KR20150106457A - Optical-film material, optical film, method for manufacturing polarizer, and polarizer - Google Patents

Abstract

According to the present invention, there is provided an optical film material capable of providing a polarizing plate having a thin film thickness, which comprises a layer made of a stretched film having a rubbed surface, an optically anisotropic layer and an optically isotropic acrylic polymer layer, The anisotropic layer is a layer formed by polymerizing the above-mentioned liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound directly coated on the above surface, and the acrylic polymer layer is formed of a polymerizable composition containing the liquid crystal compound (Meth) acrylate directly applied to the surface of the layer to be cured, and the film thickness of the acrylic polymer layer is larger than the film thickness of the optically anisotropic layer . The present invention also provides an optical film obtained by peeling a layer comprising a stretched film from the optical film material, a polarizing plate comprising the optical film, and a method of producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an optical film material, an optical film, a method of manufacturing a polarizer, and a polarizer,

The present invention relates to an optical film material, an optical film, a method for producing a polarizing plate, and a polarizing plate.

As the market for smart phones and tablet PCs expands, more and more thinner displays are being demanded. In such a flow, various films such as an acryl-based polymer film and a cycloolefin-based polymer film have been attempted to be used as a protective film of a polarizing plate in addition to cellulose acylate-based polymer films conventionally used as transparent and low birefringent optical films (For example, Patent Document 1).

JP-A-2009-175222

Films such as the above-mentioned acryl-based polymer films and cycloolefin-based polymer films are expensive and easily poured at the time of handling, and there is room for improvement for practical use. Further, from the viewpoint of thinning of the display, it is considered that the demand for a thin film optical film having a retardation based on the above polymer film is also increased.

An object of the present invention is to provide an optical film of a thin film and a polarizing plate of the thin film. Disclosure of the Invention The present invention is directed to a thin film optical film having a retardation, a polarizing plate having an optical film as a protective film, and a method for producing a polarizing plate. An object of the present invention is to provide an optical film material capable of efficiently supplying an optical film of a thin film having a controlled retardation.

The thin film may be manufactured and transported as a laminated material to prevent the above-mentioned dents and scratches, or for convenience of handling. The present inventors have found that a film capable of functioning as a laminate film for forming a thin film is used as a temporary support to apply a composition containing a polymerizable compound onto a support, To prepare a polymer film. However, there has been a problem in that the releasability of the branched polymer and the acrylic polymer film is insufficient. As a result of further intensive studies by the present inventors for solving this problem, it has been found that by forming an optically anisotropic layer formed of a liquid crystal compound before formation of an acrylic polymer layer on a branched state, Is improved, and a controlled phase difference can be given. The inventors of the present invention have found that when a thin film (optically anisotropic layer) having a retardation formed by photo-curing a composition containing a liquid crystal compound is formed directly on a support without an orientation film interposed therebetween, And it is possible to peel off without defect. Conventionally, even if the inventors of the present invention attempted trial and error, a thin film (optically anisotropic layer) having a retardation formed by photo-curing of a composition containing a liquid crystal compound could not be peeled off from the branched body without defects, The thin film was prone to difficult problems that are liable to be broken at the time of peeling from the branching body.

Based on the above findings, the present inventors have repeatedly studied to complete the present invention. That is, the present invention provides the following [1] to [21].

[1] A method of manufacturing a polarizing plate comprising a layer made of a stretched film, an optically anisotropic layer, and an optically isotropic acrylic polymer layer,

The layer made of the stretched film has a rubbed surface,

The optically anisotropic layer is a layer formed by polymerizing the liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound directly coated on the surface,

The acrylic polymer layer is a layer formed by curing a polymerizable composition containing (meth) acrylate directly applied to the surface of a layer formed of the polymerizable composition containing the above liquid crystal compound, and

Wherein the film thickness of the acrylic polymer layer is larger than the film thickness of the optically anisotropic layer.

[2] The optical film material according to [1], wherein the stretched film is a polyethylene terephthalate film or a cycloolefin polymer film.

[3] The optical film material according to [1], wherein the stretched film is a polyethylene terephthalate film.

[4] The optical film material according to any one of [1] to [3], wherein the optically anisotropic layer has a film thickness of 0.5 μm to 5 μm.

[5] The optical film material described in any one of [1] to [3], wherein the optically anisotropic layer has a thickness of 0.5 μm to 3 μm.

[6] The optical film material according to any one of [1] to [5], wherein the liquid crystal compound is a compound having two or more (meth) acryl groups.

[7] The optical film material according to any one of [1] to [6], wherein the acrylic polymer layer is a layer formed by polymerizing (meth) acrylate by irradiating a polymerizable composition containing (meth) acrylate.

[8] The optical film material according to any one of [1] to [7], wherein the acrylic polymer layer has a thickness of 50 μm or less.

[9] An optical film comprising the optically anisotropic layer and the acrylic polymer layer obtained by peeling a layer comprising a stretched film from the optical film material described in any one of [1] to [8].

[10] A method for producing an optical film material according to any one of [1] to [8]

(1) rubbing at least one side of the stretched film,

(2) applying a polymerizable composition containing a liquid crystal compound to the rubbed surface of the stretched film,

(3) applying a polymerizable composition containing a direct (meth) acrylate to a layer formed of the above-mentioned polymerizable composition containing a liquid crystal compound,

(4) A process for producing a liquid crystal composition comprising curing the polymerizable composition containing the liquid crystal compound and the polymerizable composition containing the (meth) acrylate.

[11] The production method according to [10], wherein the curing is performed by light irradiation.

[12] The production method according to [11]

(1) rubbing at least one side of the stretched film,

(2) applying a polymerizable composition containing a liquid crystal compound directly to the rubbed surface of the stretched film,

(2-2) irradiating a polymerizable composition containing the liquid crystal compound described above to polymerize the liquid crystal compound to form an optically anisotropic layer,

(3) applying the above-mentioned (meth) acrylate-containing polymerizable composition directly to the optically anisotropic layer,

(3-2) A manufacturing method comprising the steps of: (1) irradiating a polymerizable composition containing the (meth) acrylate to polymerize the (meth) acrylate to form an acrylic polymer layer.

[13] A method for producing a polarizing plate,

(1) Preparing the optical film material described in any one of [1] to [8]

(2) peeling the layer comprising the stretched film of the optical film material,

(3) A method of manufacturing comprising laminating an optical film after peeling of the optical film material or the stretched film, on a film including a polarizer.

[14] The optical film material is laminated on the film including the polarizer on the side of the acrylic polymer layer as viewed from the optically anisotropic layer, and then the layer comprising the stretched film of the optical film material is peeled off [13] ≪ / RTI >

[15] The production method according to [13], wherein the layer comprising the stretched film of the optical film material is peeled off, and thereafter the optical film after peeling of the layer comprising the stretched film is laminated on the film containing the polarizer.

[16] A polarizing plate comprising an optically anisotropic layer and an optically isotropic acrylic polymer layer and a polarizer,

Wherein the optically anisotropic layer is a layer formed by polymerizing the liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound,

The acrylic polymer layer is a layer formed by curing a polymerizable composition containing (meth) acrylate directly applied to the surface of a layer formed of the polymerizable composition containing the liquid crystal compound,

Wherein the film thickness of the acrylic polymer layer is larger than the film thickness of the optically anisotropic layer.

[17] A polarizing plate comprising the optical film and the polarizer according to [9].

[18] The polarizer according to [16] or [17], wherein the optically anisotropic layer and the polarizer are in direct contact with each other.

[19] The polarizer according to [16] or [17], wherein the acrylic polymer layer and the polarizer are in direct contact with each other.

[20] A film comprising a cellulose acylate film,

The polarizer according to any one of [16] to [19], wherein the optical film, the polarizer, and the cellulose acylate film are in this order.

[21] The polarizer according to any one of [16] to [20], wherein the hard coat layer is provided on the outermost layer on the side of the optical film viewed from the polarizer.

