JP5477186B2 - Optically anisotropic film, polarizing plate, and liquid crystal display device - Google Patents

Description

  The present invention relates to an optically anisotropic film, a polarizing plate, and a liquid crystal display device.

  In the liquid crystal display device, for example, an optical film having optical compensation performance is used to improve optical characteristics such as viewing angle characteristics. As such an optical film, an optical film containing a polymerizable liquid crystal compound and having a liquid crystal layer in which the polymerizable liquid crystal compound is aligned and has optical anisotropy is known. Then, as a method of forming such a liquid crystal layer (also referred to as an optically anisotropic layer), first, a liquid crystal that improves the orientation of the polymerizable liquid crystal compound contained in the liquid crystal layer on a transparent film substrate or the like. A step of applying a composition for forming an alignment layer and curing it by irradiating ultraviolet rays to form a liquid crystal alignment layer, and then a liquid crystal layer forming composition containing a polymerizable liquid crystal compound on the liquid crystal alignment layer And a step of forming a liquid crystal layer by fixing the orientation after applying the product and orienting the polymerizable liquid crystal compound.

  When the liquid crystal layer molding is performed with a coating mold, there are problems of orientation of liquid crystal material and coating unevenness. Therefore, Patent Documents 1 to 5 disclose a method for improving orientation using a fluoroaliphatic group-containing polymer or a fluorosurfactant in which a part of a long-chain alkyl group is fluorine-substituted. The problem is that the liquid crystal layer is peeled off from the transparent film substrate due to heating and humidification of the polarizing plate produced from the above, or when the film is wound into a roll in long coating, the liquid crystal coating is not on the side opposite to the liquid crystal layer. There is a problem that the transfer of the activator occurs on the coated surface, and the adhesiveness deteriorates and peels off when being bonded to the polarizer.

  In addition, when the polarizing plate is bonded to the panel, the fluorosurfactant contained in the liquid crystal layer makes the adhesion between the liquid crystal surface and the adhesive insufficient, and the polarizing plate itself is peeled off from the panel. It was.

JP 2008-231396 A JP 2008-194659 A JP 2008-197170 A JP 2005-165239 A JP 2005-165240 A

  Accordingly, an object of the present invention is an optically anisotropic film in which a liquid crystal compound is fixed in a state inclined with respect to the thickness direction of the liquid crystal layer, and there is no problem of alignment of liquid crystal material and coating unevenness, and Excellent adhesion between the liquid crystal layer and the transparent film substrate, and even when the film is wound into a roll, there is no transfer of the activator from the liquid crystal layer to the opposing surface, and excellent adhesion to the polarizer. An object of the present invention is to provide an optically anisotropic film having good adhesion to a pressure-sensitive adhesive.

  Further, a polarizing plate using such an optically anisotropic film as a protective film, and a liquid crystal display device including the polarizing plate, particularly a twisted nematic liquid crystal display device excellent in viewing angle, gradation inversion, color shift, and blurring Is to provide.

  The above object of the present invention is achieved by the following configurations.

  1. In an optically anisotropic film formed by laminating a liquid crystal alignment layer and a liquid crystal layer on a film substrate, the liquid crystal layer contains a fluorine-siloxane graft polymer and a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is a liquid crystal layer An optically anisotropic film, which is inclined with respect to the thickness direction and is fixed in an inclined state.

  2. The above 1 characterized in that the fluorine-siloxane graft polymer is a copolymer obtained by reacting a fluorine resin having a radical polymerizable unsaturated bond moiety via a urethane bond with one-end radical polymerizable polysiloxane. The optically anisotropic film as described.

  3. 3. The optically anisotropic film as described in 1 or 2 above, wherein the fluorine-siloxane graft polymer is contained in an amount of 0.01 to 1% by mass with respect to the polymerizable liquid crystal compound.

  4). 4. The optically anisotropic film as described in any one of 1 to 3, wherein the polymerizable liquid crystal compound contains a discotic compound.

  5. 5. The optically anisotropic film as described in any one of 1 to 4, wherein the liquid crystal layer contains a photopolymerization initiator in an amount of 0.1 to 30% by mass with respect to the polymerizable liquid crystal compound.

  6). 6. The optically anisotropic film according to any one of 1 to 5, wherein the film base material contains diacetyl cellulose having an acetyl group substitution degree of 2.1 to 2.6.

  7). A polarizing plate comprising the optically anisotropic film according to any one of 1 to 6 on at least one surface of a polarizer.

  8). A twisted nematic liquid crystal display device comprising the polarizing plate described in 7 above on at least one surface of a liquid crystal cell.

  According to the present invention, there is provided an optically anisotropic film in which a liquid crystal compound is fixed in a state inclined with respect to the thickness direction of the liquid crystal layer, and there is no problem of alignment of liquid crystal material and coating unevenness, and the liquid crystal Excellent adhesion between the layer and the transparent film substrate, and even when the film is wound into a roll, there is no transfer of the activator from the liquid crystal layer to the opposite surface, and adhesion with the polarizer is excellent. An optically anisotropic film having good adhesion to the agent can be provided.

  Further, a polarizing plate using such an optically anisotropic film as a protective film, and a liquid crystal display device including the polarizing plate, particularly a twisted nematic liquid crystal display device excellent in viewing angle, gradation inversion, color shift, and blurring Can be provided.

1 is a schematic cross-sectional view illustrating an example of an optically anisotropic film 10. FIG. It is the schematic which shows the basic composition of the manufacturing apparatus 20 of an optical anisotropic film. It is the schematic which shows the basic composition of the manufacturing apparatus 31 of the resin film by a solution casting method. It is the schematic which shows the basic composition of the manufacturing apparatus 41 of the resin film by a melt casting film forming method.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  The optically anisotropic film of the present invention is an optically anisotropic film obtained by laminating a liquid crystal alignment layer and a liquid crystal layer on a film substrate, wherein the liquid crystal layer contains a fluorine-siloxane graft polymer and a polymerizable liquid crystal compound. The polymerizable liquid crystal compound is tilted with respect to the thickness direction of the liquid crystal layer, and is fixed in the tilted state. In such a configuration, sufficient liquid crystal orientation of the liquid crystal layer is imparted. Improves coating unevenness and is excellent in adhesion between the liquid crystal layer and the transparent film substrate, and even when the film is wound up in a roll, there is no transfer of the activator from the liquid crystal layer to the opposing surface and adhesion to the polarizer The present invention provides an optically anisotropic film having excellent properties and excellent adhesion between the liquid crystal layer surface and the pressure-sensitive adhesive.

[Optically anisotropic film]
An optically anisotropic film according to an embodiment of the present invention includes a film substrate, a liquid crystal alignment layer formed on the film substrate, and a polymerizable liquid crystal compound formed on the liquid crystal alignment layer. And a liquid crystal layer containing a fluorine-siloxane graft polymer.

  The optically anisotropic film is not particularly limited as long as it has the above configuration. Specifically, the optical anisotropic film 10 provided with the layer structure shown in FIG. 1 etc. are mentioned, for example.

  First, as the optical anisotropic film 10, for example, as shown in FIG. 1A, a liquid crystal alignment layer 13 and a liquid crystal layer 14 are laminated on a film substrate 11 and the liquid crystal alignment layer 13. What is a laminated body is mentioned. In FIG. 1A, the liquid crystal alignment layer 13 and the liquid crystal layer 14 are shown as the functional layer 12.

  The optically anisotropic film 10 is not limited to the functional layer 12 including only the liquid crystal alignment layer 13 and the liquid crystal layer 14 as shown in FIG. It may be. Specifically, for example, as shown in FIG. 1B, a first intermediate layer 15 may be provided as the functional layer 12 between the liquid crystal alignment layer 13 and the liquid crystal layer 14. As shown in (c), as the functional layer 12, a second intermediate layer 16 may be provided between the film substrate 11 and the liquid crystal layer 14. Further, both the first intermediate layer 15 and the second intermediate layer 16 may be provided. Examples of the first intermediate layer 15 include an alignment film, an antistatic layer, and an antiglare layer. Examples of the second intermediate layer 16 include an antistatic layer, an elution suppressing layer, and an antiglare layer. Etc.

  The optically anisotropic film of the present invention is characterized in that the liquid crystal layer 14 contains a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is inclined with respect to the thickness direction of the liquid crystal layer.

  The inclination angle is preferably in the range of 5 to 50 ° with respect to the thickness direction of the liquid crystal layer, and more preferably in the range of 28 ° ± 2 ° with respect to the thickness direction of the liquid crystal layer. Is preferable. The tilt angle of the polymerizable liquid crystal compound with respect to the thickness direction is determined by using a birefringence meter capable of tilt measurement (for example, KOBRA-31WR manufactured by Oji Scientific Instruments, Axoscan manufactured by Opto Science Co., Ltd., Spectroscopic Ellipsometer DVA36VW manufactured by Mizoji Optical Co., Ltd.). It can be determined by measuring in an atmosphere of 23 ° C. and 55% RH, and 10 points at different sites are measured, and the average value is taken as the average inclination angle.

  The method of inclining is not particularly limited, but can be generally adjusted by selecting a polymerizable liquid crystal compound or an alignment film material or by selecting a rubbing treatment method. . Moreover, the inclination angle of the polymerizable liquid crystal compound on the surface side (air side) can be generally adjusted by selecting a polymerizable liquid crystal compound or another compound used together with the polymerizable liquid crystal compound. Examples of the compound used together with the polymerizable liquid crystal compound include a plasticizer, a surfactant, a polymerizable monomer and a polymer. Further, the degree of change in the tilt angle can be adjusted by the same selection as described above.

  In order to perform the rubbing treatment, first, an alignment film is formed on the film substrate, and the surface of the formed alignment film can be obtained by rubbing as follows.

  For example, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyacylate fiber, or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

  In industrial implementation, this is achieved by bringing a rotating rubbing roll into contact with the film substrate on which the alignment film is formed. However, the roundness, cylindricity, and deflection (eccentricity) of the rubbing roll are achieved. ) Is preferably 30 μm or less. The wrap angle of the film on the rubbing roll is preferably 0.1 to 90 °.

  However, as described in JP-A-8-160430, a stable rubbing treatment can be obtained by winding 360 ° or more.

  As for the conveyance speed of a film, 1-100 m / min is preferable. It is preferable to select an appropriate rubbing angle in the range of 0 to 60 °. When used in a liquid crystal display device, the angle is preferably 40 to 50 °. 45 ° is particularly preferred.

  As another method, when a liquid crystal layer containing a polymerizable liquid crystal compound is formed on an alignment film of a film substrate and irradiated with light that is not polarized, that is, in the same mode as natural light, from the oblique direction, the photosensitive liquid crystal compound in the polymerizable liquid crystal compound is exposed. The sex site can be obliquely oriented. Unlike rubbing treatment, light can be irradiated on the entire surface without any gaps, so an improvement in yield can be expected. Furthermore, it is a preferable method because it is possible to easily make a multi-domain by diverting a photolithography technique and generate a large pretilt angle.

  Further, the optically anisotropic film 10 preferably has in-plane retardations Ro and Rt determined by the following formulas (1) and (2) of 0 ≦ Ro ≦ 200 nm and 30 ≦ Rt ≦ 400 nm. Preferably, 30 ≦ Ro ≦ 100 nm and 50 ≦ Rt ≦ 300 nm. Further, the variation of Rt and the width of distribution are preferably less than ± 10%, more preferably less than ± 5%. More preferably, it is less than ± 1%, and most preferably, there is no fluctuation of Rt.

Ro = (nx−ny) × d (1)
Rt = {(nx + ny) / 2−nz} × d (2)
Here, nx represents the refractive index in the slow axis direction in the plane of the film, ny represents the refractive index in the direction perpendicular to the slow axis in the plane of the film, and nz represents the thickness direction of the film. Refractive index is shown, d shows the thickness (nm) of a film. Each refractive index can be measured at a wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55% RH using, for example, KOBRA-21ADH manufactured by Oji Scientific Instruments.

<Fluorine-siloxane graft polymer>
In the present invention, the liquid crystal layer of the optically anisotropic film contains a fluorine-siloxane graft polymer, so that there is no problem of tilt alignment of the liquid crystal material and coating unevenness, and adhesion between the liquid crystal layer surface and the pressure-sensitive adhesive. It is necessary to improve the quality.

  Fluorine-siloxane graft polymer refers to a polymer obtained by copolymerizing polysiloxane or organopolysiloxane containing siloxane or organosiloxane alone to at least a fluorine-based resin by grafting. It is a compound shown in.

  Examples of the fluorine-siloxane graft polymer include (A) an organic solvent-soluble fluororesin having a radically polymerizable unsaturated bond moiety via a urethane bond [hereinafter also referred to as radically polymerizable fluororesin (A)], (B) One-end radical polymerizable polysiloxane represented by the following general formula (1) and / or one-end radical polymerizable polysiloxane represented by the following general formula (2) [hereinafter referred to as one-end radical polymerizable polysiloxane (B) And (C) a radically polymerizable fluorine resin (A) and a radically polymerizable monomer that does not react other than the polymerization reaction by a double bond under the radical polymerization reaction conditions [hereinafter, radically polymerizable fluorine resin ( (Also referred to as C)], and compounds formed by graft copolymerization.

In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), aryl group ( For example, a phenyl group), a cycloalkyl group (for example, a cyclohexyl group), etc. can be mentioned. R ¹ is preferably a hydrogen atom or a methyl group. R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other, and R ² , R ³ , R ⁴ , and R ⁵ is preferably each independently a methyl group or a phenyl group, and R ⁶ is preferably a methyl group, a butyl group or a phenyl group. N is an integer of 2 or more, preferably an integer of 10 or more, more preferably an integer of 30 or more.

