 0.5 mm. The obtained liquid crystal display device was designated as a liquid crystal display device G-1.

<< Evaluation of wet heat durability >>
Each of the polarizing plates prepared in Examples 201 to 204 and Comparative Example was attached to a glass as a sample, and allowed to stand for 24 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, and then room temperature (25 ° C. The state of cracks generated in the sample when returned to () was observed visually or with a stereomicroscope (SMZ1500, manufactured by Nikon Corporation), and evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: Cracks cannot be observed visually in a 10 cm square, and the pattern lines maintain linearity.
B: Although cracks cannot be visually observed in a 10 cm square, the linearity of the pattern line is not maintained.
C: One crack is generated in 10 cm square.
D: One or more cracks that can be visually observed in a 10 cm square, and cannot be used as a product.

<< Evaluation of pattern accuracy >>
Arbitrary 5 points were selected every 1 m in the MD direction of the produced optical film, and a total pitch of 1080 stripes was measured using a measuring machine manufactured by Mitutoyo Corporation. The variation of the maximum and minimum values with respect to the average value of 5 points was evaluated, and evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: ± 0.02% or less B: ± 0.02% to 0.05%
C: ± 0.05% to 0.1%
D: More than ± 0.1%.

  From the said table | surface, it turns out that the pattern retarder films FPR-1-4 of this invention are excellent in wet heat durability compared with the pattern retarder film CFPR1-4 of a comparative example. From Comparative Examples 201 and 203, it can be seen that the pattern accuracy deteriorates when the surface temperature of the film in the ultraviolet irradiation process is set to a high temperature in order to improve the wet heat durability. The deterioration of pattern accuracy is caused by the thin support deformed by heat. On the other hand, the optical film of the present invention can lower the temperature in the same process, so that the wet heat durability is improved. Good pattern accuracy can be maintained. Furthermore, even if it is a case where thickness of a support body is made thin, it turns out that the same effect is shown.

  When the stereoscopic image liquid crystal display device incorporating the polarizing plate of each example was adjusted to the whole halftone, and unevenness was evaluated, unevenness was not observed from any direction.

<Example 301>
(Preparation of alkali saponified support 2)
In Example 201, a triacetyl cellulose film containing a UV absorber having a thickness of 60 μm was unwound in the form of a roll in the same manner as in Example 201 except that the antiglare layer was not applied. The prepared support 2 was produced.

(Preparation of support 2 with alignment film)
In the coating liquid 1 for forming an alignment film in Example 201, the amount of the compound (1-a) represented by the general formula (I) is 0.24 parts by mass, and the photoacid generator (S-1) is added. An alignment film coating solution 2 was produced in the same manner as in Example 201 except that the above was not performed. Furthermore, the alignment film coating solution 2 was continuously applied on the support 2 subjected to the alkali saponification treatment in the same manner as in Example 201 to form the support 2 with alignment film.
────────────────────────────────────
Composition of coating liquid 2 for alignment film formation ────────────────────────────────────
Polymer material for alignment film (P-1) 2.4 parts by mass of compound (1-a) represented by general formula (I) 0.24 parts by mass of radical polymerization initiator (Irgacure 2959, manufactured by Ciba Specialty Chemicals) )
0.18 parts by weight Methanol 16.5 parts by weight IPA (isopropanol) 7.2 parts by weight water 73.55 parts by weight ──────────────────────── ────────────

(Formation of first optically anisotropic layer)
The rubbing treatment was continuously performed on the alignment film side of the support 2 with the alignment film thus prepared. At this time, the longitudinal direction of the long film and the conveying direction are parallel, and the angle formed between the longitudinal direction of the film and the rotation axis of the rubbing roller is 75 ° (clockwise) (when the longitudinal direction of the film is 90 °). The rotation axis of the rubbing roller is 15 °).