The present invention provides an optical film material, a thin film optical film having a retardation, and a thin and high-performance polarizer capable of efficiently supplying a thin film optical film having a retardation.

Fig. 1 is a view showing an example of the layer structure of the polarizing plate of the present invention.

Hereinafter, the present invention will be described in detail.

In the present specification, " " is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

The term " polarizing plate " in this specification means a polarizing plate having a long polarizing plate and a polarizing plate that is cut to a size that is mounted on a liquid crystal display device (in this specification, " &Quot; and the like) is used to mean both of the polarizing plate. The term " polarizing plate " means a laminate having at least a film on one side of the " polarizer ", while the term " polarizer " do.

In the present specification, the term "(meth) acrylate" means "either or both of acrylate and methacrylate". "(Meth) acrylic acid" and the like are also the same.

In the present specification, Re (?) And Rth (?) Represent the in-plane retardation and the retardation in the thickness direction at the wavelength?, Respectively. Re (?) Is measured by introducing light having a wavelength of? Nm in the film normal direction in KOBRA 21ADH or WR (manufactured by Oji Instruments Co., Ltd.). In the selection of the measurement wavelength? Nm, the wavelength selection filter can be manually changed, or the measurement value can be converted by a program or the like to be measured.

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (?) Is calculated by the following method.

Rth (?) Is defined as an inclination axis (rotation axis) of Re (?) On the in-plane slow axis (determined by KOBRA 21ADH or WR) (in the case where there is no slow axis, Light having a wavelength of? Nm is incident from the oblique direction in a 10-degree step from the normal direction to the normal direction of the film with respect to the film normal direction to measure six points in total, and the assumed values of the measured retardation value and the average refractive index, KOBRA 21ADH or WR is calculated based on the film thickness value.

In the above case, in the case of a film having a slow axis in the plane as a rotation axis from the normal direction and a direction in which the value of the retardation becomes zero at a certain tilt angle, the retardation value at an inclination angle larger than the tilt angle, KOBRA 21ADH or WR is calculated.

Further, the retardation value is measured from arbitrary oblique directions by using the slow axis as a tilting axis (rotation axis) (in a case where there is no slow axis, an arbitrary direction in the film plane is taken as the rotation axis) Rth may be calculated from the following equations (11) and (12) based on the assumed value and the inputted film thickness value.

Equation (11)

The above Re (&thetas;) represents the retardation value in the inclined direction from the normal direction.

In the expression (11), nx represents the index of refraction in the surface axial direction in the surface, ny represents the index of refraction in the direction orthogonal to nx in the surface, and nz represents the index of refraction in the direction perpendicular to nx and ny. d is the film thickness.

(12): Rth = {(nx + ny) / 2 - nz} xd

In the formula (12), nx represents the refractive index in the surface axial direction in the surface, ny represents the refractive index in the direction orthogonal to nx in the surface, and nz represents the refractive index in the direction orthogonal to nx and ny. d is the film thickness.

In the case where the film to be measured is a film which can not be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (?) Is calculated by the following method.

Rth (?) Is obtained by changing Re (?) From -50 degrees to +50 degrees in 10 degree steps with respect to the normal direction of the film, with the slow axis (determined by KOBRA 21ADH or WR) Light having a wavelength of? Nm is incident from the oblique direction, 11 points are measured, and KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the inputted film thickness value.

In the above measurement, a value of a catalog of various polymer films (JOHN WILEY & SONS, INC) and various optical films can be used as an assumption of an average refractive index. When the value of the average refractive index is not already known, it can be measured with an Abbe refractometer. The values of the average refractive index of the main optical film are as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49) and polystyrene (1.59). By inputting the assumptions of these average refractive indices and the film thickness, KOBRA 21ADH or WR calculates nx, ny, nz. Nz = (nx - nz) / (nx - ny) is further calculated from the calculated nx, ny, and nz.

In the present specification, when there is no particular addition to the measurement wavelength, the measurement wavelength is 550 nm. For example, Re is denoted simply as Re (550).

In the present specification, as for angles (e.g., angles such as " 90 DEG ") and their relations (e.g., "orthogonal", "parallel", and "crossed at 45" Includes a range of allowable errors in the art to which the present invention belongs. For example, within a range of an exact angle of less than +/- 10 degrees, and an error with a strict angle is preferably not more than 5 degrees, more preferably not more than 3 degrees. Means that Re (550)? 10 nm and Rth (550)? 10 nm, preferably Re (550)? 5 nm or less and Rth (550)? 5 nm, in which the retardation is substantially 0.

≪ Optical film, optical film material >

In the present specification, the optical film means a film that can be used for optical members such as various optical devices such as various display devices, light emitting devices, and polarizing plates. In the present invention, it is preferable that the optical film has a film thickness of, for example, about 100 μm or less, about 60 μm or less, about 40 μm or less, about 25 μm or less, about 10 μm or about 5 μm or less. The optical film is also preferably transparent (for example, a light transmittance of 80% or more). The optical film may be either low birefringence or high birefringence. It is preferable to have controlled birefringence.

In the present specification, the optical film material means a material for supplying an optical film. The optical film material may be any material capable of providing an optical film by peeling off a layer comprising a stretched film functioning as a branching material and may be any material that can be used as a transfer material for transferring the optical film to another material. The optical film material itself may be an optical film.

The optical film material of the present invention comprises a layer made of a stretched film, an optically anisotropic layer, and an acrylic polymer layer formed by curing a polymerizable composition containing (meth) acrylate. In the optical film material of the present invention, the stretched film layer and the optically anisotropic layer, and the optically anisotropic layer and the acrylic polymer layer are in direct contact with each other.

The optical film and the optical film material may include other functional layers such as a protective layer, an antistatic layer, a hard coat layer, and an adhesive layer in addition to the above layers.

<Polarizer>

The polarizing plate of the present invention includes an optical film and a polarizer including an optically anisotropic layer and an optically isotropic acrylic polymer layer. The optical film may be disposed on either one side or both sides of the polarizer. It is preferable that a protective layer (protective film) is disposed on the other surface when the optical film is disposed on one of the polarizers. A protective layer may be disposed between the polarizer and the optical film. In the optical film of the polarizing plate of the present invention, the optically anisotropic layer and the acrylic polymer layer may be laminated in this order from the polarizer side, or the acrylic polymer layer and the optically anisotropic layer may be laminated in this order. Either the optically anisotropic layer or the acrylic polymer layer may be in direct contact with the polarizer.

An example of the layer structure of the polarizing plate of the present invention is shown in Fig.

The film thickness of the polarizing plate is not particularly limited, but may be about 50 탆 to 500 탆. In particular, the polarizing plate of the present invention can be formed into a thin film of 200 占 퐉 or less, 150 占 퐉, 120 占 퐉, 100 占 퐉, 90 占 퐉, 80 占 퐉, 70 占 퐉 or less.

Hereinafter, the optical film material and each layer in the polarizing plate, the optical film material, and the method for producing the polarizing plate will be described in detail.

[Stretched film]

The stretched film used in the optical film material of the present invention is not particularly limited and may be a uniaxially stretched film or a biaxially stretched film but is preferably a uniaxially stretched film. The stretched film is preferably a stretched thermoplastic resin film. Examples of the thermoplastic resin include polyester polymers such as polyethylene terephthalate and the like, cycloolefin polymers (for example, norbornene resin (Zeonex manufactured by Zeon Corporation, Zeonoa, manufactured by JSR Corporation) (Polyethylene terephthalate), polyethylene terephthalate (PET), polyethylene terephthalate (PET), polyethylene terephthalate (PET), polyethylene terephthalate (PET) and the like.

The film thickness of the layer made of the stretched film may be about 10 탆 to 1000 탆, preferably 25 탆 to 250 탆, and more preferably 30 탆 to 90 탆.

In the optical film material of the present invention, the stretched film layer has a rubbed surface, and an optically anisotropic layer is directly formed on the rubbed surface.

The rubbing treatment can be generally carried out by rubbing the surface of the film containing the polymer as a main component in a certain direction with a paper or cloth. A general method of the rubbing treatment is described in, for example, &quot; Liquid Crystal Handbook &quot; (published by Maruzen Co., October 30, 2000).