In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other, and R ⁸ , R ⁹ , R ¹⁰ , And R ¹¹ are each independently preferably a methyl group or a phenyl group, and R ¹² is preferably a methyl group, a butyl group, or a phenyl group. p is an integer of 0 to 10, preferably an integer of 10 or more, more preferably an integer of 30 or more. q is an integer of 2 or more.

  Next, (A) the organic solvent-soluble fluororesin having a radical polymerizable unsaturated bond moiety via a urethane bond will be described in detail.

  The radical polymerizable fluororesin (A) can be obtained by reacting an organic solvent-soluble fluororesin (A-1) having a hydroxyl group with a radical polymerizable monomer (A-2) having an isocyanate group.

  The organic solvent-soluble fluororesin having a hydroxyl group (A-1) is not particularly limited as long as it contains at least a hydroxyl group-containing monomer portion and a polyfluoroparaffin portion as its constituent components. The repeating unit includes a repeating unit represented by the following general formula (3) and a repeating unit represented by the following general formula (4).

In the formula, R ²¹ and R ²² may be the same or different independently for each repeating unit, and may be a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), a C 1-10 carbon atom. Carbon number substituted with one or more alkyl groups (for example, methyl group or ethyl group), aryl groups having 6 to 8 carbon atoms (for example, phenyl group), halogen atoms (for example, fluorine atom or chlorine atom) 1 to 10 alkyl groups (for example, trifluoromethyl group, 2,2,2-trifluoroethyl group, or trichloromethyl group) or halogen atoms (for example, fluorine atoms or chlorine atoms) are substituted with one or more And an aryl group having 6 to 8 carbon atoms (for example, a pentafluorophenyl group), and x is an integer of 2 or more.

In the formula, R ²³ is independently a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group or an ethyl group), carbon, independently for each repeating unit. An aryl group having 6 to 8 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atoms or chlorine atoms) (for example, a trifluoromethyl group, 2,2,2-trifluoroethyl group or trichloromethyl group), or an aryl group having 6 to 8 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, penta R ²⁴ is a divalent group selected from OR ^25a group, CH ₂ OR ^25b group, and COOR ^25c group independently for each repeating unit. R ^25a , R ^25b , and R ^25c are each an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, or a hexamethylene group), a cyclohexane having 6 to 10 carbon atoms. An alkylene group (for example, cyclohexylene group), an alkylidene group having 2 to 10 carbon atoms (for example, isopropylidene group), and a divalent group selected from 6 to 10 carbon atoms, y is an integer of 2 or more.

  Furthermore, the organic solvent-soluble fluororesin (A-1) having a hydroxyl group may contain a repeating unit represented by the following general formula (5) as other constituent components.

In the formula, R ²⁶ is independently a hydrogen atom, a halogen atom (eg, a fluorine atom or a chlorine atom), or an alkyl group having 1 to 10 carbon atoms (eg, a methyl group or an ethyl group) independently for each repeating unit. An alkyl group having 6 to 10 carbon atoms (for example, a phenyl group), an alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atoms or chlorine atoms) (for example, trifluoromethyl) Group, 2,2,2-trifluoroethyl group, or trichloromethyl group), or an aryl group having 6 to 10 carbon atoms substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) (for example, a pentafluorophenyl ^{group), R 27} is independently in each repeat ^unit, an ^{oR 28a} group or ^{OCOR 28b group, R 28a} and ^{R 28b} are hydrogen atoms A halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group having 1 to 10 carbon atoms (for example, a methyl group or an ethyl group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), a carbon number of 6 1 to 10 cycloalkyl groups (for example, cyclohexyl group), alkyl groups having 1 to 10 carbon atoms (for example, trifluoromethyl group, 2) substituted with one or more halogen atoms (for example, fluorine atom or chlorine atom) , 2,2-trifluoroethyl group, or trichloromethyl group), or an aryl group having 6 to 10 carbon atoms (eg, pentafluoro) substituted with one or more halogen atoms (eg, fluorine atom or chlorine atom). Z is an integer of 2 or more.

  The organic solvent-soluble fluororesin (A-1) having a hydroxyl group contains a repeating unit represented by the general formula (5), so that the solubility in an organic solvent is improved.

  The hydroxyl value of the organic solvent-soluble fluororesin (A-1) having a hydroxyl group is preferably 5 to 250, more preferably 10 to 200, and still more preferably 20 to 150. Here, when the hydroxyl value is less than 5, the amount of the radically polymerizable monomer (A-2) having an isocyanate group is remarkably reduced, so that the reaction mixture tends to become cloudy. On the other hand, when the hydroxyl value exceeds 250, the compatibility with the below-mentioned one-terminal radical polymerizable polysiloxane [component (B)] is deteriorated, and graft copolymerization may not proceed. Moreover, the organic solvent soluble fluororesin (A-1) having a hydroxyl group may have a free carboxylic acid group.

  The organic solvent-soluble fluororesin (A-1) having a hydroxyl group can be prepared by a known method or a commercially available product can be used. Commercially available products include vinyl ether fluoropolymers (Lumiflon LF-100, LF-200, LF-302, LF-400, LF-554, LF-600, LF-986N; manufactured by Asahi Glass Co., Ltd.), allyl ether fluoropolymers (Cefalcoat PX-40, A606X, A202B, CF-803; manufactured by Central Glass Co., Ltd.), vinyl carboxylate / acrylic ester fluoropolymer (Zaflon FC-110, FC-220, FC-250, FC-275, FC) -310, FC-575, XFC-973; manufactured by Toagosei Co., Ltd.) or vinyl ether / vinyl carboxylate fluororesin (Fluonate; manufactured by DIC Corporation).

  The organic solvent-soluble fluororesin (A-1) having a hydroxyl group can be used alone or in combination of two or more.

  The radically polymerizable monomer (A-2) having an isocyanate group is not particularly limited as long as it is a monomer containing an isocyanate group and a radically polymerizable moiety, but has an isocyanate group. It is preferable to use a radical polymer monomer having no other functional group (for example, a hydroxyl group or a polysiloxane chain).

  As the radically polymerizable monomer (A-2) having a suitable isocyanate group, for example, a radically polymerizable monomer represented by the following general formula (6) or a radical represented by the following general formula (7) It is preferable to use a polymerizable monomer.

In the formula, R ³⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or hexyl group), an aryl group having 6 to 10 carbon atoms (e.g., phenyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclohexyl ^{group, R 37} is 1 oxygen atom or a carbon atoms 10 linear or branched divalent hydrocarbon group), for example, an alkylene group having 1 to 10 carbon atoms (for example, methylene group, ethylene group, trimethylene group, or tetramethylene group), 2 to 2 carbon atoms 10 alkylidene groups (for example, isopropylidene group), arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, or xylylene group), or carbon atoms A number 3-10 cycloalkylene group (e.g., cyclohexylene).

In the formula, R ⁴¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or hexyl group), an aryl group having 6 to 10 carbon atoms (e.g., phenyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclohexyl ^{group, R 42} is 1 oxygen atom or a carbon atoms 10 linear or branched divalent hydrocarbon group), for example, an alkylene group having 1 to 10 carbon atoms (for example, methylene group, ethylene group, trimethylene group, or tetramethylene group), 2 to 2 carbon atoms 10 alkylidene groups (for example, isopropylidene group), arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, or xylylene group), or carbon atoms A number 3-10 cycloalkylene group (e.g., cyclohexylene).

  Specific examples of the radical polymerizable monomer (A-2) include methacryloyl isocyanate, 2-isocyanatoethyl methacrylate, or m- or p-isopropenyl-α, α-dimethylbenzyl isocyanate.

  In the reaction for preparing the radical polymerizable fluororesin (A) from the organic solvent soluble fluororesin (A-1) having a hydroxyl group and the radical polymerizable monomer (A-2) having an isocyanate group, a radical having an isocyanate group is used. The amount of the polymerizable monomer (A-2) is preferably 0.001 mol or more and less than 0.1 mol, more preferably 0, per 1 equivalent of the hydroxyl group of the organic solvent-soluble fluororesin (A-1) having a hydroxyl group. The reaction is carried out in an amount of 0.01 mol or more and less than 0.08 mol.

  When the radically polymerizable monomer (A-2) having an isocyanate group is less than 0.001 mol, graft copolymerization becomes difficult, the reaction mixture becomes cloudy, and it is not preferable because two layers are separated over time. Moreover, when it is 0.1 mol or more, gelation tends to occur during graft copolymerization, which is not preferable. The reaction of the organic solvent-soluble fluororesin (A-1) having a hydroxyl group and the radical polymerizable monomer (A-2) having an isocyanate group is performed at room temperature to 80 ° C. in the absence of a catalyst or in the presence of a catalyst. Can do.

  The radical polymerizable fluororesin (A) thus obtained is used in an amount of 2 to 70% by mass, preferably 4 to 60% by mass, based on the total amount of the fluorine-siloxane graft polymer used. When the radically polymerizable fluororesin (A) is less than 2% by mass relative to the total amount of the fluorine-siloxane graft polymer used, the stability during graft polymerization may decrease. Gelation may occur during polymerization.

  Next, the above-described one-end radical polymerizable polysiloxane (B) will be described. Examples of commercially available one-terminal radical polymerizable polysiloxane (B) include Silaplane FM-0711 (number average molecular weight 1,000, manufactured by Chisso Corporation), Silaplane FM-0721 (number average molecular weight 5,000, CHISSO Co., Ltd.), Silaplane FM-0725 (number average molecular weight 10,000, manufactured by Chisso Corporation), X-22-174DX (number average molecular weight 4,600, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. it can.

  In addition, the one-end radical polymerizable polysiloxane (B) is a single-end radical polymerizable polysiloxane represented by the general formula (1), or a mixture of two or more kinds, or the general formula (2). The one-end radical-polymerizable polysiloxane can be used alone or as a mixture of two or more kinds. Furthermore, one or more of the one-end-radical-polymerizable polysiloxanes represented by the general formula (1) can be used. And one or more of the one-terminal radically polymerizable polysiloxanes represented by the general formula (2) can be used in combination.

  These single terminal radically polymerizable polysiloxanes (B) are used in an amount of 4 to 40% by mass, preferably 10 to 30% by mass, based on the total amount of the fluorine-siloxane graft polymer. When the one-terminal radical polymerizable polysiloxane (B) is less than 4% by mass with respect to the total amount of the fluorine-siloxane graft polymer, the slipping property may be insufficient, and when it exceeds 40% by mass, Unreacted monomer components increase, which may lead to undesirable situations such as softening of the coating film and bleeding of unreacted monomer components.

  Next, the radical polymerizable monomer (C) that does not react with the radical polymerizable fluororesin (A) other than the polymerization reaction by a double bond under the radical polymerization reaction condition will be described.

  The radical polymerizable monomer (C) that does not react with the radical polymerizable fluororesin (A) under a radical polymerization reaction condition other than the polymerization reaction by a double bond is, for example, styrene, p-methylstyrene, p-chloro. Styrenic monomers such as methylstyrene or vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (methacrylate, i -Butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (Meta) Acrelay , (Meth) acrylate monomers having a hydrocarbon group such as adamantyl (meth) acrylate, phenyl (meth) acrylate, or benzyl (meth) acrylate; fluorine atoms of these (meth) acrylate monomers (Meth) acrylate monomers substituted with atoms, chlorine atoms, bromine atoms, etc .; vinyl esters such as vinyl acetate, vinyl benzoate, or vinyl ester of branched monocarboxylic acid (Beova; manufactured by Shell Chemical Co., Ltd.) Monomers; acrylonitrile monomers such as acrylonitrile or methacrylonitrile; vinyl ether monomers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; (meth) acrylamide, dimethyl ( (Meth) acrylamide, or Acrylamide monomers such as acetone acrylamide; vinylpyridine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, 4- (N , N-dimethylamino) styrene, or a basic nitrogen-containing vinyl compound monomer such as N- {2- (meth) acryloyloxyethyl} piperidine; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meta ) Epoxy group-containing vinyl compound monomers such as acrylate or 3,4-epoxyvinylcyclohexane; (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid 2- (Meth) acryloyloxyethanesulfone Acid or acidic vinyl compound monomers such as mono {2- (meth) acryloyloxyethyl} acid phosphate; p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or these ε-caprolactone adducts, hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, α, β-ethyl such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid Adduct of renically unsaturated carboxylic acid and ε-caprolactone, or α, β-ethylenically unsaturated carboxylic acid and butyl glycidyl ether, phenyl glycidyl ether, branched monocarboxylic acid glycidyl ester (Cardura E, Shell Chemistry) Hydroxyl group-containing vinyl compound monomers such as adducts with epoxy compounds such as those manufactured by KK; Silane compounds such as vinyltrimethoxysilane, γ-methacryloxyethyltrimethoxysilane, and γ-methacryloxyethylmethyldimethoxysilane Olefin monomers such as ethylene or propylene; halogenated olefin monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene, or chlorotrifluoroethylene; Other maleimide, vinyl sulfone, etc. Can be mentioned.

  The radical polymerizable monomer (C) that does not react other than the polymerization reaction with the radical polymerizable fluororesin (A) under the radical polymerization reaction conditions may be used alone or in combination of two or more. From the viewpoint of copolymerization, a (meth) acrylate monomer is preferably used.