  A first optically anisotropic layer coating liquid (A) containing a discotic liquid crystal compound having the following composition was continuously applied to the prepared alignment film with a # 3.6 wire bar. The conveyance speed (V) of the film was 18 m / min. In order to dry the solvent of the coating solution and to mature the orientation of the discotic liquid crystal compound, the film was heated with warm air of 115 ° C. for 90 seconds, then heated with warm air of 80 ° C. for 60 seconds, and irradiated with UV at 80 ° C. The alignment of the liquid crystal compound was fixed. The thickness of the first optical anisotropic layer was 1.8 μm. The average tilt angle of the disc surface of the discotic liquid crystal compound with respect to the film surface was 90 °, and it was confirmed that the discotic liquid crystal compound was aligned perpendicular to the film surface. The angle of the slow axis was parallel to the rotation axis of the rubbing roller, and was 15 ° when the film longitudinal direction was 90 ° (film width direction was 0 °).

────────────────────────────────────
Composition of the first optically anisotropic layer coating solution (A) ────────────────────────────────────
Discotic liquid crystalline compound E-2 80 parts by mass Discotic liquid crystalline compound E-3 20 parts by mass alignment film interface alignment agent (II-1) 0.9 parts by mass alignment film interface alignment agent (III-1) 0.08 Part by mass Air interface alignment agent (P-2) 0.2 part by mass photopolymerization initiator (Irgacure 907, manufactured by BASF) 3.0 parts by mass polyfunctional monomer (ethylene oxide-modified trimethylolpropane triacrylate (Biscoat 360, Osaka) 10 parts by weight of the following polymer (A) 1.0 part by weight methyl ethyl ketone 223 parts by weight ─────────────────────────── ─────────

(Polymer (A))

(Formation of second optically anisotropic layer)
The produced first optically anisotropic layer was continuously rubbed. At this time, the longitudinal direction of the long film and the transport direction are parallel, and the angle formed between the longitudinal direction of the film and the rotation axis of the rubbing roller is −75 ° (counterclockwise) (the longitudinal direction of the film is 90 °). Then, the rotation axis of the rubbing roller is 165 °).

  A second optically anisotropic layer coating solution (A) containing a rod-like liquid crystal compound having the following composition was continuously applied onto the produced first optically anisotropic layer with a # 2.7 wire bar. The conveyance speed (V) of the film was 41 m / min. In order to dry the solvent of the coating solution and ripen the alignment of the rod-like liquid crystal compound, the liquid crystal compound was fixed by heating at 60 ° C. for 60 seconds and UV irradiation at 60 ° C. The thickness of the second optical anisotropic layer was 0.8 μm. The average inclination angle of the long axis of the rod-like liquid crystal compound with respect to the film surface was 0 °, and it was confirmed that the liquid crystal compound was aligned horizontally with respect to the film surface. The angle of the slow axis was orthogonal to the rotation axis of the rubbing roller, and was 75 ° when the film longitudinal direction was 90 ° (film width direction was 0 °).

────────────────────────────────────
Composition of the second optically anisotropic layer coating solution (A) ―――――――――――――――――――――――――――――――――――― -
80 parts by mass of the following rod-like liquid crystal compound (A) 20 parts by mass of the following rod-like liquid crystal compound (B) Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass sensitizer (Kayacure DETX, Nippon Kayaku ( 1 part by mass air interface control agent (P-3) 0.3 part by mass methyl ethyl ketone 193 parts by mass ――――――――――――――――――――――――― ――――――――――――

<Example 302>
In the coating liquid (A) for the first optically anisotropic layer of Example 301, the air interface control agent (P-2) was used as the fluoroaliphatic group-containing polymer 1, and the coating liquid for the first optically anisotropic layer (B The optical film 302 was produced in the same manner as in Example 301 except that.

<Example 303>
An optical film 303 was produced in the same manner as in Example 302 except that the UV temperature was changed to 70 ° C. in the formation of the first optical anisotropic layer in Example 301.

<Example 304>
An optical film 304 was produced in the same manner as in Example 301 except that the UV temperature was changed to 70 ° C. in the formation of the first optical anisotropic layer in Example 302.

<Example 305>
An optical film 305 was produced in the same manner as in Example 302 except that the UV temperature was changed to 60 ° C. in the formation of the first optical anisotropic layer in Example 301.

<Example 306>
An optical film 306 was produced in the same manner as in Example 302 except that the UV temperature was changed to 60 ° C. in the formation of the first optical anisotropic layer in Example 302.