As a method of changing the rubbing density, a method described in "Liquid Crystal Handbook" (Maruzen Publishing Co.) can be used. The rubbing density (L) is quantified by the following formula (A).

(A) L = N1 (1 + 2? Rn / 60v)

In the formula (A), N is the number of times of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of revolutions of the roller (rpm), and v is the stage moving speed (second speed).

In order to increase the rubbing density, it is necessary to increase the number of times of rubbing, increase the contact length of the rubbing roller, increase the radius of the roller, increase the number of revolutions of the roller, and slow the moving speed of the stage. On the other hand, do.

As a condition for the rubbing treatment, reference may be made to the disclosure of Japanese Patent No. 4052558.

[Optically anisotropic layer]

The optically anisotropic layer is a layer having optical characteristics that is not isotropic, in which one direction of incidence is not substantially zero when the retardation is measured. The optically anisotropic layer in the optical film used in the present invention is formed by polymerizing a liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound. The polymerizable composition contains a liquid crystal compound having at least one polymerizable group and may be one that polymerizes the liquid crystal composition by light irradiation. It is preferable that the polymerizable composition is formed by being coated on a branched support. Particularly, it is preferable that the stretched film is formed by being directly applied on the rubbed surface. The liquid crystal compound molecules in the layer can be aligned by drying the applied layer again at room temperature or the like or by heating (for example, heating at 50 ° C to 150 ° C, preferably at 80 ° C to 120 ° C). It is only necessary that the optically anisotropic layer is formed by light irradiation and polymerization and immobilization.

The film thickness of the optically anisotropic layer is 10 占 퐉 or less, 8 占 퐉, 7 占 퐉, 6 占 퐉, 5 占 퐉, 4 占 퐉, 3 占 퐉, 2 占 퐉, 1.9 占 퐉, 1.8 占 퐉, Less than or equal to 1 탆, more preferably 0.2 탆 or more, 0.3 탆 or more, 0.4 탆 or more, 0.5 탆 or more, 0.6 탆 or less 0.7 탆 or more, 0.8 탆 or more, and 0.9 탆 or more. The film thickness of the optically anisotropic layer is preferably smaller than the film thickness of the acrylic polymer layer.

(Liquid crystal compound)

Examples of the liquid crystal compound include a rod-like liquid crystal compound and a discotic liquid crystal compound.

Examples of the rod-like liquid crystal compound include azomethines, azoxysilanes, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano- Alkoxy-substituted phenylpyrimidines, phenyl dioxanes, tolans, and alkenylcyclohexyl benzonitriles are preferably used. In addition to the low-molecular liquid crystalline molecules described above, polymeric liquid crystalline molecules can also be used.

It is more preferable to fix the orientation of the rod-like liquid crystal compound by polymerization, and as the polymerizable rod-like liquid crystal compound, Chem., 190, 2255 (1989), Advanced Materials 5, 107 (1993), U.S. Pat. Nos. 4683327, 5622648, 5770107, WO95 / 22586, Japanese Patent Application Laid-Open Nos. 97/00600, 98/23580, 98/52905, 1-272551, 6-16616, 7-110469, 11-80081, The compounds disclosed in Patent Publications 2001-328973 and 2013-050583 can be used. The polymerizable rod-shaped liquid crystal compound is preferably a polymerizable rod-shaped liquid crystal compound represented by the following general formula (1).

???????? Q ¹ -L ¹ -Cy ¹ -L ² - (Cy ² -L ³ ) n-Cy ³ -L ⁴ -Q ² ?????

(In the general formula (1), Q ¹ and Q ² are each independently a polymerizable group, L ¹ and L ⁴ are each independently a divalent linking group, L ² and L ³ are each independently a single bond or a divalent linking group , Cy ¹ , Cy ² and Cy ³ are bivalent cyclic groups and n is 0, 1, 2 or 3,

The polymerizable rod-shaped liquid crystal compound represented by the general formula (1) will be described below.

In the general formula (1), Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably an addition polymerization (including ring-opening polymerization) or a condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

[Chemical Formula 1]

Among these, preferred examples of the polymerizable group include an acryl group and a methacryl group. Particularly, it is preferable that both of Q ¹ and Q ^{2 in} the general formula (1) are an acrylic group or a methacryl group. By using these groups, there is a tendency that the adhesion with the acrylic polymer layer formed by curing the polymerizable composition containing (meth) acrylate becomes good.

In the general formula (1), L ¹ and L ⁴ each independently represent a divalent linking group. L ¹ and L ⁴ are each independently selected from the group consisting of -O-, -S-, -CO-, -NR-, -C═N-, a divalent chained group, a divalent cyclic group, Lt; / RTI &gt; R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. R is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom.

An example of a divalent linking group consisting of a combination is shown below. Here, the left side is coupled to Q (Q ¹ or Q ² ) and the right side is coupled to Cy (Cy ¹ or Cy ³ ).

L-1: -CO-O-2 chain type -O-

L-2: chain-group of -CO-O-2, -O-CO-

L-3: chain-group of -CO-O-

L-4: a cyclic group of -CO-O-2, a cyclic group of -O-2,

L-5: a cyclic group of -CO-O-2, a cyclic group of -O-2, -CO-O-

L-6: a chain of -CO-O-2, a cyclic group of -O-2, -O-CO-

L-7: chain-group of -CO-O-2, chain-group of -O-2,

L-8 is a chain type of -CO-O-2, -O-2 is a cyclic-2-valent chain type, -CO-O-

L-9: chain-group of -CO-O-2 chain-group of -O-2-chain-group of -valent -O-

L-10: chain of -CO-O-2, cyclic group of -O-CO-2,

L-11: a cyclic group of -CO-O-2, a cyclic group of -O-CO-2, -CO-O-

L-12: a cyclic group of -CO-O-2, a cyclic group of -O-CO-

L-13: a chain form of -CO-O-2, a chain form of -O-CO-2,

L-14: chain-group of -CO-O-2 chain-group -CO-O-

L-15: chain-group of -CO-O-2 chain-group-O-CO-

L-16: a cyclic group of -CO-O-2, a cyclic group of -O-CO-O-

L-17: a cyclic group of -CO-O-2, a cyclic group of -O-CO-O-

L-18: a cyclic group of -O-CO-O-2, a cyclic group of -O-CO-

L-19: chain-group of -CO-O-2 chain-group-O-CO-O-

L-20: chain-group of -CO-O-2 chain-group of -O-CO-O-2 chain-

L-21: chain-group of -CO-O-2 chain-group -O-CO-O-

The divalent chained group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferable, and an alkylene group and an alkenylene group are more preferable.

The alkylene group may have a branch. The number of carbon atoms of the alkylene group is preferably from 1 to 12, more preferably from 2 to 10, and most preferably from 2 to 8.

The alkylene moiety of the substituted alkylene group is the same as the alkylene group. Examples of the substituent include a halogen atom.

The alkenylene group may have a branch. The number of carbon atoms of the alkenylene group is preferably from 2 to 12, more preferably from 2 to 10, and most preferably from 2 to 8.

The alkylene moiety of the substituted alkylene group is the same as the alkylene group. Examples of the substituent include a halogen atom.

The alkynylene group may have a branch. The carbon number of the alkynylene group is preferably from 2 to 12, more preferably from 2 to 10, and most preferably from 2 to 8.

The alkynylene moiety of the substituted alkynylene group is the same as the alkynylene group. Examples of the substituent include a halogen atom.

Specific examples of the divalent chained group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene and 2-butynylene .

The definitions and examples of the divalent cyclic group are the same as the definitions and examples of Cy ¹ , Cy ² and Cy ³ which will be described later.

In the general formula (1), L ² or L ³ are each independently a single bond or a divalent linking group. L ² and L ³ are each independently selected from the group consisting of -O-, -S-, -CO-, -NR-, -C═N-, a divalent chain group, a divalent cyclic group and combinations thereof Or a single bond. R is preferably an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, most preferably a hydrogen atom Do. The divalent chained group and the divalent cyclic group have the same definitions as L ¹ and L ⁴ .