  The radically polymerizable monomer (C) that does not react with the radically polymerizable fluororesin (A) except for a polymerization reaction by a double bond under the radical polymerization reaction conditions is 15 to 94% by mass with respect to the total amount of the fluorine-siloxane graft polymer. Preferably, it is used in the range of 30 to 70% by mass. If it is less than 15% by mass, it is difficult to adjust the glass transition point of the copolymer, and if it exceeds 94% by mass, the slipperiness becomes insufficient.

  Sum of radically polymerizable polysiloxane (B) having one terminal and radically polymerizable monomer (C) that does not react other than the polymerization reaction by a double bond with the radically polymerizable fluororesin (A) under radical polymerization reaction conditions The ratio of the mass of the radical polymerizable fluororesin (A) to the mass [that is, A / (B + C); hereinafter may be referred to as “fluororesin / acrylic ratio”] is in the range of 2/1 to 1/50. Preferably there is. Fluorine resin / acrylic ratio: When A / (B + C) is less than 2/1, gloss is lowered. Moreover, when the fluororesin / acryl ratio exceeds 1/50, the stability of the blended polymer may be lowered.

  Radicals that do not react other than the polymerization reaction with the radically polymerizable fluororesin (A) and a double bond under the radical polymerization reaction conditions under the radically polymerizable fluororesin (A), the one-end radically polymerizable polysiloxane (B) In order to prepare a fluorine-siloxane graft polymer using the polymerizable monomer (C), a known polymerization method can be used, and in particular, a solution radical polymerization method or a non-aqueous dispersion radical polymerization method is most used. Simple and preferred.

  Examples of the fluorine-siloxane graft polymer include (A) an organic solvent-soluble fluororesin having a radical polymerizable unsaturated bond moiety via a urethane bond, (B) the general formula (1) and / or the general formula (2). ), And (D) one-end radical polymerizable alkoxy polyalkylene glycol represented by the following general formula (8)), and (E): components (A), (B), Radical polymerizable monomers other than (D) can also be produced from graft copolymerization obtained by random copolymerization.

In the formula, R ¹³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. R ¹⁴ is a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group. R ¹⁵ is a hydrocarbon group which may be substituted with a linear or branched halogen atom having 1 to 10 carbon atoms, preferably an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group). ), A phenyl group, or an alkyl-substituted phenyl group. l is an integer greater than or equal to 1, Preferably it is an integer of 2-100. M is an arbitrary integer, preferably 0 to 10, more preferably 0.

  The radical-polymerizable fluororesin (A) and the one-end radical-polymerizable polysiloxane (B) represented by the general formula (1) or the general formula (2) are as described above. The polyalkylene glycol (D) will be described.

  As the one-end radical polymerizable alkoxy polyalkylene glycol (D), a known one can be used. Specifically, Blemmer PME-100, PME-200, PME-400, PME-4000, 50POEP-800B (manufactured by NOF Corporation), LIGHT ESTER MC, MTG, 130MA, 041MA (manufactured by Kyoeisha Chemical Co., Ltd.), Light acrylate BO-A, EC-A, MTG-A, 130A (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

  Moreover, the one terminal radically polymerizable alkoxy polyalkylene glycol (D) can be used individually or in mixture of 2 or more types. One-terminal radically polymerizable alkoxy polyalkylene glycol (D) is used in an amount of 1 to 25% by mass, preferably 1 to 15% by mass, based on the total amount of the fluorine-siloxane graft polymer.

  Here, if the one-terminal radical polymerizable alkoxy polyalkylene glycol (D) is less than 1% by mass or exceeds 25% by mass with respect to the total amount of the fluorine-siloxane graft polymer, the stain resistance may be insufficient.

  Next, the radical polymerizable monomer (E) other than the components (A), (B), and (D) will be described. Examples of the radical polymerizable monomer (E) other than the components (A), (B), and (D) include styrene-based monomers such as styrene, p-methylstyrene, p-chloromethylstyrene, and vinyltoluene. Mer: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate , Phenyl (meth) acrylate Or (meth) acrylate monomers having a hydrocarbon group such as benzyl (meth) acrylate; the hydrogen atoms of these (meth) acrylate monomers are replaced with fluorine atoms, chlorine atoms, bromine atoms, etc. (Meth) acrylate monomers; vinyl ester monomers such as vinyl acetate, vinyl benzoate, or vinyl ester of branched monocarboxylic acid (Beova: Shell Chemical Co., Ltd.); acrylonitrile, or methacrylonitrile Acrylonitrile monomers such as; vinyl ether monomers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, or diacetone acrylamide Monomer: vinyl pyri , N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, 4- (N, N-dimethylamino) styrene, or N- {2- (meth) acryloyloxyethyl} piperidine and other basic nitrogen-containing vinyl compound monomers; glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or 3,4-epoxyvinylcyclohexane Epoxy group-containing vinyl compound monomers such as (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid Or mono {2- (meth) acryloyloxyethyl} acido Acid vinyl compound monomers such as sulfate; p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or ε-caprolactone adduct thereof, (meth) acrylic acid, crotonic acid, Addition product of α, β-ethylenically unsaturated carboxylic acid and ε-caprolactone such as maleic acid, fumaric acid, itaconic acid or citraconic acid, hydroxyalkyl ester of the above α, β-ethylenically unsaturated carboxylic acid Kind, Is a hydroxyl group-containing vinyl such as an adduct of an α, β-ethylenically unsaturated carboxylic acid and an epoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, or a branched carboxylic acid glycidyl ester (Cardura E; manufactured by Shell Chemical Co., Ltd.) Compound monomers; silane compound monomers such as vinyltrimethoxysilane, γ-methacryloxyethyltrimethoxysilane, γ-methacryloxyethylmethyldimethoxysilane; olefin monomers such as ethylene and propylene; vinyl chloride And halogenated olefin monomers such as vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene, or chlorotrifluoroethylene; and other maleimides and vinyl sulfones.

  These monomers may be used alone or in admixture of two or more, and a (meth) acrylate type is preferably used mainly from the viewpoint of copolymerization.

  The radically polymerizable monomer (E) other than the components (A), (B), and (D) is 28 to 92% by mass, preferably 30 to 70% by mass, based on the total amount of the fluorine-siloxane graft polymer used. Used in a range.

  Here, when the radical polymerizable monomer (E) is less than 28% by mass with respect to the total amount of the fluorine-siloxane graft polymer used, it is difficult to adjust the glass transition point of the copolymer, and when it exceeds 92% by mass, The slipperiness becomes insufficient.

  One-end radical polymerizable polysiloxane (B), the above-mentioned one-end alkoxy polyalkylene glycol (D), radical polymerizable monomers (E) other than components (A), (B), and (D) The ratio of the used mass of the radically polymerizable fluororesin (A) to the total used mass (ie, A / (B + D + E); hereinafter sometimes referred to as “fluororesin / acryl ratio”) is 2/1 to 1 / A range of 50 is preferred. When the fluororesin / acryl ratio is less than 2/1, the gloss may decrease. Moreover, when the fluororesin / acryl ratio exceeds 1/50, the stability may be lowered.

  Other than the radically polymerizable fluororesin (A), the one-end radical polymerizable polysiloxane (B), the one-end alkoxypolyalkylene glycol (D), and the components (A), (B), and (D) In order to prepare a copolymer using the radically polymerizable monomer (E), any known polymerization method can be used. Among them, a solution radical polymerization method or a non-aqueous dispersion radical polymerization method can be used. Is the most convenient and particularly preferred.

  The fluorine-siloxane graft polymer is composed of (A) an organic solvent-soluble fluororesin having a radical polymerizable unsaturated bond moiety via a urethane bond, (B) the above general formula (1): and / or the above general formula (2 And (F) a radically polymerizable monomer having one radical polymerizable double bond and at least one fluoroalkyl group in the molecule, and (G) a component (A), (B), and can be produced from a graft copolymer obtained by copolymerizing a radical polymerizable monomer other than (F).

  The radical-polymerizable fluororesin (A) and the one-end radical-polymerizable polysiloxane (B) represented by the general formula (1) or the general formula (2) are as described above. The radical polymerizable monomer (F) having a radical polymerizable double bond and at least one fluoroalkyl group will be described.

  The radical polymerizable monomer (F) having one radical polymerizable double bond and at least one fluoroalkyl group in the molecule is, for example, perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, Perfluorodecylethylene, 1-methoxy- (perfluoro-2-methyl-1-propene), 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl ( (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl 2-hydroxypropyl (meth) acrylate, 2- (par Luooctyl) ethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 3-perfluorodecyl-2-hydroxypropyl (meth) acrylate 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-3-methylhexyl) ethyl ( And (meth) acrylate, 2- (perfluoro-3-methyloctyl) ethyl (meth) acrylate, 2- (perfluoro-3-methyldecyl) ethyl (meth) acrylate, and the like. Commercially available products include acrylic esters 3FE, 4FE, 5FE, 8FE, 17FE (Mitsubishi Rayon Co., Ltd.), biscoat 3F, 3FM, 4F, 8F, 8FM (Osaka Organic Chemical Co., Ltd.), light esters M-3F, M- 4F, M-6F, FM-108, Light acrylate FA-108 (manufactured by Kyoeisha Chemical Co., Ltd.), M-1110, M-1210, M-1420, M-1620, M-1633, M-1820, M-1833, M-2020, M-3420, M-3433, M-3620, M-3633, M-3820, M-3833, M-4020, M-5210, M-5410, M-5610, M-5810, M- 7210, M-7310, R-1110, R-1210, R-1420, R-1433, R-1620, R-1633, R-1820, R-1 33, R-2020, R-3420, R-3433, R-3620, R-3633, R-3820, R-3833, R-4020, R-5210, R-5410, R-5610, R-5810, R-7210, R-7310 (manufactured by Daikin Industries), HFIP-M, HFIP-A, TFOL-M, TFOL-A, PFIP-A, HpIP-AE, HFIP-I (manufactured by Central Glass Co., Ltd.) be able to.

  The radical polymerizable monomer (F) having one radical polymerizable double bond and at least one fluoroalkyl group in the molecule may be used alone or in combination of two or more.

  The radical polymerizable monomer (F) having one radical polymerizable double bond and at least one fluoroalkyl group in the molecule is 1 to 50 mass based on the total amount of the fluorine-siloxane graft polymer used. %, Preferably in the range of 2-40% by weight. If the amount is less than 1% by mass, the stability may be insufficient. If the amount exceeds 50% by mass, the price of the copolymer increases, which is not practical.

  The radical polymerizable monomer (G) other than the components (A), (B), and (F) will be described. The radical polymerizable monomer (G) other than the components (A), (B), and (F) is, for example, a styrene-based monomer such as styrene, p-methylstyrene, p-chloromethylstyrene, or vinyltoluene. Body; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Phenyl (meth) acrylate, Is a (meth) acrylate monomer having a hydrocarbon group such as benzyl (meth) acrylate; vinyl ester such as vinyl acetate, vinyl benzoate, or vinyl ester of branched monocarboxylic acid (Beova: manufactured by Shell Chemical Co., Ltd.) Monomers; acrylonitrile monomers such as acrylonitrile or methacrylonitrile; vinyl ether monomers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; (meth) acrylamide, dimethyl ( Acrylamide monomers such as (meth) acrylamide or diacetone acrylamide; vinylpyridine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) Acry Basic nitrogen-containing vinyl compound monomers such as amide, 4- (N, N-dimethylamino) styrene, or N- {2- (meth) acryloyloxyethyl} piperidine; glycidyl (meth) acrylate, 3,4 -Epoxy cyclohexyl methyl (meth) acrylate, or epoxy group-containing vinyl compound monomers such as 3,4-epoxyvinylcyclohexane; (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, acidic vinyl compound monomers such as p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, or mono {2- (meth) acryloyloxyethyl} acid phosphate; p-hydroxymethylstyrene, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate Or an α, β-ethylenically unsaturated carboxylic acid such as ε-caprolactone adduct, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, or citraconic acid and ε-caprolactone. Adduct, hydroxyalkyl esters of the above α, β-ethylenically unsaturated carboxylic acid, or α, β-ethylenically unsaturated carboxylic acid and butyl glycidyl ether, phenyl glycidyl ether, branched carboxylic acid glycidyl ester ( Mosquito Hydroxyl-containing vinyl compound monomers such as adducts with epoxy compounds such as Jurass E; manufactured by Shell Chemical Co .; vinyltrimethoxysilane, γ-methacryloxyethyltrimethoxysilane, γ-methacryloxyethylmethyldimethoxysilane Silane compound monomers such as ethylene; olefin monomers such as propylene; halogenated olefin monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene, or chlorotrifluoroethylene Other examples include maleimide and vinyl sulfone.

  The radically polymerizable monomers (G) other than the components (A), (B), and (F) may be used alone or in admixture of two or more, mainly from the viewpoints of copolymerizability and yellowing resistance. To (meth) acrylates are preferably used.

  The said component (G) is 4-93 mass% with respect to the fluorine-siloxane graft polymer whole quantity to be used, Preferably it is used in 20-80 mass%. If it is less than 4% by mass, it is difficult to adjust the glass transition point of the copolymer, and if it exceeds 93% by mass, the stain resistance is insufficient.

  Ratio of used mass of component (A) to total used mass of component (B), component (F), and component (G) (ie, A / (B + F + G); hereinafter referred to as “fluororesin / acrylic ratio”) Is preferably in the range of 2/1 to 1/50. When the fluororesin / acryl ratio is less than 2/1, the gloss may decrease. Further, when the fluororesin / acryl ratio exceeds 1/50, the water repellency and oil repellency may be lowered.