<Example 307>
In the second optically anisotropic layer coating liquid (A) of Example 301, 5 parts by mass of a polyfunctional monomer (ethylene oxide-modified trimethylolpropane triacrylate (Biscoat 360, manufactured by Osaka Organic Chemical Co., Ltd.)) was further added, An optical film 307 was produced in the same manner as in Example 301 except that the second optically anisotropic layer coating liquid (B) was produced.

<Example 308>
In the second optically anisotropic layer coating liquid (A) of Example 302, 5 parts by mass of a polyfunctional monomer (ethylene oxide-modified trimethylolpropane triacrylate (Biscoat 360, manufactured by Osaka Organic Chemical Co., Ltd.)) was further added, An optical film 308 was produced in the same manner as in Example 302 except that the second optically anisotropic layer coating solution (B) was produced.

<Example 309>
In the formation of the second optical anisotropic layer of Example 307, an optical film 309 was produced in the same manner as in Example 307 except that the drying temperature was 60 ° C.

<Example 310>
An optical film 310 was produced in the same manner as in Example 308 except that the drying temperature was changed to 60 ° C. in the formation of the second optical anisotropic layer in Example 308.

<Example 311>
In the formation of the first optical anisotropic layer of Example 301, after forming the alignment film in the same manner as in Example 301, except that the following first optical anisotropic layer coating liquid (C) was used, In the same manner as in Example 301, a first optical anisotropic layer was formed to produce a first optical anisotropic layer film. Furthermore, the adhesive was laminated | stacked with the roll toe roll on the 1st optically anisotropic layer of the 1st optically anisotropic layer film.
On the other hand, the second optical anisotropic layer was formed by the following method.
In the production of the support (PK-1) of Example 101, a support (PK-2) having a thickness of 80 μm was produced in the same manner as in Example 101 except that the inner layer thickness was 74 μm. This support (PK-2) was not subjected to alkali treatment, and an alignment film was formed on the support (PK-2) in the same manner as in Comparative Example 101. Further, a second optical anisotropic layer is formed on the alignment film in the same manner as in Example 301, and the alignment film and the second optical anisotropic layer are stacked in this order on the support (PK-2). A film for the second optically anisotropic layer was produced.
The first optical anisotropic layer film with an adhesive obtained by the above method and the second optical anisotropic layer film were bonded together by roll-to-roll. Thereafter, the support (PK-2) of the film for the second optical anisotropic layer is peeled off, whereby the alignment film, the first optical anisotropic layer, the pressure-sensitive adhesive, and the second optical anisotropy are formed on the support. An optical film 311 in which layers were laminated in this order was produced. At this time, the angle formed by the slow axes of the first optical anisotropic layer and the second optical anisotropic layer was 60 °.

────────────────────────────────────
Composition of the first optically anisotropic layer coating solution (C) ────────────────────────────────────
Discotic liquid crystalline compound E-2 80 parts by mass Discotic liquid crystalline compound E-3 20 parts by mass alignment film interface alignment agent (II-1) 0.9 parts by mass alignment film interface alignment agent (III-1) 0.08 Part by mass fluoroaliphatic group-containing polymer 1 0.2 part by mass air interface aligning agent (P-3) 0.05 part by mass fluoroaliphatic group-containing polymer 2 0.05 part by mass photopolymerization initiator (Irgacure 907, BASF Corporation) 3.0 parts by weight polyfunctional monomer (ethylene oxide modified trimethylolpropane triacrylate (Biscoat 360, manufactured by Osaka Organic Chemical Co., Ltd.)) 10 parts by weight methyl ethyl ketone 223 parts by weight ───────────── ───────────────────────

<Example 312>
An optical film 312 was produced in the same manner as in Example 311 except that the second optically anisotropic layer coating solution (A) in Example 311 was changed to the second optically anisotropic layer coating solution (B). .

<Examples 313 to 324>
Optical films 313 to 324 were produced in the same manner as in Examples 301 to 312 except that the thickness of the support in Examples 301 to 312 was changed to 40 μm.