Preferred divalent linking groups for L ² or L ³ include -COO-, -OCO-, -OCOO-, -OCONR-, -COS-, -SCO-, -CONR-, -NRCO-, -CH ₂ CH ₂ -, -C = C-COO-, -C = N-, -C = NN = C- and the like.

In the general formula (1), n is 0, 1, 2 or 3. When n is 2 or 3, two L ³ may be the same or different, and two Cy ^{2 may} be the same or different. n is preferably 1 or 2, and more preferably 1.

In the formula ^{(1), Cy 1, Cy} 2 and Cy ³ are each independently a divalent cyclic group.

The ring contained in the cyclic group is preferably a five-membered ring, a six-membered ring, or a seven-membered ring, more preferably a five-membered ring or a six-membered ring, and most preferably a six-membered ring.

The ring included in the cyclic group may be a condensed ring. However, it is more preferable that the condensed ring is rounded.

The ring contained in the cyclic group may be an aromatic ring, an aliphatic ring, or a heterocyclic ring. Examples of aromatic rings include benzene rings and naphthalene rings. Examples of aliphatic rings include cyclohexane rings. Examples of heterocycles include pyridine rings and pyrimidine rings.

As the cyclic group having a benzene ring, 1,4-phenylene is preferable. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. As the cyclic group having a pyrimidine ring, pyrimidine-2,5-diyl is preferable.

The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, An acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms, and an alkylcarbamoyl group having 2 to 6 carbon atoms Acylamino group.

Examples of polymerizable rod-shaped liquid crystalline compounds represented by the general formula (1) are shown below, but examples of the polymerizable rod-shaped liquid crystalline compounds of the present invention are not limited thereto.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

As the rod-like liquid crystal compound, it is preferable to use at least one compound represented by the following general formula (2) in addition to the polymerizable rod-shaped liquid crystal compound represented by the general formula (1).

In general formula (2)

M ¹ - (L ¹ ) p-Cy ¹ -L ² - (Cy ² -L ³ ) n-Cy ³ - (L ⁴ ) qM ²

(In the general formula (2), M ¹ and M ² each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, -SCN, -CF ₃ , A nitro group, or Q ¹ , but at least one of M ¹ and M ² represents a group other than Q ¹ .

Here, Q ¹ , L ¹ , L ² , L ³ , L ⁴ , Cy ¹ , Cy ² , Cy ³ and n have the same meanings as the groups represented by the general formula (1). P and q are 0 or 1.)

When M ¹ and M ² do not represent Q ¹ , M ¹ and M ² are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a cyano group, more preferably a carbon number An alkyl group having 1 to 4 carbon atoms, or a phenyl group, and p and q are preferably 0.

The preferable mixing ratio of the compound represented by the general formula (2) in the mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the compound represented by the general formula (2) is 0.1% to 40% , More preferably 1% to 30%, and still more preferably 5% to 20%.

Hereinafter, preferred examples of the compound represented by the formula (2) are shown, but the present invention is not limited thereto.

[Chemical Formula 6]

(7)

The discotic liquid crystalline compound can be prepared by a method similar to that described in the literature (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981) J. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J Am. Chem. Soc., Vol.116, page 2655 (1994)). The polymerization of a discotic liquid crystalline compound is described in JP-A-8-27284. In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic phase core of the discotic liquid crystalline compound. However, when the polymerizable group is directly coupled to the core of the disc, it becomes difficult to maintain the aligned state in the polymerization reaction. Thus, a connector is introduced between the discotic core and the polymerizable group. That is, the photo-curing type discotic liquid crystalline compound is preferably a compound represented by the following formula (3).

In general formula (3)

D (-L-P) n

(In the general formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12)

Preferable specific examples of the dentate core (D), the divalent linking group (L) and the polymerizable group (P) in the formula (3) are D1 to D15 described in JP-A-2001-4837 L1 to L25, and (P1) to (P18), and the contents described in this publication can be preferably used.

The compound represented by the general formulas (1) to (3) is contained in an amount of 80 mass% or more, 90 mass% or more, or 95 mass% or more, and 99.99 mass% or less , 99.98 mass% or less, and 99.97 mass% or less. Particularly, the content of the acrylic group or the methacrylic group-containing compound is preferably 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 99.99 mass% or less, 99.98 mass% or less, 99.97 mass% By weight or less.

The liquid crystal compound may be fixed in any alignment state among horizontal alignment, vertical alignment, oblique alignment, and torsional alignment. In the present specification, the term "horizontal orientation" means that in the case of rod-like liquid crystal, the molecular long axis is parallel to the horizontal plane of the transparent support. In the case of circular liquid crystal, But it is not required to be strictly parallel, and in this specification, it is assumed that the inclination angle formed with the horizontal plane means an orientation of less than 10 degrees. The optically anisotropic layer in the optical film material of the present invention preferably includes a rod-like liquid crystal compound immobilized in a horizontally aligned state.

(menstruum)

As a solvent used for preparing a coating liquid when preparing a composition containing a liquid crystal compound as a coating liquid, an organic solvent or water or a mixed solvent thereof is preferably used. Examples of the organic solvent include amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, heterocyclic compounds such as pyridine, hydrocarbons such as benzene and hexane, (For example, chloroform, dichloromethane), esters (e.g., methyl acetate, butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (e.g., tetrahydrofuran, -Dimethoxyethane), and alkyl alcohols (e.g., methanol, ethanol, propanol). Two or more kinds of solvents may be mixed and used. Of these, alkyl halides, esters, ketones and mixed solvents thereof are preferred.

The same solvent may be used for the composition for producing an acrylic polymer layer described later.

(Orientation fixation)

The polymerization reaction of the liquid crystal compound may be a photopolymerization reaction. As the photopolymerization reaction, any of radical polymerization and cation polymerization may be used, but radical polymerization is preferable. Examples of the radical photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2367661 and 2367670), acyloin ethers (described in U.S. Patent No. 2448828), α-hydrocarbon substituted aromatic acyloin compounds A combination of triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Patent No. 3549367), acrylequinone compound (described in U.S. Patent No. 2722512), a polynuclear quinone compound (described in U.S. Patent Nos. 3046127 and 2951758) (Disclosed in Japanese Patent Application Laid-Open No. 60-105667, US Patent No. 4239850), and oxadiazole compounds (described in US Patent No. 4212970). Examples of the cationic photopolymerization initiator include an organic sulfonium salt type, an iodonium salt type, a phosphonium salt type and the like, preferably an organic sulfonium salt type, and a triphenylsulfonium salt is particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate and the like are preferably used.

The amount of the photopolymerization initiator to be 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. The light irradiation for the polymerization of the liquid crystal compound is preferably conducted using ultraviolet rays. The irradiation energy is preferably 10 mJ / cm 2 to 10 J / cm 2, more preferably 25 to 1000 mJ / cm 2. The roughness is preferably 10 to 2000 mW / cm2, more preferably 20 to 1500 mW / cm2, still more preferably 40 to 1000 mW / cm2. The irradiation wavelength preferably has a peak at 250 to 450 nm, more preferably 300 to 410 nm. In order to promote the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions.

(Horizontal alignment agent)

(1) to (3) and monomers represented by the general formula (4) described in paragraphs 0098 to 0105 of JP-A No. 2009-69793 are added to the polymerizable composition containing the liquid crystal compound By containing at least one kind of used fluorine homopolymer or copolymer, the molecules of the liquid crystal compound can be oriented substantially horizontally. When the liquid crystal compound is horizontally aligned, its inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, still more preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

The addition amount of the horizontal alignment agent is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.02 to 1% by mass, based on the mass of the liquid crystal compound. Further, the compounds represented by the general formulas (1) to (4) described in paragraphs 0098 to 0105 of JP-A No. 2009-69793 may be used alone or in combination of two or more.