  In order to prepare the fluorine-siloxane graft polymer using the components (A), (B), (F), and (G), a known polymerization method can be used, among which a solution radical polymerization method or a non-aqueous dispersion radical is used. The polymerization method is the simplest and is particularly recommended.

  Examples of the solvent used for the above-described polymerization include aromatic hydrocarbon compounds such as toluene, xylene, or a mixture of aromatic hydrocarbons (Solvesso 100, manufactured by Esso Petroleum Corporation); n-hexane, cyclohexane, octane, Aliphatic and alicyclic hydrocarbon compounds such as mineral spirits or kerosene; ester compounds such as ethyl acetate, n-butyl acetate, i-butyl acetate, or butyl cellosolve acetate; methanol, ethanol, n-propanol, i- Examples include alcohol compounds such as propanol, n-butanol, i-butanol, ethylene glycol, propylene glycol, ethyl cellosolve, and butyl cellosolve, and these solvents can be used alone or in combination of two or more. .

  The synthesis can be carried out in a conventional manner using various radical polymerization initiators such as azo compounds or peroxide radical polymerization initiators. The polymerization time is not particularly limited, but a range of 1 to 48 hours is usually selected. The polymerization temperature is usually 30 to 120 ° C, preferably 60 to 100 ° C. The polymerization can also be carried out by adding a known chain transfer agent such as butyl mercaptan, dodecyl mercaptan, or α-methylstyrene dimer, if necessary. The molecular weight of the graft polymer is not particularly limited, but the mass average molecular weight is preferably in the range of about 5000 to 2000000 (more preferably about 10 to 1000000) by GPC (gel permeation chromatography) in terms of polystyrene. It is. Here, if the weight average molecular weight of the graft polymer is less than 5,000, the film-forming property may be deteriorated, and if it exceeds 2,000,000, there is a risk of gelation during polymerization.

  Moreover, as a commercial item of a fluorine-siloxane graft polymer, Fuji Chemical Industry Co., Ltd. ZX-022H, ZX-007C, ZX-049, ZX-047-D etc. can be mentioned.

  The fluorine-siloxane graft polymer is preferably contained in an amount of 0.01 to 1% by weight, more preferably 0.1 to 0.8% by weight, based on the polymerizable liquid crystal compound. If the amount is less than 0.01% by mass, the effect of eliminating coating unevenness does not appear and alignment defects increase, and if it exceeds 1% by mass, roll transferability deteriorates.

<Liquid crystal layer>
The liquid crystal layer 14 according to the embodiment of the present invention contains a polymerizable liquid crystal compound in addition to the fluorine-siloxane graft polymer. It does not specifically limit as a polymerizable liquid crystal compound, The conventionally well-known polymerizable liquid crystal compound etc. which are contained in a liquid crystal layer are mentioned.

  Specifically, for example, those having a rod-like mesogen group or a disk-like mesogen group in the molecule can be mentioned.

<Bar-shaped liquid crystal compound>
The polymerizable liquid crystal compound having a rod-like mesogenic group in the molecule is inclined 5 to 50 ° with respect to the thickness direction of the liquid crystal layer, and is fixed in an inclined state. That is, the liquid crystal layer 14 contains, for example, a polymerizable liquid crystal compound having a rod-shaped mesogenic group in the molecule, and the mesogenic group tilts the major axis direction of the liquid crystal layer by 5 to 50 °. After the alignment, the orientation is fixed.

  The polymerizable liquid crystal compound having a rod-shaped mesogen group in the molecule may be a polymerizable liquid crystal containing the rod-shaped mesogen group and a polymerizable functional group, and at least any of the main chain and the side chain. On the other hand, it may be a polymer liquid crystal containing the rod-shaped mesogen group or a polymer liquid crystal containing the rod-shaped mesogen group and a polymerizable functional group. By containing the polymerizable functional group, at the time of immobilization, for example, after cooling to less than the liquid crystal transition temperature, it is possible to further immobilize the orientation by polymerizing while cooling, This is preferable because it can be cured as an optically anisotropic layer. In view of the orientation of the mesogenic group and the moldability of the optically anisotropic layer by polymerization, a polymerizable liquid crystal is preferable.

  The mesogenic group is not particularly limited, but is preferably a rod-shaped mesogenic group that can be tilted. Specific examples include functional groups containing an ester group, a cyano group, an alkyl group, and an aryl group. Moreover, as said mesogenic group, 1 type of each said mesogenic group may be contained, and it may contain combining 2 or more types.

  The polymerizable functional group is not particularly limited, and it is preferable that polymerization can be performed while maintaining the orientation after the orientation. Specifically, for example, the polymerization may be initiated by heat, or the polymerization may be initiated by irradiation with active rays such as ultraviolet rays. That is, in the case of the polymerizable liquid crystal, it may be thermosetting or actinic ray curable. In addition, when the polymerizable liquid crystal compound is polymerized at a temperature lower than the liquid crystal transition temperature, it is preferable that the polymerizable liquid crystal compound is not heated so much that an actinic ray curable one is more preferable.

  Specific examples of the polymerizable functional group include a vinyl group such as an acryloyl group, a methacryloyl group and a vinyl ether, an epoxy group, and an oxetanyl group. Moreover, the said polymerizable functional group may be used independently and may be used in combination of 2 or more type. The polymerizable liquid crystal may contain one polymerizable functional group in the molecule, or may contain two or more.

  Specific examples of the polymerizable functional group include an acryloyl group, a vinyl group such as methacryloyl group and vinyl ether, and an epoxy group. Moreover, the said polymerizable functional group may be used independently and may be used in combination of 2 or more type. The polymerizable liquid crystal may contain one polymerizable functional group in the molecule, or may contain two or more.

  In the present invention, the polymerizable liquid crystal compound is particularly preferably a compound represented by the following general formula (L).

In the formula, m represents 0 or 1, W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹ and Y ² each independently represent —COO. -Or -OCO-, and r and s each independently represent an integer of 2 to 18, the 1,4-phenylene group present in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, One or more alkanoyl groups, cyano groups, or halogen atoms may be substituted.

  Although the specific example of a compound represented by general formula (L) below is shown, it is not limited to this.

(Wherein j and k each independently represents an integer of 2 to 18)
Specific examples of the polymerizable liquid crystal compound that are commercially available include UCL018 manufactured by DIC Corporation, and Palio Color LC242 manufactured by BASF Corporation.

<Discotic liquid crystal compound>
Examples of discotic liquid crystalline compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), and azacrown and phenylacetylene macrocycles. Further, as a discotic liquid crystal compound, those having a structure in which these are generally used as a mother nucleus of a molecular center, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. Contains and exhibits liquid crystallinity. However, the molecule itself is not limited to these as long as it has negative uniaxiality and can give a certain orientation. Further, in the present invention, the optically anisotropic layer formed from the discotic liquid crystal compound does not have to be the final compound, for example, a low molecular weight discotic liquid crystal compound is formed by heat, light, or the like. It includes a group that has a reactive group and is consequently polymerized or cross-linked by reaction with heat, light or the like, resulting in a high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic liquid crystal compound are described in JP-A-8-50206. The polymerization of discotic liquid crystal compounds is described in JP-A-8-27284.

  In order to fix the discotic liquid crystal compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the core of the discotic structure of the discotic liquid crystal compound. However, when the polymerizable group is directly connected to the discotic structure core, it becomes difficult to maintain the alignment state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Therefore, the discotic liquid crystal compound having a polymerizable group is preferably a compound represented by the following general formula (d).

Formula (d) D (-LP) n
In the formula, D is a core of a discotic structure, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12. The discotic liquid crystalline compound is also described in WO01 / 88574A1, page 58, line 6 to page 65, line 8.

  Examples of the compound that can be used with the discotic liquid crystalline compound include a plasticizer, a surfactant, a polymerizable monomer, and a polymer.

  Plasticizers, surfactants and polymerizable monomers that can be used with the discotic liquid crystalline compound are compatible with the discotic liquid crystalline compound and can change the tilt angle of the discotic liquid crystalline compound or can be aligned. Any compound can be used as long as it does not inhibit the above. Among these, polymerizable monomers (eg, compounds having a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group) are preferable. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline compound. Moreover, the adhesion between the alignment film and the optically anisotropic layer can be enhanced by using a mixture of monomers having 4 or more reactive functional groups.

  As the polymer used together with the discotic liquid crystalline compound, any polymer can be used as long as it has compatibility with the discotic liquid crystalline compound and can change the tilt angle of the discotic liquid crystalline compound. A cellulose ester can be mentioned as an example of a polymer. Preferred examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order not to inhibit the orientation of the discotic liquid crystalline compound, the amount of the polymer added is generally in the range of 0.1 to 10% by mass, and in the range of 0.1 to 8% by mass with respect to the discotic liquid crystalline compound. It is more preferable that it is in the range of 0.1 to 5% by mass.

  The liquid crystal layer is generally formed by applying a solution in which a discotic liquid crystal compound and other compounds are dissolved in a solvent, applying the solution onto an alignment film, drying, and then heating to a discotic nematic phase formation temperature, followed by an alignment state (discotic nematic phase). ) Is maintained and cooled. Alternatively, the liquid crystal layer is formed by applying a solution obtained by dissolving a discotic liquid crystalline compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature, followed by polymerization (by irradiation with UV light, etc.) and further cooling. At this time, the temperature for forming the nematic phase can be regarded as the liquid crystal alignment temperature (Tlc) in the present invention, and it is preferable that Td (1.0)> Tm> Tg (film)> Tlc is satisfied. This is because the liquid crystal alignment temperature for forming the desired optical anisotropy in the optical anisotropic layer satisfies the above relationship at a temperature lower than the glass transition temperature (Tg (film)) of the support, Can be aligned at the liquid crystal alignment temperature, and this is preferable from the viewpoint of reducing variations in the retardation value of the liquid crystal layer.

  In addition to the polymerizable liquid crystal compound, the liquid crystal layer forming composition used for forming the liquid crystal layer 14 according to the embodiment of the present invention may contain a photopolymerization initiator. In the case of polymerization by irradiation with an electron beam, a photopolymerization initiator is not required. However, in the case of polymerization generally used, for example, polymerization by ultraviolet (UV) irradiation, the polymerization is promoted. Therefore, it is preferable to contain a photopolymerization initiator. By doing so, polymerization temperature can be made low and the said fixation can be performed suitably.

  Although it does not specifically limit as said photoinitiator, Specifically, for example, benzyl (bibenzoyl), benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, benzoyl methyl benzoate, 4-benzoyl-4 ' -Methyldiphenyl sulfide, benzylmethyl ketal, dimethylaminomethylbenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3'-dimethyl-4-methoxybenzophenone, methylobenzoyl Formate, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -ON 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 1- And chloro-4-propoxythioxanthone. Moreover, these may be used independently and may be used in combination of 2 or more type.

  As content of the said photoinitiator, it is preferable to contain 0.1-30 mass% with respect to the said polymeric liquid crystal compound, It is preferable that it is 0.1-20 mass%, 0.1-10 mass % Is more preferable, and 0.5 to 5% by mass is even more preferable. If the content of the photopolymerization initiator is too small, the effect of the photopolymerization initiator tends not to be exhibited.If the content is too large, the polymerizability of the polymerizable liquid crystal compound is lowered and the molecular weight is lowered. There exists a tendency for abrasion resistance etc. to fall.

  Further, the liquid crystal layer forming composition may contain a sensitizer as long as the object of the present invention is not impaired. Although it does not specifically limit as said sensitizer, Specifically, Nippon Kayaku Co., Ltd. Kayacure DETX etc. are mentioned, for example.

  Moreover, as a method of forming the liquid crystal layer 14, a method of preparing a liquid liquid crystal layer forming composition containing a solvent and coating the liquid crystal layer forming composition on the liquid crystal alignment layer is preferable. Thereby, it is possible to more effectively utilize the effect of suppressing the occurrence of coating unevenness due to the fluorine-siloxane graft polymer contained in the liquid crystal layer.

  The solvent for the liquid crystal layer forming composition is not particularly limited as long as the polymerizable liquid crystal compound can be dissolved. Moreover, it is preferable that it is a solvent which does not change the property etc. of a transparent film base material. Specifically, for example, hydrocarbons such as benzene, toluene, xylene, n-butylbenzene, diethylbenzene, and tetralin; ethers such as methoxybenzene, 1,2-dimethoxybenzene, and diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, and 2,4-pentanedione; esters such as ethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; 2 Amido solvents such as pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide; chloroform, dichloromethane Halogen solvents such as carbon tetrachloride, dichloroethane, tetrachloroethane, tritrichloroethylene, tetrachloroethylene, chlorobenzene, and orthodichlorobenzene; t-butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene Examples include alcohols such as glycol monomethyl ether, ethyl cellosolve, and butyl cellosolve; phenols such as phenol and parachlorophenol. These may be used alone or in combination of two or more. By using a combination of two or more solvents, it is possible to enhance the solubility of liquid crystallized foods and the like, and to suppress the modification of the film substrate.

  In addition, among the solvents, for example, hydrocarbon solvents, glycol monoether acetate solvents and the like are preferable as the solvent used alone. Moreover, as a preferable combination of the solvent used in combination of 2 or more types, a combination of ethers or ketones and glycols and the like can be mentioned.

  Moreover, since the solid content concentration of the composition for forming a liquid crystal layer varies depending on the solubility of the polymerizable liquid crystal compound or the like, the film thickness of the liquid crystal layer to be produced, etc., it cannot be generally specified, but usually 1 to 60 It is preferable that it is mass%, and it is more preferable that it is 3-40 mass%.