<Examples 325 to 327>
Optical films 325 to 327 were produced by the following method.
<Production of support>
(Preparation of core layer cellulose acylate dope)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution.
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Cellulose acetate having a degree of acetyl substitution of 2.88 100 parts by weight The following ester oligomer 10 parts by weight additive A 4 parts by weight additive B 2 parts by weight methylene chloride (first solvent) 430 parts by weight Methanol (second solvent) 64 parts by weight
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Ester oligomer

Additive A

Additive B

(Preparation of outer layer cellulose acylate dope)
10 parts by mass of the following matting agent solution was added to 90 parts by mass of the core layer cellulose acylate dope to prepare an outer layer cellulose acetate solution.
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Silica particles having an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)
2 parts by mass Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass Core layer Cellulose acylate dope 1 part by mass
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(Preparation of cellulose acylate film)
Three layers of the core layer cellulose acylate dope and the outer layer cellulose acylate dope were cast simultaneously on a drum at 20 ° C. from the casting port. The film was peeled off in a state where the solvent content was approximately 20% by mass, both ends in the width direction of the film were fixed with tenter clips, and the film was dried while being stretched 1.1 times in the lateral direction in a state where the residual solvent was 3 to 15%. Then, by conveying between the rolls of the heat treatment apparatus, the film was further dried to produce a cellulose acylate film having a thickness of 20 μm.

  An alignment film was formed on the support (cellulose acylate film) prepared in the same manner as in Example 301 using alignment film forming coating solution 2 of Example 301, and then Examples 307, 308, and 312 A first optical anisotropic layer was formed by the same method. In addition, UV temperature at the time of forming a 1st optically anisotropic layer was 50 degreeC. Further, a second optical anisotropic layer was formed on the first optical anisotropic layer in the same manner as in Examples 307, 308, and 312 to prepare optical films 325 to 327.

<Examples 328 to 330>
Examples 307, 308, 312 of Examples 307, 308, 312 were changed to the second optically anisotropic layer coating liquid (C) shown below, except that the second optically anisotropic coating liquid (B) was changed. Optical films 328 to 330 were produced in the same manner as described above.

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Composition of the second optically anisotropic layer coating solution (C) ―――――――――――――――――――――――――――――――――――― -
Rod-like liquid crystal compound (A) 80 parts by mass The following rod-like liquid crystal compound (C) 14 parts by mass The following rod-like liquid crystal compound (D) 2.2 parts by mass polyfunctional monomer (ethylene oxide-modified trimethylolpropane triacrylate (Biscoat 360, Osaka) 5 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 3 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass air interface controller (P -3) 0.3 parts by mass methyl ethyl ketone 193 parts by mass ―――――――――――――――――――――――――――――――――――――

Rod-shaped liquid crystal compound (C)

Rod-shaped liquid crystal compound (D)

<Examples 331 to 334>
In the second optical anisotropic coating liquid (B) of Examples 307, 308, 319, and 320, 1 part by weight of the fluoroaliphatic group-containing polymer 3 was added, and the second optical anisotropic layer coating liquid (D) was added. Optical films 331 to 334 were produced in the same manner as in Examples 307, 308, 319, and 320 except that they were produced.

Fluoroaliphatic group-containing polymer 3

<Comparative Examples 301-306>
Examples 302, 304, 306, 314, 316, and 318, except that the compound (1-a) was not used in the alignment film forming coating solutions of Examples 302, 304, 306, 314, 316, and 318. Optical films 335 to 340 were produced in the same manner.

<Comparative Examples 307 and 308>
Optical films 341 and 342 were produced in the same manner as in Comparative Examples 301 and 304, except that the UV temperature was set to 100 ° C. in the formation of the first optical anisotropic layer in Comparative Examples 301 and 304.

<Comparative Example 309>
An optical film 343 was produced in the same manner as in Example 325 except that the compound (1-a) was not used in the alignment film-forming coating solution 2 of Example 325.