(Other additives)

The polymerizable composition containing a liquid crystal compound may contain other necessary additives, but it is preferable that the polymerizable composition does not contain a so-called chiral agent.

[Acrylic polymer layer]

The optical film material and the optical film include an acrylic polymer layer formed by curing a polymerizable composition containing (meth) acrylate. In the optical film material or the optical film, as the acrylic polymer layer, a polymerizable composition containing a (meth) acrylate monomer is directly applied to the surface of the optically anisotropic layer or the optically anisotropic layer before curing, and the coating layer is cured Layer is used. In the present specification, the term "layer formed of a polymerizable composition containing a liquid crystal compound" is sometimes referred to as an optically anisotropic layer or an optically anisotropic layer before curing.

The acrylic polymer layer may be optically isotropic. The optical isotropy means that the absolute value of the in-plane retardation (Re (550)) is 10 nm or less and the absolute value of the retardation in the thickness direction (Rth) is 10 nm or less.

That is, it is preferable that the acrylic polymer layer does not correspond to, for example, a polymer layer obtained by polymerizing a liquid crystal compound having an acrylate group. The (meth) acrylate-containing polymerizable composition for forming the acrylic polymer layer preferably has a content of the liquid crystal compound of less than 80 mass%, less than 70 mass%, less than 60 mass%, less than 50 mass%, less than 40 mass% %, Less than 30 mass%, less than 20 mass%, less than 10 mass%, less than 5 mass%, or less than 1 mass%.

The (meth) acrylate in the polymerizable composition containing (meth) acrylate for forming the acrylic polymer layer is not particularly limited as long as it is a compound containing an acryloyl group or a methacryloyl group. The number of the acryloyl group or the methacryloyl group in the compound may be one or two or more (for example, two, three, four, etc.). The molecular weight of the (meth) acrylate may be 5000 or less, preferably 3000 or less, more preferably 2,000 or less, and particularly preferably 1,000 or less. Examples of the (meth) acrylate include (meth) acrylic acid and various esters thereof (such as methyl (meth) acrylate).

The polymerizable composition containing (meth) acrylate for forming the acrylic polymer layer may contain a polymerizable compound other than (meth) acrylate.

The acrylic polymer may be, for example, a copolymer of polymethyl (meth) acrylate, (meth) acrylic acid and various esters thereof, a copolymer of styrene and (meth) acrylic acid or various (meth) acrylic acid esters, ) Acrylic acid or copolymers of various (meth) acrylic acid esters. Preferred examples include copolymers of methyl (meth) acrylate and (meth) acrylic acid, copolymers of allyl (meth) acrylate and (meth) acrylic acid, benzyl (meth) acrylate and poly And the like. These polymers may be used alone or in combination of plural kinds.

The acrylic polymer layer may be thermally polymerized or photopolymerized with (meth) acrylate and other monomers, but it is particularly preferable that the acrylic polymer layer is photopolymerized. The photopolymerization reaction may be carried out by directly applying a (meth) acrylate-containing polymerizable composition to a layer formed of a polymerizable composition containing a liquid crystal compound, and coating the layer. The light irradiation for the photopolymerization reaction may be carried out under the same conditions as the light irradiation for the polymerization of the above-mentioned liquid crystal compound, and the light irradiation for polymerization of the liquid crystal compound may simultaneously polymerize the (meth) acrylate.

As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator are appropriately used in accordance with the method.

Examples of the photopolymerization initiator include a visceral polyketal dopyl compound disclosed in U.S. Patent No. 2367660, an acyloin ether compound described in U.S. Patent No. 2448828, an α-hydrocarbon described in U.S. Patent No. 2722512 , A combination of a triarylimidazole dimer and a p-amino ketone described in U.S. Patent No. 3549367, or a combination of a triarylimidazole dimer and a p-aminoketone described in U.S. Patent Nos. 3046127 and 2951758, Trihalomethyl-s-triazine compounds described in Japanese Patent Publication No. 51-48516 and trihalomethyl-triazine compounds described in U.S. Patent No. 4239850, compounds described in U.S. Patent No. 4212976 And trihalomethyloxadiazole compounds described in the specification. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferable. In addition, "polymerization initiator C" described in JP-A-11-133600 is also preferable.

The amount of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.2 to 10% by mass, based on the solid content of the polymerizable composition for forming the acrylic polymer layer.

A polymer having a high Tg as a polymer in the acrylic polymer layer may be used in order to impart hard coatability to the acrylic polymer layer. The Tg is preferably 50 DEG C or higher, more preferably 80 DEG C or higher, and even more preferably 100 DEG C or higher. To increase the Tg of the polymer, a polar group such as a hydroxyl group, a carboxylic acid group or an amino group may be introduced. Examples of the high Tg polymer include a reaction product of alkyl (meth) acrylates such as polymethyl (meth) acrylate and polyethyl (meth) acrylate, a copolymer of alkyl (meth) acrylate and (meth) (Meth) acrylate such as hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, a reaction product of an alkyl (meth) acrylate and a hydroxyl group- A copolymer of a half ester which is a reaction product with an acid anhydride such as phthalic anhydride, and the like.

In order to impart hard coatability, a layer obtained by polymerizing at least one layer containing a bifunctional or higher functional polymerizable monomer and a polymerizable polymer by light irradiation or heat may be used. Examples of the reactive group include a vinyl group, an allyl group, an epoxy group, an oxetanyl group, and a vinyl ether group in addition to the (meth) acryl group. Examples of the polymerizable polymer include polymerizable group-containing acrylates such as glycidyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate and glycerol 1,3- , A reaction product of a polymerizable group-containing acrylate with a copolymer of (meth) acrylic acid, and a multi-component copolymer with other monomers.

The film thickness of the acrylic polymer layer is not more than 60 탆, not more than 50 탆, not more than 40 탆, not more than 30 탆, not more than 25 탆, or not more than 15 탆, further not less than 2 탆, not less than 3 탆, , 4.5 m or more, or 5 m or more. In the optical film material of the present invention, the film thickness of the acrylic polymer layer is preferably larger than the film thickness of the optically anisotropic layer. By making the film thickness of the acrylic polymer layer larger than the film thickness of the optically anisotropic layer, the laminate including the acrylic polymer layer and the optically anisotropic layer can be easily peeled off from the stretched film. The ratio of the film thickness of the acrylic polymer layer to the film thickness of the optically anisotropic layer may differ depending on the respective film thicknesses. For example, the "film thickness of the acrylic polymer layer" / "film thickness of the optically anisotropic layer" 6 to 5, 5 to 4, 4 to 3, 3 to 2, 2 to 1.5, 1.5 to 1.1, and so on. It is usually preferable to increase the film thickness of the acrylic polymer layer / the film thickness of the optically anisotropic layer as the film thickness of each film becomes smaller.

(Application method)

The application of the composition at the time of forming the optically anisotropic layer or the acrylic polymer layer can be carried out by various methods such as dip coating method, air knife coating method, spin coating method, slit coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method Or the extrusion coating method (U.S. Patent No. 2681294). Two or more layers may be coated simultaneously. Methods of simultaneous coating are described in U.S. Patent Nos. 2761791, 2941898, 3508947, and 3526528, and Harazaki Yuzo, Coating Engineering, 253 pages, Asakura Bookstore (1973).

&Lt; Polarizing plate production method >

The polarizing plate of the present invention can be produced, for example, as follows.

The layer comprising the stretched film of the above-mentioned optical film material is peeled off, and the optical film after peeling of the layer composed of the stretched film is laminated on the film including the polarizer. Alternatively, the above-mentioned optical film material is laminated on a film containing a polarizer, and then the layer comprising the stretched film is peeled off. Both films may be bonded by an adhesive layer during lamination.

[Film containing polarizer]

The film containing the polarizer may be composed of only a polarizer, and may include, in addition to the polarizer, a protective layer, another protective film, a layer containing a polymer having a cyclic olefin structure described later, and the like.