  Moreover, you may make the said composition for liquid-crystal layer formation contain the following additive in the range which does not impair the objective of this invention other than said each composition.

  As the additive, for example, a polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol and a monobasic acid or polybasic acid; Polyurethane (meth) acrylate obtained by reacting a group and a compound having two isocyanate groups with each other and then reacting the reaction product with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin , Epoxy resins such as novolac type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, ( Meta) Acry A photopolymerizable compound such as epoxy (meth) acrylate obtained by reacting an acid, a photopolymerizable liquid crystal compound having an acrylic group or a methacryl group, an onium salt described in JP-A-2007-45993, and a fluorinated compound An acrylate polymer etc. are mentioned. Addition of the additive improves the curability of the liquid crystal layer forming composition, increases the mechanical strength of the resulting liquid crystal layer, and improves its stability.

  Further, the content of the additive is selected within a range that does not impair the object of the present invention, and is generally preferably 40% by mass or less of the composition for forming a liquid crystal layer, and 20% by mass or less. It is preferable that

  Further, the liquid crystal layer forming composition containing a solvent may contain a surfactant other than the fluorine-siloxane graft polymer according to the present invention. Specifically, for example, cationic surfactants such as imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives; polyoxyethylene-polyoxypropylene condensates, primary or secondary alcohol ethoxylates , Alkylphenol ethoxylates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonate formalin condensates, etc. Surfactants; amphoteric surfactants such as laurylamidopropylbetaine and laurylaminoacetic acid betaine; nonionic surfactants such as polyethylene glycol fatty acid esters and polyoxyethylene alkylamine And the like. What is necessary is just to select suitably content of surfactant in the range which does not impair the effect of the said fluorine-siloxane graft polymer which concerns on this invention.

  The thickness of the liquid crystal layer 14 is preferably 0.1 to 10 μm, and more preferably 0.2 to 5 μm.

  The liquid crystal layer 14 preferably has an in-plane retardation Ro determined by the above formula (1) of 0 to 10 nm. Moreover, it is preferable that the thickness direction retardation Rt calculated | required by the said Formula (2) is -500--100nm.

<Liquid crystal alignment layer>
As shown in FIG. 1, the liquid crystal alignment layer 13 that enhances the alignment of the polymerizable liquid crystal compound is formed on the film base 11 or on the second intermediate layer 16 when the second intermediate layer 16 is provided. It is formed. The liquid crystal alignment layer 13 includes, for example, a resin such as an actinic radiation curable resin and may be subjected to a rubbing treatment, or includes a resin such as an actinic radiation curable resin and the alignment agent. Also good.

  The actinic radiation curable resin may be any resin that can be cured by actinic radiation such as ultraviolet rays. Specifically, for example, vinyl group, allyl group, acryloyl group, methacryloyl group, isopropenyl group, epoxy group, and oxetanyl are used. And those having a polymerizable functional group such as a group. In particular, the liquid crystal alignment layer according to the present invention preferably contains an acrylic polymer.

  Moreover, as said actinic radiation curable resin, what has two or more said polymerizable functional groups and becomes a crosslinked structure or network structure by irradiating actinic radiation is preferable. The active ray is preferably ultraviolet rays from the viewpoint of workability. That is, the actinic radiation curable resin is preferably an ultraviolet curable resin.

  In addition, the liquid crystal alignment layer 13 contains not only the actinic radiation curable resin but also a cellulose ester resin, which indicates adhesion between the upper layer of the liquid crystal alignment layer 13 and the lower layer of the liquid crystal alignment layer 13, specifically In particular, the adhesiveness with the liquid crystal layer 14 and the adhesiveness with the film substrate 11 can be enhanced, and in particular, the adhesiveness under high temperature and high humidity can be enhanced. The content is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the actinic radiation curable resin. Although it does not specifically limit as said cellulose-ester resin, For example, the cellulose-ester resin etc. which comprise a transparent film base material are mentioned. Specifically, what is illustrated below is mentioned as a cellulose-ester resin of a transparent film base material, for example.

  The liquid crystal alignment layer 13 preferably has a thickness of 1.2 to 3 μm. If it is too thin, there is a tendency that the effect of promoting the alignment of the polymerizable liquid crystal compound in the liquid crystal layer 14 and the effect of improving the adhesiveness as described above are hardly exhibited. Furthermore, the effect of preventing the components of the film substrate 11 from eluting into the liquid crystal layer 14 also tends to be reduced. On the other hand, if it is too thick, the resulting optically anisotropic film becomes unnecessarily thick and tends to hinder the thinning of the optically anisotropic film.

<Film base>
The film substrate 11 is not particularly limited as long as it is transparent and can be used as a substrate for an optically anisotropic film. Here, being transparent means that the transmittance of visible light is 60% or more, preferably 80% or more, and more preferably 90% or more. Specific examples of the film substrate 11 include a resin film having high transparency.

  Specific examples of the resin for the resin film include polyester resins such as cellulose ester resin, polyester resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyethylene terephthalate resin, and polyethylene naphthalate resin. , Polyethylene resin, polypropylene resin, cellophane, cellulose diacetate resin, cellulose acetate butyrate resin, cellulose acetate propionate resin, polyvinylidene chloride resin, polyvinyl alcohol resin, ethylene vinyl alcohol resin, syndiotactic polystyrene resin, polycarbonate resin, Norbornene resin, polymethylpentene resin, polyether ketone resin, polyether ketone imide resin, polyamide resin , Fluorine resin, nylon resin, cycloolefin resin, polymethyl methacrylate resin and acrylic resins. Among these, a cellulose ester film containing a cellulose ester resin is preferable.

<Cellulose ester resin>
The cellulose ester resin is preferably a cellulose acetate resin, a cellulose propionate resin, a cellulose butyrate resin, a cellulose acetate butyrate resin, or a cellulose acetate propionate resin. Among them, a cellulose acetate resin or a cellulose acetate propionate resin is preferably used. .

  As one preferred embodiment, a cellulose acetate propionate resin, which is a mixed fatty acid ester of cellulose in which X and Y are in the following ranges, where X is the substitution degree of the acetyl group and Y is the substitution degree of the propionyl group, Preferably used.

Formula (I) 2.0 ≦ X + Y ≦ 2.6
Formula (II) 0.1 ≦ Y ≦ 1.2
Furthermore, a cellulose acetate propionate (total acyl group substitution degree = X + Y) resin of 2.4 ≦ X + Y ≦ 2.6 and 1.4 ≦ X ≦ 2.3 is preferable. Among them, a cellulose acetate propionate resin (total acyl group substitution degree = X + Y) of 2.4 ≦ X + Y ≦ 2.6, 1.7 ≦ X ≦ 2.3, and 0.1 ≦ Y ≦ 0.9 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These cellulose ester resins can be synthesized by a known method.

  Moreover, as a cellulose acetate resin which is another preferable embodiment in this invention, it is preferable that it is a diacetyl cellulose whose acetyl group substitution degree is 2.1-2.6. The degree of acetyl group substitution is determined by the method prescribed in ASTM-D817-96.

  The cellulose acetate used in the present invention can be produced by a conventional method such as a sulfuric acid catalyst method, an acetic acid method, or a methylene chloride method, and the raw material is preferably wood pulp.

  Cellulose acetate is usually pulp (cellulose) activated with acetic acid or the like (activation step), and then triacetate is prepared with acetic anhydride using a sulfuric acid catalyst (acetylation step). It can be produced by adjusting the degree of acetylation by aging (saponification / aging process).

  In this method, the activation step can be performed by treating pulp (cellulose) by, for example, spraying acetic acid or hydrous acetic acid, or immersing in acetic acid or hydrous acetic acid. Cellulose) It is 10-100 mass parts with respect to 100 mass parts, Preferably it is 20-80 mass parts, More preferably, it is about 30-60 mass parts.

  The usage-amount of acetic anhydride in an acetylation process (acetylation process) can be selected in the range used as the said acetylation degree, for example, 230-300 mass parts with respect to 100 mass parts of pulp (cellulose), Preferably it is 240-290. The amount is about mass parts, more preferably about 250 to 280 parts by mass.

  In the acetylation step, acetic acid is usually used as a solvent. The usage-amount of acetic acid is 200-700 mass parts with respect to 100 mass parts of pulp (cellulose), for example, Preferably it is 300-600 mass parts, More preferably, it is about 350-500 mass parts.

  As the acetylation or aging catalyst, sulfuric acid is usually used. The usage-amount of a sulfuric acid is 1-15 mass parts normally with respect to 100 mass parts of cellulose, Preferably it is 5-15 mass parts, Especially about 5-10 mass parts. Saponification and aging can be performed at a temperature of about 50 to 70 ° C., for example.

  In order to improve the optical properties of cellulose acetate, the cellulose acetate produced may be treated with an oxidizing agent at an appropriate stage in the cellulose acetate production process, for example, after completion of acetylation, saponification or aging.

  Examples of the oxidizing agent include hydrogen peroxide; peracids such as performic acid, peracetic acid, and perbenzoic acid; and organic peroxides such as diacetyl peroxide. The oxidizing agent can be used alone or in combination of two or more.

  Preferred oxidizing agents include oxidizing agents that are easy to remove from cellulose acetate and have low persistence, such as hydrogen peroxide, performic acid, and peracetic acid, with hydrogen peroxide and peracetic acid being particularly preferred. The amount of the oxidizing agent used can be selected according to the level of optical properties desired, for example, 0.01 to 5 parts by mass, preferably 0.1 to 2.5 parts by mass with respect to 100 parts by mass of cellulose acetate. In particular, it is about 0.1 to 1 part by mass.

  The treatment with the oxidizing agent can be performed at, for example, about 20 to 100 ° C., preferably about 30 to 70 ° C., depending on the type of the oxidizing agent.

  Cellulose acetate used in the present invention is cellulose acetate L-30, L-40, L-50, L-70 (manufactured by Daicel Chemical Industries), Ca398-6, Ca398-10, Ca398-30, Ca394-60S. Commercial products such as (manufactured by Eastman Chemical Japan Co., Ltd.) can be used.

  The resin film may contain a plasticizer and fine particles. Moreover, when manufacturing a resin film, the ultraviolet absorber may contain in the range which does not inhibit the hardening of the resin composition which is the raw material. The manufacturing method of the resin film which is such a film base material is mentioned later.

  The thickness of the film substrate 11 is preferably thinner in order to achieve a thinner optically anisotropic film, but is preferably 20 μm or more in order to prevent breakage during production. The thickness here means an average film thickness, and 20 to 200 locations in the film width direction are measured with a contact-type film thickness meter manufactured by Mitutoyo Corporation, and the average value of the measured values is Defined as film thickness. Further, the width, physical properties, shape, and the like of the film substrate 11 are not particularly limited, and can be appropriately selected according to the purpose of the optically anisotropic film to be manufactured. The width of the film is preferably 1000 to 4000 mm from the viewpoint of use in a large liquid crystal display device, use efficiency of the film during polarizing plate processing, and production efficiency.

<Method for producing optically anisotropic film>
The optically anisotropic film of the present invention comprises a step of applying a composition for forming a liquid crystal alignment layer on the film substrate 11, and a liquid crystal alignment layer 13 by irradiating the liquid crystal alignment layer forming composition with active rays. Forming a liquid crystal layer forming composition containing a fluorine-siloxane graph, a polymer, and a polymerizable liquid crystal compound on the liquid crystal alignment layer, and heating the liquid crystal layer forming composition Thus, it can be produced by a production method comprising an alignment step of aligning the polymerizable liquid crystal compound and an immobilization step of forming a liquid crystal layer by fixing the aligned polymerizable liquid crystal compound. Specifically, it is manufactured as follows. Here, as shown to Fig.1 (a), it consists only of the said film base material 11, the said liquid crystal aligning layer 13, and the said liquid crystal layer 14, and the said 1st intermediate | middle layer 15 and the 2nd intermediate | middle layer 16 are not provided. The optically anisotropic film will be described.

  First, the liquid crystal alignment layer 13 is formed on the film substrate 11.

  Specifically, a composition for forming a liquid crystal alignment layer containing the actinic radiation curable resin or the like is applied onto the film substrate 11. The composition for forming a liquid crystal alignment layer may contain, for example, the cellulose ester resin, an organic solvent, a photopolymerization initiator, and the like in addition to the actinic radiation curable resin.

  The organic solvent is not particularly limited as long as it can dissolve the actinic radiation curable resin. Specifically, for example, alcohols such as isopropyl alcohol, ethers such as methylene chloride, dioxolane and propylene glycol monomethyl ether, esters such as ethyl acetate and methyl acetate, ketones such as acetone and methyl ethyl ketone, and diacetone alcohol Ketone alcohols and the like. Among these, alcohols such as isopropyl alcohol and ethers such as propylene glycol monomethyl ether are preferable, and a mixed solvent of isopropyl alcohol and propylene glycol monomethyl ether is more preferable. Moreover, these may be used independently and may be used in combination of 2 or more type. Moreover, as solid content concentration of the said composition for liquid crystal aligning layer formation, although it changes with compositions etc., it is preferable that it is about 0.1-80 mass%, for example.

  As the photopolymerization initiator, it is only necessary to contribute to the initiation of the curing reaction of the actinic radiation curable resin. Specifically, for example, α-hydroxy ketone, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone And derivatives thereof. Among these, α-hydroxy ketone and derivatives thereof are preferable. Moreover, these may be used independently and may be used in combination of 2 or more type. Moreover, it is preferable that content of a photoinitiator is about 0.1-1 mass part with respect to 100 mass parts of said actinic radiation curable resins, for example.