(Preparation of polarizing film)
A polyvinyl alcohol (PVA) film having a thickness of 80 μm is dyed by immersing it in an aqueous iodine solution having an iodine concentration of 0.05% by mass at 30 ° C. for 60 seconds, and then in an aqueous boric acid solution having a boric acid concentration of 4% by mass. The film was vertically stretched to 5 times the original length while being immersed for 2 seconds, and then dried at 50 ° C. for 4 minutes to obtain a polarizing film having a thickness of 20 μm.
The cellulose acylate film (T1) was immersed in an aqueous sodium hydroxide solution at 55 ° C. at 1.5 mol / liter, and then the sodium hydroxide was sufficiently washed away with water. Then, after being immersed in a diluted sulfuric acid aqueous solution at 0.005 mol / liter at 35 ° C. for 1 minute, it was immersed in water to sufficiently wash away the diluted sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
(Saponification of polarizing film protective film)
After immersing the cellulose acylate film in an aqueous sodium hydroxide solution at 55 ° C. at 1.5 mol / liter, the sodium hydroxide was sufficiently washed away with water. Then, after being immersed in a diluted sulfuric acid aqueous solution at 0.005 mol / liter at 35 ° C. for 1 minute, it was immersed in water to sufficiently wash away the diluted sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.
(Production of circularly polarizing plate)
The support side of the optical films of Examples 301 to 330 and Comparative Examples 301 to 309 described above, the polarizing film, and the polarizing film protective film were bonded using a polyvinyl alcohol-based adhesive. At this time, the angle formed by the absorption axis of the polarizing film and the slow axis of the first optical anisotropic layer is 15 °, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer The polarizing film, the optical film, and the polarizing film protective film were cut into single sheets and bonded together so that the angle was 75 °. In this way, circularly polarizing plates 301 to 339 were produced.

<Production of organic EL display device>
Disassemble the GALAXY SII manufactured by SAMSUNG equipped with an organic EL panel, peel off the circularly polarizing plate, and paste the circularly polarizing plates manufactured in the above examples and comparative examples so that no air enters, and display the organic EL display. A device was made. About the produced organic EL display device, the uniformity of the optical film was evaluated in a bright room with an illuminance of 200 lux. Uniformity was evaluated with respect to the streaky unevenness that occurred in the plane of the optical film, based on the visibility of color change visually as the following criteria.

<< Visibility of color change of optical film >>
-Evaluation criteria-
A: A color change is not visually recognized at all, and does not become a problem as a product.
B: Although the streaky unevenness can be visually recognized slightly, the color change of the display device is not visually recognized and does not cause a problem as a product.
C: Streaky unevenness was clearly visible, but the color change of the display device was only slightly visible, and this does not cause a problem as a product.
D: Since there are a plurality of streaky irregularities and the color change of the display device is clearly visually recognized, it cannot be used as a product.

<< Damp heat durability of optical film >>
Each optical film produced in each Example and Comparative Example was affixed to glass as a sample, left for 24 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, and then returned to room temperature (25 ° C.). The state of cracks generated in the sample was observed visually or with a stereomicroscope (SMZ1500, manufactured by Nikon Corporation) and evaluated based on the following evaluation criteria. The results are shown in Table 5.
-Evaluation criteria-
A: A crack cannot be observed visually in a 10 cm square, and does not cause a problem as a product.
B: Although one crack is generated in 10 cm square, it does not cause a problem as a product.
C: One or more cracks that can be observed visually in a 10 cm square, and cannot be used as a product.

  It turns out that the optical films 301-334 of Examples 301-334 are excellent in wet heat durability, even if it is a form of a circularly-polarizing plate compared with the optical films 335-343 of Comparative Examples 301-309. In particular, even when the UV temperature was lowered for the purpose of thinning and improving the support, the optical film of the present invention had good wet heat durability.