[Polarizer]

Polarizers include dye-based polarizers and polyene-based polarizers that use iodine-based polarizers and dichroic dyes. The iodine-based polarizer and the dye-based polarizer are generally produced by using a polyvinyl alcohol-based film. Any polarizer may be used in the present invention. For example, the polarizer is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. For example, Japanese Patent Application Laid-Open No. 2009-237376 discloses a polarizer composed of polyvinyl alcohol (PVA) and a dichroic molecule. The thickness of the polarizer may be 50 탆 or less, preferably 30 탆 or less, and more preferably 20 탆 or less. The film thickness of the polarizer may be 1 占 퐉 or more, 5 占 퐉 or more, or 10 占 퐉 or more.

[Protective layer (protective film)]

The polarizing plate may include a protective layer. For example, a protective film may be formed on one or both surfaces of the polarizer, and a film containing the polarizer may be used. In the transfer material, a protective layer may be formed on the outermost side of the optically anisotropic layer, preferably on the outermost side. Alternatively, a protective layer may be formed on either one or both surfaces after the transfer material or the transfer material and the film including the polarizer are adhered to each other.

The protective layer may be formed to directly contact the other layer by, for example, directly coating and drying the protective layer forming composition on the surface on which the protective layer is formed, It may be bonded. The adhesive or pressure-sensitive adhesive may be the same as the adhesive used for adhesion between a transfer material and a film containing a polarizer.

As the protective layer, a cellulose acylate-based polymer film, an acrylic polymer film, or a cycloolefin-based polymer film can be used. With regard to the cellulose acylate-based polymer, reference can be made to the description of the cellulose acylate-based resin disclosed in Japanese Patent Application Laid-Open No. 2011-237474. As the cycloolefin-based polymer film, reference can be made to the disclosure of JP-A-2009-175222 and JP-A-2009-237376.

The protective layer may contain, for example, at least 70% by mass, at least 80% by mass, at least 90% by mass, at least 95% by mass, at least 99% by mass of the polymer 100% by mass.

The film thickness of the protective layer may be 100 占 퐉 or less, 50 占 퐉 or less, 30 占 퐉 or less, 20 占 퐉 or less and 10 占 퐉 or less and 1 占 퐉 or more, 5 占 퐉 or more, or 10 占 퐉 or more.

[Adhesive layer]

The adhesive layer may be formed of an adhesive. In this specification, &quot; adhesion &quot; is used as a concept including &quot; adhesion &quot;. As the adhesive, there is no particular limitation, but a curable adhesive of an epoxy compound which does not contain an aromatic ring in the molecule as shown in Japanese Patent Laid-Open Publication No. 2004-245925, a curable adhesive of 360-450 nm described in JP-A- An active energy ray-curable adhesive comprising a photopolymerization initiator having a molar extinction coefficient at a wavelength of 400 or more and an ultraviolet ray curable compound as essential components, and a (meth) acrylic compound described in JP-A-2008-174667 (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule, (b) a (meth) acrylic compound having a hydroxyl group in the molecule and having only one polymerizable double bond, and (c) An active energy ray-curable adhesive containing ethylene oxide modified acrylate or nonylphenol ethylene oxide modified acrylate, and the like There.

[Layer containing a polymer having a cyclic olefin structure]

The polarizing plate of the present invention preferably comprises a layer containing a polymer having an annular olefin structure. The layer containing a polymer having a cyclic olefin structure has the same meaning as the cycloolefin-based polymer film, and a layer containing a polymer having a cyclic olefin structure is included, thereby imparting moisture permeability to the polarizing plate. The water vapor permeability means the property that water does not pass through but water vapor passes through.

The layer containing a polymer having a cyclic olefin structure may be an acrylic polymer layer. That is, the polymerizable composition containing (meth) acrylate may be a layer containing a monomer having a cyclic olefin structure and forming a polymer together with (meth) acrylate by the above curing. Alternatively, a layer containing a polymer having a cyclic olefin structure may be disposed between the optical film and the polarizer.

The thickness of the layer containing a polymer having a cyclic olefin structure may be 30 占 퐉 or less, preferably 20 占 퐉 or less, more preferably 10 占 퐉 or less, more preferably 1 占 퐉 or more, 5 占 퐉 or more, or 10 占 퐉 or more do.

[Hard coat layer]

The polarizing plate of the present invention may include a hard coat layer. The hard coat layer may be included as the outermost layer and is preferably included in the outermost layer on the optical film side as viewed from the polarizer. As the hard coat layer, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2012-103689.

In the present specification, the hard coat layer refers to a layer in which the pencil hardness of the transparent support is raised by forming the layer. Practically, the pencil hardness (JIS K5400) after hard coat layer lamination is preferably H or more, more preferably 2H or more, and most preferably 3H or more. The thickness of the hard coat layer is preferably 0.4 to 35 mu m, more preferably 1 to 30 mu m, and most preferably 1.5 to 20 mu m. For details of the composition, reference can be made to the disclosure of Japanese Laid-Open Patent Publication No. 2012-103689.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, reagents, amounts of substances, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

&Lt; Production and Evaluation of Optical Film Material >

[Formation of optically anisotropic layer]

The coating liquid prepared in accordance with the formulation of the coating liquid (A) shown in the following Table 1 was applied to a rubbing-treated fusing film-forming extended PET (thickness 75 占 퐉) using a wire bar and dried at room temperature for 30 seconds, And then subjected to UV irradiation for 6 to 12 seconds at an output of 60% with a Fusion D bulb (lamp 90 mW / cm) to prepare an optically anisotropic layer having a film thickness shown in Table 4. It was confirmed that the average inclination angle of the rod-like liquid crystalline compound with respect to the film surface was 0 °, and that the rod-like liquid crystal was aligned horizontally with respect to the film surface.

[Chemical Formula 8]

[Formation of acrylic polymer layer]

The coating liquid prepared by the prescription of the coating liquid (B) shown in the following Table 2 was coated on the prepared optically anisotropic layer by using a wire bar, dried at 60 DEG C for 150 seconds, further subjected to a nitrogen purge oxygen concentration of about 0.1% Irradiated with ultraviolet light having an illuminance of 400 mW / cm &lt; 2 &gt; and an irradiation dose of 300 mJ / cm &lt; 2 &gt; using an air-cooled metal halide lamp (manufactured by EI Graphics Co., Ltd.) of 160 W / Of acrylic polymer layers were formed to obtain optical film materials of Examples 1 to 3 and Comparative Examples 1 to 3.

[Chemical Formula 9]

[Example having an orientation layer]

(Preparation of Coating Solution AL-1 for Orientation Layer)

The following composition was prepared and filtered with a polypropylene filter having a pore diameter of 30 mu m to be used as an alignment layer coating liquid AL-1.

───────────────────────────────────────────

Composition of Coating Solution for Orientation Layer (%)

───────────────────────────────────────────

Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.)  3.23

Polyvinyl pyrrolidone (Luvitec K30, manufactured by BASF)  1.50

Distilled water 57.11

Methanol 38.16

───────────────────────────────────────────

The alignment film coating liquid of the above composition was applied to a wire straight support (PET (thickness: 75 占 퐉 manufactured by Fuji Film)). Dried for 60 seconds in warm air at 60 DEG C, and further for 120 seconds in warm air at 100 DEG C. [ The thickness of the alignment film was 0.7 mu m. On the surface of the orientation layer, a coating liquid prepared by the prescription of the coating liquid (A) shown in Table 1 was applied by using a wire bar. Thereafter, an optically anisotropic layer and an acrylic polymer layer were formed in the same manner as in Example 2, and optical film materials of Comparative Examples 4 and 5 were produced.

[Example of using branching not subjected to rubbing treatment]

An optically anisotropic layer and an acrylic polymer layer were formed in the same manner as in Example 2 except that the PET film (thickness 75 mu m), which was not subjected to rubbing treatment, was used as the branching material, and an optical film material of Comparative Example 6 was produced .

[Example using acrylic polymer solution]

(Adjustment of acrylic polymer solution)

The following composition was prepared and used as the acrylic polymer solution P-1.