  The coating method is not particularly limited, and a known coating method can be used. Specific examples include a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, an air doctor coater, a die coater, a dip coater, and an ink jet method. And as application | coating thickness, although it changes also with the solid content density | concentration etc. of the said composition for liquid crystal aligning layer formation, specifically, it is the thickness which the thickness of the liquid crystal aligning layer formed falls in the said range, for example. Preferably there is.

  The liquid crystal alignment layer 13 is formed by irradiating the composition for forming a liquid crystal alignment layer applied on the film substrate 11 with active rays.

  Next, the liquid crystal layer 14 is formed on the liquid crystal alignment layer 13.

  Specifically, a liquid crystal layer forming composition containing the fluorine-siloxane graft polymer and a polymerizable liquid crystal compound is applied onto the liquid crystal alignment layer 13. The composition for forming a liquid crystal layer may contain, for example, an organic solvent, a photopolymerization initiator, and the like in addition to the fluorine-siloxane graph, the polymer, and the polymerizable liquid crystal compound. The organic solvent is not particularly limited as long as it can dissolve the fluorine-siloxane graft polymer and the polymerizable liquid crystal compound. Specifically, for example, alcohols such as isopropyl alcohol, esters such as methylene chloride, dioxolane and propylene glycol monomethyl ether acetate, esters such as ethyl acetate and methyl acetate, ketones such as acetone and methyl ethyl ketone, and diacetone Examples include ketone alcohols such as alcohol. Among these, those having a relatively high boiling point such as propylene glycol monomethyl ether acetate are preferable. Moreover, these may be used independently and may be used in combination of 2 or more type. Moreover, as solid content concentration of the said composition for liquid-crystal layer formation, although it changes with compositions etc., it is preferable that it is about 0.1-80 mass%, for example.

  The photopolymerization initiator may be contained in the liquid crystal layer forming composition when a polymerizable liquid crystal compound having a polymerizable functional group is used. In that case, the photopolymerization initiator is not limited as long as it can contribute to the initiation of the curing reaction of the polymerizable liquid crystal compound, and examples thereof include those similar to the photopolymerization initiator of the liquid crystal alignment layer forming composition. Examples include α-hydroxyketone, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Among these, α-hydroxy ketone and derivatives thereof are preferable. Moreover, these may be used independently and may be used in combination of 2 or more type. Moreover, it is preferable that content of a photoinitiator is about 0.1-1 mass part with respect to 100 mass parts of said polymeric liquid crystal compounds, for example.

  The coating method is not particularly limited, and a known coating method can be used, and the same coating method as the liquid crystal alignment layer forming composition can be used. Specific examples include a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, an air doctor coater, a die coater, a dip coater, and an ink jet method. The coating thickness varies depending on the solid content concentration of the liquid crystal layer forming composition, and specifically, for example, the thickness of the liquid crystal layer to be formed is within the above range. Is preferred.

  Then, the polymerizable liquid crystal compound is aligned by heating the liquid crystal layer forming composition applied on the liquid crystal alignment layer 13 that has been subjected to the rubbing treatment to a temperature higher than the liquid crystal transition temperature of the polymerizable liquid crystal compound. The alignment time takes about 1 to 10 minutes, for example. Thereafter, the liquid crystal layer forming composition is cooled below the liquid crystal transition temperature of the polymerizable liquid crystal compound, the orientation is fixed, and the liquid crystal layer forming composition is irradiated with actinic rays. By doing so, the orientation is more fixed, and the liquid crystal layer 14 in which the polymerizable liquid crystal compound is tilted is formed.

  Formation of the functional layers 12 such as the liquid crystal alignment layer 13 and the liquid crystal layer 14 can also be performed by, for example, an optical anisotropic film manufacturing apparatus as shown in FIG. In addition, as a manufacturing apparatus of an optical anisotropic film, it is not limited to what is shown in FIG. 2, The thing of another structure may be sufficient.

  FIG. 2 is a schematic diagram showing a basic configuration of the optically anisotropic film manufacturing apparatus 20. The optical anisotropic film manufacturing apparatus 20 includes an unwinding device 21, a coating device 22, a first temperature adjusting device 23, a second temperature adjusting device 24, a curing device 25, a winding device 26, and the like.

  The unwinding device 21 supplies a film to be processed such as a transparent film base material to the coating device 22 or the like. The unwinding device 21 includes, for example, an unwinding roller wound so that the film to be processed can be unwound, and supplies the film to be processed to the coating device 22 and the like by rotating the unwinding roller. is there.

  The coating device 22 applies a liquid crystal alignment layer forming composition or a liquid crystal layer forming composition on the surface of the film to be processed supplied from the unwinding device 21. The coating device 21 can use a general coating device without limitation. Specifically, for example, the above-described coating apparatus and the like can be mentioned. In addition, when a plurality of layers are applied and formed on the film to be processed, the coating may be simultaneously applied in multiple layers with a single application device such as an extrusion die having a multi-manifold. A plurality of apparatuses may be arranged side by side and applied sequentially.

  When the liquid crystal alignment layer is formed, the first temperature adjusting device 23 heats and drys the liquid crystal alignment layer forming composition applied on the film to be processed. When forming a liquid crystal layer, the liquid crystal layer forming composition applied on the film to be treated is heated to align the polymerizable liquid crystal compound in the liquid crystal layer forming composition. The first temperature control device 23 may employ, for example, a convection drying method using hot air, a radiant drying method using radiant heat such as infrared rays, or the like.

  When the second temperature adjusting device 24 forms a liquid crystal alignment layer, for example, the liquid crystal alignment layer forming composition applied on the film to be processed is cooled to form a liquid crystal alignment layer forming composition before curing. Decrease the fluidity of In the case of forming a liquid crystal layer, the liquid crystal layer forming composition applied on the film to be treated is cooled, and not only the fluidity of the liquid crystal layer forming composition before curing is lowered, but also the liquid crystal layer forming The polymerizable liquid crystal compound in the composition for use is fixed. The second temperature adjusting device 24 may employ, for example, a convection drying method using cold air.

  The curing device 25 is applied onto a film to be processed, and the composition subjected to the above treatment is irradiated with active rays to be cured. Specifically, active ray irradiation apparatuses, such as an ultraviolet irradiation apparatus, are mentioned, for example.

  The winding device 26 winds up the optically anisotropic film obtained as described above. The winding device 26 is, for example, a device that includes a rotatable winding roller and winds the optically anisotropic film by rotating the winding roller.

<Method for producing film substrate>
As described above, the film substrate is not particularly limited as long as it can be used as a substrate for an optically anisotropic film. Specifically, for example, a resin film obtained by a solution casting film forming method or a melt casting film forming method described later can be used, and a resin film obtained by a melt casting film forming method is preferable. Used. If it is such a resin film, a film thickness is uniform and it can be conveniently used as a base material of an optically anisotropic film. In addition, the manufacturing method of the cellulose-ester film which is a resin film suitable as a film base material is demonstrated here.

(Solution casting film forming method)
First, the case where a resin film is manufactured by the solution casting film forming method will be described.

  The solution casting film forming method includes a casting step in which a resin solution (dope) in which a transparent resin is dissolved is cast on a traveling support to form a casting film (web), and the casting film is A film forming method comprising a peeling step for peeling from the support as a film, a stretching step for stretching the peeled film, and a drying step for drying the film by transporting the stretched film with a plurality of transport rollers. is there. For example, it is performed by a resin film manufacturing apparatus using a solution casting film forming method as shown in FIG. In addition, as a manufacturing apparatus of a resin film, it is not limited to what is shown in FIG. 3, The thing of another structure may be sufficient.

  FIG. 3 is a schematic diagram showing a basic configuration of a resin film manufacturing apparatus 31 by a solution casting method. The resin film manufacturing apparatus 31 includes an endless belt support 32, a casting die 33, a peeling roller 34, a stretching apparatus 35, a drying apparatus 36, a winding apparatus 37, and the like. The casting die 13 casts a resin solution (dope) 38 in which a transparent resin is dissolved on the surface of the endless belt support 32. The endless belt support 32 is formed into a film by forming a web made of the dope 38 cast from the casting die 33 and drying it while being conveyed. The peeling roller 34 peels the film from the endless belt support 32. The stretching device 35 stretches the peeled film. The drying device 36 dries the stretched film while being conveyed by a conveyance roller. The winding device 37 winds the dried film into a film roll.

  The casting die 33 is supplied with a dope from a dope supply pipe connected to the upper end. Then, the supplied dope is discharged from the casting die 33 to the endless belt support 32, and a web is formed on the endless belt support 32.

  As shown in FIG. 1, the endless belt support 32 is a metal endless belt having a mirror surface and traveling infinitely. As the belt, for example, a belt made of stainless steel or the like is preferably used from the viewpoint of peelability of the film. From the viewpoint of effectively utilizing the width of the endless belt support 32, the width of the casting film cast by the casting die 33 is preferably 80 to 99% with respect to the width of the endless belt support 32. . And in order to finally obtain a resin film with a width of 1000 to 4000 mm, the width of the endless belt support 32 is preferably 1800 to 5000 mm. Further, instead of the endless belt support, a rotating metal drum (endless drum support) having a mirror surface may be used.

  And the said endless belt support body 32 dries the solvent in dope, conveying the cast film (web) formed on the surface. The drying is performed, for example, by heating the endless belt support 32 or blowing heated air onto the web. At that time, although the temperature of the web varies depending on the dope solution, the range of −5 to 70 ° C. is preferable and the range of 0 to 60 ° C. is preferable in consideration of the conveyance speed and productivity accompanying the evaporation time of the solvent. More preferred. The higher the temperature of the web, the faster the solvent can be dried. However, when the temperature is too high, the web tends to foam or the flatness tends to deteriorate.

  When heating the endless belt support 32, for example, a method of heating the web on the endless belt support 32 with an infrared heater, a method of heating the back surface of the endless belt support 32 with an infrared heater, the back surface of the endless belt support 32 And a method of heating by blowing heated air, and the like can be selected as needed.

  In addition, when blowing heated air, the wind pressure of the heated air is preferably 50 to 5000 Pa in consideration of the uniformity of solvent evaporation and the like. The temperature of the heating air may be dried at a constant temperature, or may be supplied in several steps in the running direction of the endless belt support 32.

  The time from casting the dope on the endless belt support 32 to peeling the web from the endless belt support 32 varies depending on the film thickness of the resin film to be produced and the solvent used. Considering the peelability from the belt support 32, it is preferably in the range of 0.5 to 5 minutes.

  The transport speed of the cast film by the endless belt support 32 is preferably about 50 to 200 m / min, for example. Moreover, it is preferable that the ratio (draft ratio) of the transport speed of the cast film with respect to the traveling speed of the endless belt support 32 is about 0.8 to 1.2. When the draft ratio is within this range, the cast film can be stably formed. For example, if the draft ratio is too large, there is a tendency to cause a phenomenon called neck-in in which the cast film is reduced in the width direction, and if so, a wide film cannot be formed.

  The peeling roller 34 is in contact with the surface of the endless belt support 32 on which the dope 38 is cast, and the dried web (film) is peeled by applying pressure to the endless belt support 32 side. . When the film is peeled from the endless belt support 32, the film is stretched in the film transport direction (machine direction: MD direction) by the peeling tension and the subsequent transport tension. For this reason, it is preferable that the peeling tension and the conveyance tension when peeling the film from the endless belt support 32 are 50 to 400 N / m.

  Further, the total residual solvent amount of the film when the film is peeled off from the endless belt support 32 is the peelability from the endless belt support 32, the residual solvent amount at the time of peeling, the transportability after peeling, and the result after transporting and drying. Considering the physical properties of the resin film and the like, it is preferably 30 to 200% by mass.

  The stretching device 35 stretches the film peeled from the endless belt support 32 in a direction (Transverse Direction: TD direction) orthogonal to the web conveyance direction. Specifically, both ends in a direction perpendicular to the film transport direction are gripped with a clip or the like, and the distance between the opposing clips is increased to extend in the TD direction. And the said extending | stretching apparatus 35 may be provided with the apparatus which cut | disconnects the area | region which was holding the clip. Further, the stretching device 35 may not be provided.

  The drying device 36 includes a plurality of transport rollers, and dries the film while transporting the film between the rollers. In that case, you may dry using heating air, infrared rays, etc. independently, and you may dry using heating air and infrared rays together. It is preferable to use heated air from the viewpoint of simplicity. The drying temperature varies depending on the amount of residual solvent in the film, but it is determined by appropriately selecting the amount of residual solvent within the range of 30 to 180 ° C. in consideration of drying time, unevenness of shrinkage, stability of the amount of expansion and contraction, etc. That's fine. Moreover, it may be dried at a constant temperature, or may be divided into two to four stages of temperature, and may be divided into several stages of temperature. Further, the film can be stretched in the MD direction while being conveyed in the drying device 36. The amount of residual solvent in the film after the drying treatment in the drying device 36 is preferably 0.01 to 15% by mass in consideration of the load of the drying process, the dimensional stability expansion / contraction ratio during storage, and the like.

  The winding device 37 winds the film having a predetermined residual solvent amount on the winding core to a required length by the drying device 36. The temperature at the time of winding is preferably cooled to room temperature in order to prevent scratches and loosening due to shrinkage after winding. The winder to be used can be used without any particular limitation, and may be a commonly used one, such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress. Can be wound up.

  The resin film which can be used as a film base material according to the embodiment of the present invention is obtained by the process as described above.

  The composition of the resin solution used in the solution casting film forming method will be described.