10: optical film, 12: optically anisotropic layer, 12a: first retardation region, 12b: second retardation region, 14: alignment film, 16: support, 20: polarizing plate (circular polarizing plate), 22 : Polarizing film, 100: liquid crystal display device, 101: liquid crystal cell, 102: optical film, 103: polarizing film, 104: polarizing plate, 200: organic EL display device, 201: organic EL panel, 202: λ / 4 plate, 203: Polarizing film, 204: Circular polarizing plate, 300: Stereoscopic image display device, 301: Liquid crystal cell, 302: Pattern retarder film, 303: Polarizing film, 304: Polarizing plate

Claims (19)

It has a support, an alignment film, and an optically anisotropic layer containing a liquid crystalline compound in this order, and the alignment film is composed of polyvinyl alcohol having a polymerizable group, a polyfunctional acrylamide compound, and a polyfunctional methacrylamide compound. Having a selected polyfunctional acrylamide compound ,
The optical film whose thickness of the said support body is 20-60 micrometers . 2. The optical film according to claim 1, wherein the polyfunctional acrylamide compound comprises a total of two or more structures represented by —L-acrylamide group and a structure represented by —L-methacrylamide group; L represents a single bond or a divalent linking group. The optical film according to claim 1 or 2, wherein the polyfunctional acrylamide compound comprises 3 to 6 acrylamide groups and methacrylamide groups in total. Polyfunctional acrylamide compound is contained in the molecule, the number of atoms connecting the two groups to each other selected from acrylamide group and methacrylamide group, respectively, is 4 to 40, any one of claims 1 to 3 1 An optical film according to item . The optical film according to any one of claims 1 to 4, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I):
Formula (I)
In general formula (I), Z represents an n-valent group, L represents a single bond or a divalent linking group, R represents a hydrogen atom or a methyl group, n represents an integer of 3 to 6, n Each L and R may be the same or different. Of the n —L—NH—C (═O) —CR═CH _{2 in} the general formula (I), (n−1) or (n−2) are structures having the same L (A ), and the one or two remaining a structure having a different L from the structure (a), the optical film according to claim 5. The optical film according to claim 5 or 6, wherein Z in the general formula (I) has any one of the following structures:
In the formula, * represents a binding site with L in the general formula (I). The optical film according to any one of claims 1 to 4, wherein the polyfunctional acrylamide compound is a compound represented by the following general formula (I-1);
Formula (I-1)
In general formula (I-1), R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. In the alignment film, the mass ratio of polyvinyl alcohol having a polyfunctional acrylamide compound and a polymerizable group is 1: 1 to 1: 20, the optical film according to any one of claims 1-8. In the alignment film, a polyfunctional acrylamide compound, the weight ratio of polyvinyl alcohol having a polymerizable group, 1: 5 to 1: 20, wherein the optical film is for viewing angle film, according to claim 1 to 9 The optical film of any one of these . In the alignment film, a polyfunctional acrylamide compound, the weight ratio of polyvinyl alcohol having a polymerizable group, 1: 1 to 1: 20, wherein the optical film is for patterned retarder film, according to claim 1 to 9 The optical film of any one of these . In the alignment film, a polyfunctional acrylamide compound, the weight ratio of polyvinyl alcohol having a polymerizable group, 1: 1 to 1: 20, wherein the optical film is a circularly polarizing plate, according to claim 1 to 9 The optical film according to any one of the above. A composition comprising a polyvinyl alcohol having a polymerizable group and a polyfunctional acrylamide compound selected from a polyfunctional acrylamide compound and a polyfunctional methacrylamide compound ,
The polyfunctional acrylamide compound is a compound represented by the following general formula (I-1),
A composition having a mass ratio of the polyfunctional acrylamide compound and the polyvinyl alcohol having a polymerizable group of 1: 1 to 1:20;
Formula (I-1)
In general formula (I-1), R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. The composition according to claim 13 , wherein the polyvinyl alcohol having a polymerizable group is a polyvinyl alcohol having a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group. The composition according to claim 13 or 14, which is used for an optical film. A flat image display device or a three-dimensional image display device comprising the optical film according to claim 1 . A liquid crystal display device or an organic EL display device comprising the optical film according to claim 1 . Applying the composition according to any one of claims 13 to 15 in a layer form on a support, applying a composition containing a liquid crystal compound on the surface of the layered composition in a layer form, The manufacturing method of an optical film including irradiating an ultraviolet-ray at 40-90 degreeC to the composition containing the liquid crystal compound made into the layer form. The method for producing an optical film according to claim 18 , wherein the optical film is the optical film according to claim 1 .