───────────────────────────────────────────

Composition of coating liquid for acrylic polymer layer (%)

───────────────────────────────────────────

Dianal BR (Mw280000, manufactured by Mitsubishi Rayon Co., Ltd.) 10.00

Surfactant solution  0.03

(Megafac F-176PF, manufactured by Dainippon Ink and Chemicals, Inc.)

Methylene chloride accordingly

───────────────────────────────────────────

An acrylic polymer solution P-1 having the above composition was applied to an optically anisotropic layer of wire rod as the acrylic polymer layer and dried for 120 seconds with hot air at 60 DEG C, 7 &lt; / RTI &gt;

[Example using Polymer Liquid Crystal Polymer]

(Synthesis of main chain type liquid crystal polyester)

137 parts by mass of 4-acetoxybenzoic acid, 63 parts by mass of 6-acetoxy-2-naphthoic acid and 0.01 part by mass of potassium acetate were charged into the reaction vessel, the temperature was raised to 150 DEG C with stirring and sufficiently purged with nitrogen. The temperature was further raised to 300 DEG C with stirring, and the inside of the reaction vessel was gradually depressurized while removing the generated acetic acid. In this state, stirring was continued for 1 hour to synthesize a main chain type liquid crystal polymer A represented by the following structural formula (I-1).

A small amount of the main chain type liquid crystal polymer A was sandwiched between two sheets of glass, and the temperature at which softening was started by a polarizing microscope while heating was observed, which was about 310 ° C.

Further, m and n in the following structural formula (I-1) represent molar ratios, and m: n = 73: 27.

[Chemical formula 10]

(Adjustment of Polymer Liquid Crystal Polymer Solution)

The following composition was prepared and used as the polymer liquid crystal polymer solution LC-2.

───────────────────────────────────────────

Composition of coating liquid for polymer liquid crystal polymer layer (%)

───────────────────────────────────────────

The main chain type liquid crystal polymer A 10.00

Surfactant solution  0.03

(Megafac F-176PF, manufactured by Dainippon Ink and Chemicals, Inc.)

chloroform accordingly

───────────────────────────────────────────

As an optically anisotropic layer, a layer obtained by applying the polymer liquid crystal polymer solution LC-2 to a wire bar PET support and then drying for 120 seconds with hot air at 60 DEG C was used, 8 &lt; / RTI &gt;

[Example of using an unoriented cycloolefin-based polymer film as a branching material]

An optical film material of Comparative Example 9 was obtained in the same manner as in Example 2 except that a commercially available cycloolefin based polymer film (non-stretched film) "ZEONOR ZF14" (manufactured by Nippon Zeon Co., Ltd., film thickness 100 μm) .

[Example of using a stretched cycloolefin-based polymer film as a branching material]

(Production of cycloolefin polymer film T1)

A commercially available cycloolefin polymer film "ZEONOR ZF14" (manufactured by Nippon Zeon) was stretched under the conditions described in Table 3 to obtain a film T1. Table 3 shows the film thicknesses, Re, Rth and Nz of the film T1. The slow axis of the film was parallel to the stretching direction, that is, 45 占 in the counterclockwise direction with respect to the film transport direction.

The optical film material of Example 4 was produced in the same manner as in Example 2 except that the produced film T1 was used as a branching material.

[Evaluation of characteristics of optical film material]

For the obtained optical film material, the evaluation of the characteristics was carried out based on the following criteria. The results are shown in Table 4.

(1) Evaluation of optical anisotropy

The prepared optical film was peeled off from the branching material, adhered to a glass substrate having no anisotropy, and the sample was rotated under a quenching position of a polarization microscope to confirm the optical anisotropy of the optical film material.

A: Obviously, it has a bright spot.

B: It has a weak luminous intensity.

C: It has a partially weak luminous streak.

D: It does not have a clear luminous stomach.

(2) Evaluation of adhesion between an optically anisotropic layer containing a polymerizable liquid crystal compound and an acrylic polymer layer

The produced optical film was peeled off from the branching material, and a pressure-sensitive adhesive test was carried out on both sides of the optical film material by pressing a polyester adhesive tape "NO.31B " manufactured by Nitto Co., Ltd. to obtain optically- The presence or absence of peeling of the anisotropic layer and the acrylic polymer layer was visually observed.

A: No peeling was observed at all

B: Partially peeled

C: Completely peeled

(3) Evaluation of peelability from branch lags

The prepared optical film material was cut into a size of 200 mm x 300 mm, and a layer formed by pressing a polyester adhesive tape "NO.31B " manufactured by Nitto Co., Ltd. on a layer having a side edge of 200 mm formed thereon The peelability from the retardation was evaluated according to the following criteria.

A: There is no peeling resistance, and the entire surface can be smoothly peeled off.

B: There is resistance at the time of peeling, but the entire surface can be smoothly peeled off.

C: The peeling resistance is large, and the entire surface can not be separated smoothly.

D: The peeling resistance is large, and it is cut off halfway and can be peeled only about half.

E: It can not be peeled off.

(4) Evaluation of bending resistance

The produced optical film material was peeled off from the branching material and bent at two in a wet place, and then the bent portion was observed by an optical microscope and evaluated.

A: No cracks or creases occur at every bent point.

B: There are no cracks at all bent points, but some places have been broken.

C: Cracks and dents occurred in some places.

D: Cracks and dents occurred in almost all areas.

&Lt; Production of polarizing plate &

[Formation of optical film L-1]

An optical anisotropic layer having a thickness of 1.5 占 퐉 and an acrylic polymer layer having a thickness of 5.0 占 퐉 were formed in this order on the PET in the same manner as in the formation of the optical film material of Example 1 to obtain an optical film material. Then, the branched film (PET) was peeled from the obtained optical film material to obtain an optical film.

An acrylic adhesive was used for bonding the optical film to the polarizer, and when the protective film was laminated with the protective sheet, the concave surface of the protective sheet was corona-treated, and the film was bonded using an acrylic adhesive.

[Formation of optical film L-2 having a support]

A commercially available cellulose acylate film (Fujita ZRD40, manufactured by Fuji Film Co., Ltd.) was passed through a dielectric type heating roll at a temperature of 60 占 폚 to raise the surface temperature of the film to 40 占 폚. Was applied at a coating amount of 14 ml / m 2 using a bar coater and transported for 10 seconds under a steam-type out-of-round heater manufactured by Noritake Co., Ltd., which was heated to 110 ° C. Subsequently, similarly, using a bar coater, pure water was applied at 3 ml / m &lt; 2 &gt;. Subsequently, washing with water by a fountain coater and removal of water by an air knife were repeated three times, followed by drying in a drying zone at 70 DEG C for 10 seconds, followed by drying to prepare an alkali saponified cellulose acylate film.

(Alkali solution composition)

───────────────────────────────────────────

Alkali solution composition (parts by mass)

───────────────────────────────────────────

Potassium hydroxide  4.7 parts by mass

water 15.8 parts by mass

Isopropanol 63.7 parts by mass

Surfactants

SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂ OH 1.0 part by mass

Propylene glycol 14.8 parts by mass

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[Formation of alignment film]

The above-mentioned saponified long-film cellulose acylate film was coated with an alignment film coating liquid of the following composition continuously on the wire # 14. And then dried with warm air at 60 DEG C for 60 seconds and further with hot air at 100 DEG C for 120 seconds to prepare an orientation film.

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Composition of Coating Solution for Orientation Layer (%)

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Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.)  3.23

Polyvinyl pyrrolidone (Luvitec K30, manufactured by BASF)  1.50

Distilled water 57.11

Methanol 38.16

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An optically anisotropic layer was formed in the same manner as in the above example except that a substrate (on which an alignment film was formed) before the formation of the optically anisotropic layer was used to obtain an optical film L-2 having a support.

When the optical film was laminated with the protective sheet, the protective sheet was corona-treated on the optically anisotropic layer surface, and then the protective sheet surface was bonded using an acrylic adhesive.