  The resin contained in the resin solution is not particularly limited as long as it is a resin having transparency when formed into a substrate by a solution casting film forming method or the like, but can be manufactured by a solution casting film forming method or the like. It is preferable that it is easy, has excellent adhesion to a liquid crystal alignment layer, and is optically isotropic. Specific examples of the transparent resin include cellulose ester resins such as cellulose triacetate resin. The dope used in the solution casting film forming method may contain fine particles. In this case, the fine particles to be used are appropriately selected according to the purpose of use, but are preferably fine particles that can scatter visible light when contained in a transparent resin. The fine particles may be inorganic fine particles such as silicon oxide or organic fine particles such as acrylic resin. As the solvent used in the solution casting film forming method, a solvent containing a good solvent for the transparent resin can be used, and a poor solvent may be contained within a range in which the transparent resin does not precipitate. Examples of the good solvent for the cellulose ester resin include organic halogen compounds such as methylene chloride. Moreover, as a poor solvent with respect to a cellulose ester-type resin, C1-C8 alcohols, such as methanol, etc. are mentioned, for example. The resin solution used in the solution casting film forming method may contain other components (additives) other than the transparent resin, fine particles, and solvent as long as the effects of the present invention are not impaired. Examples of the additive include a plasticizer, an antioxidant, an ultraviolet absorber, a heat stabilizer, a conductive substance, a flame retardant, a lubricant, and a matting agent.

  Moreover, the solution of a cellulose-ester-type resin is obtained by mixing said each composition. The obtained cellulose ester resin solution is preferably filtered using a suitable filter medium such as filter paper.

(Melt casting method)
Next, the case where a resin film is manufactured by the melt casting method will be described.

  The melt casting film forming method includes a casting step of casting a resin melt obtained by melting a transparent resin on a traveling support to form a casting film, and cooling the casting film to form a film. A film forming method comprising: a cooling step for forming a film; a peeling step for peeling the film from the support; and a stretching step for stretching the film by transporting the peeled film with a plurality of transport rollers. For example, it is performed by a resin film manufacturing apparatus using a melt casting film forming method as shown in FIG. In addition, as a manufacturing apparatus of a resin film, it is not limited to what is shown in FIG. 4, The thing of another structure may be sufficient.

  FIG. 4 is a schematic diagram showing a basic configuration of a resin film manufacturing apparatus 41 by a melt casting film forming method. The resin film manufacturing apparatus 41 includes a first cooling roller 42, a casting die 43, a touch roller 44, a second cooling roller 45, a third cooling roller 46, a peeling roller 47, a conveying roller 48, a stretching device 49, and a winding device. The apparatus 50 etc. are provided. The casting die 43 casts a resin melt (dope) obtained by melting a transparent resin onto the surface of the first cooling roller 42. The first cooling roller 42 forms a casting film made of a dope cast from the casting die 43, cools the casting film while transporting it, and transports the casting film to the second cooling roller 45. At that time, the thickness of the casting film is adjusted and the surface is smoothed by the touch roller 44 provided in contact with the first cooling roller 42. The second cooling roller 45 cools the cast film while transporting the cast film, and transports the cast film to the third cooling roller 46. By so doing, the cast film is used as a film. The peeling roller 47 peels the film from the third cooling roller 46. The transport roller 48 extends in the MD direction while transporting the peeled film. The stretching device 49 stretches the film in the TD direction. The winding device 50 winds the cooled and solidified film to form a film roll.

  The casting die 43 has the same configuration as the casting die 33 except that a resin melt is discharged as a dope instead of a resin solution.

  The first cooling roller 42, the second cooling roller 45, and the third cooling roller 46 are metal rollers having a mirror surface. As each of the rollers, for example, a roller made of stainless steel or the like is preferably used from the viewpoint of peelability of a cast film or a film. The width of the cast film cast by the casting die 43, the transport speed of the cast film by the first cooling roller 42, the second cooling roller 45, and the third cooling roller 46, etc. It is the same.

  The touch roller 44 has an elastic surface, and is deformed along the surface of the first cooling roller 42 by the pressing force to the first cooling roller 42, and between the first cooling roller 42, Form a nip. The touch roller 44 is not particularly limited as long as it is a touch roller conventionally used in the melt casting film forming method. Specifically, the thing made from stainless steel is mentioned, for example.

  The peeling roller 47 is in contact with the third cooling roller 46, and the film is peeled by applying pressure.

  The conveyance roller 48 includes a plurality of conveyance rollers, and can be stretched in the MD direction of the film by setting different rotation speeds for each conveyance roller.

  The stretching device 49 and the winding device 50 may be the same as the stretching device 35 and the winding device 37 in the solution casting film forming method.

  Hereinafter, the composition of the resin melt used in the melt casting film forming method will be described.

  The resin used in the melt casting film forming method can be the same as the resin in the melt casting film forming method as long as it can be heated and melted. In addition, the same composition as in the melt casting film forming method can be used for other compositions.

  The film substrate is not limited to the resin film formed by the solution casting film forming method or the melt casting film forming method, and may be a resin film formed by other methods, The resin film which laminated | stacked the layer may be sufficient.

  The film base material is a film formed by casting a resin melt containing the transparent resin and a plasticizer on a traveling support and cooling the cast film. A resin film obtained by peeling from a support, that is, a resin film formed by a melt casting method is preferable.

<Polarizing plate>
A polarizing plate according to another embodiment of the present invention includes a polarizing element and a protective film disposed on a surface of the polarizing element, and the optical anisotropic according to the embodiment of the present invention is used as the protective film. A functional film is used. The polarizing element is an optical element that emits incident light converted to polarized light, and is generally referred to as a polarizer or a polarizing film.

  As the polarizing plate, for example, a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing element produced by immersing and stretching a polyvinyl alcohol film in an iodine solution. What stuck the adhesive film is preferable. Further, the optically anisotropic film may be laminated on the other surface of the polarizing element, or a transparent protective film for another polarizing plate may be laminated. As the transparent protective film for this polarizing plate, for example, as a commercially available cellulose ester film, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UY-HA, KC8UX-RHA, KC4FR-1, KC4HR-1, KC8UCR- 3, KC8UCR-4, KC8UCR-5, KC4UESW (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used. Or you may use resin films, such as cyclic olefin resin other than a cellulose-ester film, an acrylic resin, polyester, a polycarbonate. In this case, since the saponification suitability is low, it is preferable to perform an adhesive process on the polarizing plate through an appropriate adhesive layer.

  As described above, the polarizing plate uses the optically anisotropic film as a protective film laminated on at least one surface side of the polarizing element. In that case, when the optical anisotropic film works as an optical compensation film such as a retardation film, the slow axis of the optical anisotropic film is arranged so as to be substantially parallel or orthogonal to the absorption axis of the polarizing element. Preferably it is.

  Moreover, as a specific example of the said polarizing element, a polyvinyl alcohol-type polarizing film is mentioned, for example. Polyvinyl alcohol polarizing films include those obtained by dyeing iodine on polyvinyl alcohol films and those obtained by dyeing dichroic dyes. As the polyvinyl alcohol film, a modified polyvinyl alcohol film modified with ethylene is preferably used.

  The polarizing element is obtained as follows, for example. First, a film is formed using a polyvinyl alcohol aqueous solution. The obtained polyvinyl alcohol film is uniaxially stretched and then dyed or dyed and then uniaxially stretched. And preferably, a durability treatment is performed with a boron compound.

  The thickness of the polarizing element is preferably 5 to 40 μm, more preferably 5 to 30 μm, and more preferably 5 to 20 μm.

  When a cellulose ester-based optically anisotropic film containing a cellulose ester is bonded to the surface of the polarizing element, it is preferably bonded with a water-based adhesive mainly composed of completely saponified polyvinyl alcohol. In the case of an optically anisotropic film other than the cellulose ester-based optically anisotropic film, it is preferable to perform an adhesive process on the polarizing plate through an appropriate adhesive layer.

  The polarizing plate as described above uses an optically anisotropic film according to the above embodiment as a transparent protective film, so that the optically anisotropic film is excellent in optical compensation performance and the like. An excellent polarizing plate can be obtained. Furthermore, since the optically anisotropic layer of the optically anisotropic film has high adhesiveness, its excellent optical compensation performance is maintained even in a poor environment such as high temperature and high humidity. A board is obtained.

<Liquid crystal display device>
A liquid crystal display device according to another embodiment of the present invention includes a liquid crystal cell and two polarizing plates arranged so as to sandwich the liquid crystal cell, and at least one of the two polarizing plates includes: It is a polarizing plate concerning the present invention. Note that the liquid crystal cell is a cell in which a liquid crystal substance is filled between a pair of electrodes, and by applying a voltage to the electrodes, the alignment state of the liquid crystal is changed and the amount of transmitted light is controlled. Since such a liquid crystal display device uses a polarizing plate excellent in optical compensation performance and the like, optical characteristics such as viewing angle characteristics of the liquid crystal display device can be improved. Therefore, high definition of the liquid crystal display device can be realized.

  Specific examples of the liquid crystal display device include a reflective type, a transmissive type, and a transflective type, and also include a TN type, STN type, OCB type, HAN type, VA type (PVA). Type, MVA type), IPS type and the like. Among these, the polarizing plate provided with the optically anisotropic film according to the present embodiment is suitably used in a TN liquid crystal display device.

  With the TN liquid crystal display device according to the present invention, it is possible to reduce coloration during black display due to light leakage and to obtain a liquid crystal display device with excellent visibility such as front contrast.

  In the TN liquid crystal display device according to the present invention, the rubbing axes of the two substrates sandwiching the liquid crystal cell, the absorption axes of the first polarizing plate, and the second polarizing plate are arranged orthogonally, and the liquid crystal display When the horizontal direction of the liquid crystal cell in the device is set to 0 °, the absorption axis of the first polarizing plate is in the range of 45 + 0.1 to 3 degrees as the counterclockwise angle with respect to the horizontal direction of the liquid crystal cell. Preferably, the absorption axis of the second polarizing plate is arranged at an angle in the range of 135-0.1 to 3 degrees. In the present invention, the TN liquid crystal display device having such an arrangement is referred to as an E mode.

  In the TN liquid crystal display device, the rubbing axis of the liquid crystal cell and the absorption axes of the first polarizing plate and the second polarizing plate may be arranged in parallel, which is referred to as an O mode in the present invention. .

  In the present invention, the E-mode TN liquid crystal display device is preferable because excellent results are obtained in viewing angle, gradation inversion, color shift, and blur.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
<Preparation of fluorine-siloxane graft polymer 1>
Hereinafter, commercially available product names of materials used for preparing the fluorine-siloxane graft polymer 1 are shown.

Fluororesin (A): Cefalcoat CF-803 (hydroxyl value 60, number average molecular weight 15000; manufactured by Central Glass Co., Ltd.)
One-end radical polymerizable polysiloxane (A): Silaplane FM-0721 (number average molecular weight 5000; manufactured by Chisso Corporation)
Radical polymerization initiator: Perbutyl O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
Curing agent: Sumidur N3200 (biuret type prepolymer of hexamethylene diisocyanate; manufactured by Sumika Bayer Urethane Co., Ltd.)
[Synthesis of radical polymerizable fluororesin (A)]
In a glass reactor equipped with a mechanical stirrer, thermometer, condenser and dry nitrogen gas inlet, cefal coat CF-803 (1554 parts by mass), xylene (233 parts by mass), and 2-isocyanatoethyl methacrylate (6 3 parts by mass) and heated to 80 ° C. in a dry nitrogen atmosphere. After reacting at 80 ° C. for 2 hours and confirming that the absorption of isocyanate disappeared by the infrared absorption spectrum of the sample, the reaction mixture was taken out and 50% by mass of radically polymerizable fluororesin (A) via a urethane bond. Got.

(Preparation of fluorine-siloxane graft polymer 1)
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, the synthesized radical polymerizable fluororesin (A) (26.1 parts by mass), xylene (19.5 parts by mass) ), N-butyl acetate (16.3 parts by mass), methyl methacrylate (2.4 parts by mass), n-butyl methacrylate (1.8 parts by mass), lauryl methacrylate (1.8 parts by mass), 2-hydroxyethyl Add methacrylate (1.8 parts by mass), FM-0721 (5.2 parts by mass), and perbutyl O (0.1 parts by mass), heat to 90 ° C. in a nitrogen atmosphere, and hold at 90 ° C. for 2 hours. did. Perbutyl O (0.1 part) was added, and the solution was further maintained at 90 ° C. for 5 hours to obtain a 35 mass% fluorine-siloxane graft polymer 1 solution having a weight average molecular weight of 171,000.

  The weight average molecular weight was determined by GPC. The mass% of the fluorine-siloxane graft polymer 1 was determined by HPLC (liquid chromatography).

<Preparation of fluorine-siloxane graft polymer 2>
A solution of 35 mass% fluorine-siloxane graft polymer 2 having a weight average molecular weight of 204000 was obtained by the synthesis method of Polymer 1 except that the one-end radical polymerizable polysiloxane (A) was changed to the following compound.

One-end radical polymerizable polysiloxane (B): X-22-174DX (number average molecular weight 4600; manufactured by Shin-Etsu Chemical Co., Ltd.)
<Preparation of fluorine-siloxane graft polymer 3>
Hereinafter, commercially available product names of materials newly used in the preparation of the fluorine-siloxane graft polymer 3 are shown.