[Production of cyclic olefin resin sheet T-1]

A commercially available cycloolefin-based polymer film "ZEONOR ZF14" (manufactured by Nippon Zeon) was stretched by the drawing temperature (Tg is the glass transition temperature of the cyclic olefin based resin) and the drawing ratio shown in Table 5, To obtain a resin sheet T-1.

When the polarizer and the polarizer were laminated, corona treatment was performed on one side and the PVA adhesive was applied on the corona-treated side.

[Production of acrylic resin sheet T-2]

The following acrylic resin was used. This acrylic resin is commercially available.

Dianal BR88 (trade name), manufactured by Mitsubishi Rayon Co., Ltd., mass average molecular weight 1500000 (hereinafter referred to as acrylic resin AC-1).

(Ultraviolet absorber)

The following ultraviolet absorber was used.

UV 1: Tinuvin 328 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

(Dope B preparation)

The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare Dope B. [

(Dope B Composition)

Acrylic resin AC-1 100 parts by mass

UV absorber UV 1st   2 parts by mass

Dichloromethane 300 parts by mass

ethanol  40 parts by mass

Using a band softener, the dope prepared above was uniformly softened from a flexible die to a stainless steel endless band (flexible support) with a width of 2000 mm. When the amount of residual solvent in the dope reached 40% by mass, it was peeled from the flexible support as a polymer film, conveyed without being stretched, and dried at 130 캜 in a drying zone. The obtained acrylic resin sheet T-2 had a thickness of 40 m.

When the polarizer and the polarizer were laminated, corona treatment was performed on one side and the PVA adhesive was applied on the corona-treated side.

(Cellulose acylate film)

The surface of a commercially available cellulose acylate film (Fujitak 40 μm or 80 μm, manufactured by Fuji Film Co., Ltd.) (TAC) was alkali saponified. Immersed in a 1.5-fold aqueous sodium hydroxide solution at 55 ° C for 2 minutes, washed in a washing bath at room temperature and neutralized with 0.1 N sulfuric acid at 30 ° C. And further washed in a washing bath at room temperature, and further dried with warm air at 100 ° C. Upon mating with the polarizer, the obtained saponified side was made to be the polarizer side. PVA adhesive was used as the adhesive.

[Production of Polarizer]

A roll-shaped polyvinyl alcohol film having a thickness of 80 탆 was successively stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film (polarizer) having a thickness of 20 탆.

Using the obtained optical film, polarizer, and the above-mentioned cyclic olefin resin sheet, acrylic resin sheet or cellulose acylate film, an optical film, a unidirectional polarizing plate protective sheet (including unused examples), a polarizer, And the polarizing plates of Examples 101 to 112 and Comparative Examples 101 to 105 having the structures shown in Table 6 were obtained.

[Evaluation of Curl of Polarizer]

The obtained polarizing plate was cut out to a size of 150 mm x 150 mm, and the optically anisotropic layer side was placed on a horizontal flat bed and stopped, and the following evaluations were carried out. The results are shown in Table 6 below.

A: strongly curved toward the optically anisotropic layer side.

B: Curled slightly toward the optically anisotropic layer side.

C: A little curl or little curl.

The film thicknesses of the polarizing plates of Examples 101 to 112 and Comparative Examples 101 to 105 were as shown in Table 7 below.

1 polarizer
2 optically anisotropic layer
3 Acrylic polymer layer
4 Protective film 1
5 hard coat layer
6 Protection film 2

Claims (21)

A layer made of a stretched film, an optically anisotropic layer, and an optically isotropic acrylic polymer layer,
The layer made of the stretched film has a rubbed surface,
The optically anisotropic layer is a layer formed by polymerizing the liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound directly coated on the surface,
The acrylic polymer layer is a layer formed by curing a polymerizable composition containing (meth) acrylate directly applied to the surface of a layer formed of the polymerizable composition containing the above liquid crystal compound, and
Wherein the film thickness of the acrylic polymer layer is larger than the film thickness of the optically anisotropic layer. The method according to claim 1,
Wherein the stretched film is a polyethylene terephthalate film or a cycloolefin polymer film. The method according to claim 1,
Wherein the stretched film is a polyethylene terephthalate film. 4. The method according to any one of claims 1 to 3,
Wherein the optically anisotropic layer has a thickness of 0.5 to 5 占 퐉. 4. The method according to any one of claims 1 to 3,
And the film thickness of the optically anisotropic layer is 0.5 mu m to 3 mu m. 6. The method according to any one of claims 1 to 5,
Wherein the liquid crystal compound is a compound having two or more (meth) acryl groups. 7. The method according to any one of claims 1 to 6,
Wherein the acrylic polymer layer is a layer formed by light irradiation of a polymerizable composition containing (meth) acrylate to polymerize (meth) acrylate. 8. The method according to any one of claims 1 to 7,
Wherein the acrylic polymer layer has a thickness of 50 m or less. An optical film comprising the optically anisotropic layer and the acrylic polymer layer obtained by peeling a layer comprising a stretched film from the optical film material according to any one of claims 1 to 8. The method for producing an optical film material according to any one of claims 1 to 8,
(1) rubbing at least one side of the stretched film,
(2) applying a polymerizable composition containing a liquid crystal compound to the rubbed surface of the stretched film,
(3) applying a polymerizable composition containing a direct (meth) acrylate to a layer formed of the above-mentioned polymerizable composition containing a liquid crystal compound,
(4) A method for producing an optical film material, which comprises curing the polymerizable composition containing the liquid crystal compound and the polymerizable composition containing the (meth) acrylate. 11. The method of claim 10,
Wherein the curing is performed by light irradiation. 12. The method of claim 11,
(1) rubbing at least one side of the stretched film,
(2) applying a polymerizable composition containing a liquid crystal compound directly to the rubbed surface of the stretched film,
(2-2) irradiating a polymerizable composition containing the liquid crystal compound described above to polymerize the liquid crystal compound to form an optically anisotropic layer,
(3) applying the above-mentioned (meth) acrylate-containing polymerizable composition directly to the optically anisotropic layer,
(3-2) A process for producing an optical film material, comprising the step of irradiating the above-mentioned (meth) acrylate-containing polymerizable composition to polymerize the (meth) acrylate to form an acrylic polymer layer . As a method for producing a polarizing plate,
(1) preparing an optical film material according to any one of claims 1 to 8,
(2) peeling the layer comprising the stretched film of the optical film material,
(3) A method for producing a polarizing plate, which comprises laminating an optical film after peeling of the optical film material or the stretched film, on a film including a polarizer. 14. The method of claim 13,
Wherein the optical film material is laminated on the film including the polarizer on the side of the acrylic polymer layer as viewed from the optically anisotropic layer, and then the layer comprising the stretched film of the optical film material is peeled off. 14. The method of claim 13,
Wherein a layer comprising the stretched film of the optical film material is peeled off and thereafter the optical film after peeling of the stretched film layer is laminated on the film containing the polarizer. 1. A polarizing plate comprising a polarizer and an optical film comprising an optically anisotropic layer and an optically isotropic acrylic polymer layer,
Wherein the optically anisotropic layer is a layer formed by polymerizing the liquid crystal compound by irradiating a polymerizable composition containing a liquid crystal compound,
The acrylic polymer layer is a layer formed by curing a polymerizable composition containing (meth) acrylate directly applied to the surface of a layer formed of the polymerizable composition containing the liquid crystal compound,
Wherein the film thickness of the acrylic polymer layer is larger than the film thickness of the optically anisotropic layer. A polarizing plate comprising the optical film according to claim 9 and a polarizer. 18. The method according to claim 16 or 17,
Wherein the optically anisotropic layer and the polarizer are in direct contact with each other. 18. The method according to claim 16 or 17,
Wherein the acrylic polymer layer and the polarizer are in direct contact with each other. 20. The method according to any one of claims 16 to 19,
A cellulose acylate film,
Wherein the optical film, the polarizer, and the cellulose acylate film are in this order. 21. The method according to any one of claims 16 to 20,
And a hard coat layer on the outermost layer on the optical film side as viewed from the polarizer.

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