Radical polymerizable monomer (F) having one radical polymerizable double bond and at least one fluoroalkyl group in the molecule: Light ester FM-108 (heptadecafluorodecyl methacrylate; manufactured by Kyoeisha Chemical Co., Ltd.)
Curing type acrylic resin: Desmophen A160 (hydroxyl value 90; manufactured by Sumika Bayer Urethane Co., Ltd.)
Curing agent: Coronate HX (isocyanurate type prepolymer of hexamethylene diisocyanate; manufactured by Nippon Polyurethane)
(Preparation of fluorine-siloxane graft polymer 3)
In a glass reactor equipped with a mechanical stirrer, thermometer, condenser and nitrogen gas inlet, the above synthesized radical polymerizable fluororesin (A) (36.2 parts by mass), methyl methacrylate (11.6 parts by mass) ), 2-hydroxyethyl methacrylate (4.9 parts by mass), FM-0721 (10.5 parts by mass), FM-108 (7.7 parts by mass), methacrylic acid (0.4 parts by mass), xylene (1 0.5 mass part), n-butyl acetate (60.2 mass parts) and perbutyl O (0.3 mass parts) were added, heated to 90 ° C. in a nitrogen atmosphere, and held at 90 ° C. for 2 hours. Perbutyl O (0.1 part) was added, and the solution was further maintained at 90 ° C. for 5 hours to obtain a 40 mass% fluorine-siloxane graft polymer 3 solution having a weight average molecular weight of 168,000. The weight average molecular weight was determined by GPC, and the mass% of the fluorine-siloxane graft polymer 3 was determined by HPLC.

<Preparation of fluorine-siloxane graft polymer 4>
Hereinafter, commercially available product names of materials newly used in the preparation of the fluorine-siloxane graft polymer 4 are shown.

Single-end alkoxy polyalkylene glycol (D): Blemmer PME-400 (molecular weight 470; manufactured by NOF Corporation)
(Preparation of fluorine-siloxane graft polymer 4)
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, the synthesized radical polymerizable fluororesin (A) (26.7 parts by mass), xylene (14.2 parts by mass) ), N-butyl acetate (13.7 parts by mass), methyl methacrylate (5.4 parts by mass), n-butyl methacrylate (2.7 parts by mass), lauryl methacrylate (0.9 parts by mass), 2-hydroxyethyl Add methacrylate (1.8 parts by mass), FM-0721 (1.3 parts by mass), Bremer PME-400 (1.3 parts by mass), perbutyl O (0.1 parts by mass), and in a nitrogen atmosphere at 90 ° C. And heated at 90 ° C. for 2 hours. Perbutyl O (0.1 part by mass) was added, and the solution was further maintained at 90 ° C. for 5 hours to obtain a 40% by mass fluorine-siloxane graft polymer 4 solution having a weight average molecular weight of 146000. The weight average molecular weight was determined by GPC, and the mass% of the fluorine-siloxane graft polymer 4 was determined by HPLC.

<Fluorine-siloxane graft polymer 5>
Use of commercially available fluorine-siloxane graft polymer 5 (ZX-049, manufactured by Fuji Kasei Kogyo Co., Ltd.) (polymerizable liquid crystal compound)
The following polymerizable liquid crystal compound A and polymerizable liquid crystal compound B were used as the polymerizable liquid crystal compound.

<Preparation of optically anisotropic film 1>
[Production of film substrate]
<Preparation of ester compound 1>
251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with a thermometer, stirrer, and slow cooling tube The flask is charged and gradually heated with stirring until it reaches 230 ° C. in a nitrogen stream. The ester compound 1 was obtained by making it dehydrate-condense for 15 hours, and depressurizingly distilling unreacted 1, 2- propylene glycol at 200 degreeC after completion | finish of reaction. The acid value was 0.10 and the number average molecular weight was 450.

(Silicon dioxide dispersion)
Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass (average diameter of primary particles 7 nm)
90 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. It filtered with the fine particle dispersion | distribution dilution liquid filter (Advantech Toyo Co., Ltd .: Polypropylene wind cartridge filter TCW-PPS-1N).

(Dope composition)
90 parts by mass of cellulose triacetate (cellulose triacetate synthesized from linter cotton, acetyl group substitution degree 2.88, Mn = 14000)
Ester compound 1 10 parts by weight Tinuvin 928 (manufactured by Ciba Japan Co., Ltd.) 2.5 parts by weight Silicon dioxide dispersion diluent 4 parts by weight Methylene chloride 432 parts by weight Ethanol 38 parts by weight While stirring, it completely dissolved, and Azumi Filter Paper No. No. 24 was used for filtration to prepare a dope solution.

  Next, the prepared dope solution was uniformly cast on a stainless steel band support. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off. The web of the peeled cellulose ester film was evaporated at 35 ° C., slit to 1.65 m width, 1.3 times in the TD direction (film width direction) with a tenter, and the draw ratio in the MD direction was 1.01. The film was dried at a drying temperature of 160 ° C. while being stretched at twice. The residual solvent amount at the start of drying was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C. with a number of rolls, slitting to a width of 1.49 m, applying a knurling process with a width of 15 mm and a height of 10 μm at both ends of the film, and winding it around a winding core To obtain a cellulose ester film. The residual solvent amount of the cellulose ester film was 0.2%, the film thickness was 40 μm, and the number of turns was 3900 m.

  As for the retardation value of the cellulose ester film, Ro was 5 nm and Rt was 55 nm. The retardation value is a value measured at a wavelength of 590 nm using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) after adjusting the humidity to 23 ° C. and 55% RH.

  A liquid crystal alignment layer was provided on the prepared cellulose ester film by the following procedure, and then a liquid crystal layer was provided on the liquid crystal alignment layer to prepare an optically anisotropic film 1.

On the cellulose ester film, the following liquid crystal alignment layer coating solution is applied by die coating, dried at 80 ° C. for 30 seconds, and then irradiated with an oxygen concentration of 2.0%, ultraviolet rays of 120 mJ / cm ² and an illuminance of 200 mW / cm ^2. Cured. The film thickness of the liquid crystal alignment layer after curing was 2.0 μm.

  The film was then rubbed. The film conveyance speed was 20 m / min, the surface of the alignment film was brought into contact with a rotating rubbing roll, and the rubbing angle was 45 °.

  Next, the following liquid crystal layer coating solution was applied on the liquid crystal alignment layer by a die coating to a thickness of 7 μm.

After drying at 100 ° C. for 30 seconds, the liquid crystal compound was aligned for 30 seconds. Next, the film in which the liquid crystal compound was aligned was irradiated and cured at 250 mJ / cm ² and an illuminance of 300 mW / cm ² to obtain an optical anisotropic film 1. The thickness of the liquid crystal layer was 1.6 μm. The tilt angle of the polymerizable liquid crystal compound with respect to the thickness direction is determined by using a birefringence meter capable of tilt measurement (for example, KOBRA-31WR manufactured by Oji Scientific Instruments, Axoscan manufactured by Opto Science Co., Ltd., Spectroscopic Ellipsometer DVA36VW manufactured by Mizoji Optical Co., Ltd.). The measurement was performed at 10 points in an atmosphere of 23 ° C. and 55% RH, and it was confirmed that the polymerizable liquid crystal compound was inclined in the range of 28 ° ± 2 ° with respect to the thickness direction of the liquid crystal layer. In addition, there was little variation in 10-point measurement values.

  The retardation of the optically anisotropic film 1 as a whole was 40 nm for Ro and 138 nm for Rt.

(Liquid crystal alignment layer coating solution)
25 parts by mass of polyester acrylate (Laromar LR8800 manufactured by BASF Japan Ltd.)
Propylene glycol monomethyl ether 290 parts by mass Isopropyl alcohol 685 parts by mass Photopolymerization initiator (Irgacure 184, manufactured by Ciba Japan Co., Ltd.) 0.05 parts by mass (liquid crystal layer coating solution)
Polymerizable liquid crystal compound A 10 parts by weight Polymerizable liquid crystal compound B 10 parts by weight Propylene glycol monomethyl ether acetate 80 parts by weight Photopolymerization initiator (Irgacure 184 manufactured by Ciba Japan Co., Ltd.) 1 part by weight Fluorine-siloxane graft polymer 1 1 part by mass <Preparation of optically anisotropic film 2>
The same as film 1 except that fluorine-siloxane graft polymer 2 is used instead of fluorine-siloxane graft polymer 1.

<Preparation of optically anisotropic film 3>
The same as film 1 except that fluorine-siloxane graft polymer 3 was used instead of fluorine-siloxane graft polymer 1.

<Preparation of optically anisotropic film 4>
The same as film 1 except that fluorine-siloxane graft polymer 4 was used instead of fluorine-siloxane graft polymer 1.

<Preparation of optically anisotropic film 5>
The same as film 1 except that fluorine-siloxane graft polymer 5 was used instead of fluorine-siloxane graft polymer 1.

<Preparation of optically anisotropic film 6>
The same as film 1 except that the addition amount of fluorine-siloxane graft polymer 1 was changed to 0.01 parts by mass.

<Preparation of optical anisotropic film 7>
The same as film 1 except that the addition amount of fluorine-siloxane graft polymer 1 was changed to 0.20 parts by mass.

<Preparation of optically anisotropic film 8>
The same as film 1 except that the addition amount of fluorine-siloxane graft polymer 1 is changed to 0.001 part by mass.

<Preparation of optically anisotropic film 9>
The same as film 1 except that the addition amount of fluorine-siloxane graft polymer 1 was changed to 0.30 parts by mass.

<Preparation of optical anisotropic film 10>
The same as film 1 except that the amount of photopolymerization initiator added to optically anisotropic film 1 is changed to 0.02 parts by mass.

<Preparation of optically anisotropic film 11>
The same as film 1 except that fluorine-siloxane graft polymer 1 is not added from optically anisotropic film 1.

<Preparation of optically anisotropic film 12>
The same as film 1 except that F-477 (perfluoroalkyl group / lipophilic group / hydrophilic group-containing oligomer; manufactured by DIC Corporation) was used instead of fluorine-siloxane graft polymer 1.

<Preparation of optical anisotropic film 13>
The same as film 1 except that FM-0721 (one-end radical-polymerizable polysiloxane) is used instead of fluorine-siloxane graft polymer 1.

  It was confirmed that the optically anisotropic films 2 to 10 were such that the polymerizable liquid crystal compound was inclined in the range of an average inclination angle of 28 ° ± 2 ° with respect to the thickness direction of the liquid crystal layer. On the other hand, the optically anisotropic films 11 to 13 had an average inclination angle in the range of 28 ° ± 2 °, but the dispersion of 10-point measurement values was large.

<Evaluation>
The following evaluation was implemented using the optically anisotropic films 1-13 produced above.

  The evaluation method is shown below.

<Orientation defect>
The alignment defect of the liquid crystal layer was evaluated by measuring the number of alignment defects of the optically anisotropic film using a BX51 polarizing microscope manufactured by OLYMPUS. The number represents the number per mm ² .

  The polarizing plate was placed in a crossed Nicol state, and the optically anisotropic film was set so that the in-plane slow axis was parallel to the polarization analyzer transmission axis, and the number of point defects observed at that time was evaluated.

  The smaller the number, the better the uniformity of orientation and the better.

<Adhesiveness of liquid crystal layer>
<Peel test sample preparation method>
The produced optically anisotropic film was cut into a width of 4 cm and a length of 15 cm, the surface was wiped with methanol, and the surface was soiled, and then the sample was stored for 2 hours under conditions of a temperature of 25 ° C. and a humidity of 60%.

  Then, in the length direction, using an NT cutter, with the blade inclined at 45 degrees, leave 1 cm in both ends in the width direction of the sample and 4 cm in both ends in the length direction so as not to cut the support. 6 cm cuts were made in the length direction at intervals of 5 mm.

  For one SUS plate (30 cm × 30 cm, thickness 8 mm), a pressure sensitive adhesive sheet made by Soken Chemical Co., Ltd. (PET release sheet is attached to both sides) is cut to a width of 5 cm and a length of 24 cm. The two sheets were peeled off and affixed so that a gap of 5 cm above, 5 cm below, and 3 cm left and right was opened from the edge of the SUS plate, and the other release sheet was peeled off. Then, the six optically anisotropic films with the cuts were arranged, and the optically anisotropic layer side of the central part 5 cm in the longitudinal direction of the film was attached to the adhesive on the SUS plate so that no bubbles would enter. Furthermore, the support of the film was rubbed with a commercially available plastic ruler.

  In the state as described above, after storing overnight (about 15 hours) under the condition of a temperature of 25 ° C. and a humidity of 60%, further storing in a thermostatic bath of a temperature of 90 ° C. and a humidity of 0% for 5 hours, and then removing the SUS plate, Furthermore, it was stored for 2 hours under conditions of a temperature of 25 ° C. and a humidity of 60%.

<Peel test>
Hold the edge of the coated longitudinal direction of one optical anisotropic film by hand, tilt the optical anisotropic film in the direction of 90 degrees as much as possible with respect to the SUS plate, and pull it upwards for 5 seconds. The adhesive part of the anisotropic film was peeled off.

<Adhesive evaluation of liquid crystal layer>
About the sample after peeling, five steps were evaluated by the peeling area of the optically anisotropic layer in the adhesive part of an optically anisotropic film and an adhesive sheet.

  ◎ when the optically anisotropic layer is not peeled at all, ○ when the peeled area is ~ 5%, △ when 10%, × when ~ 25%, XX when ~ 50% The case where 50% or more was peeled was defined as xxx.

<Polarizer adhesion>
<Preparation of polarizing plate>
(Alkaline saponification treatment)
Under the conditions described below, an optically anisotropic film 1 with a peelable protective film (PET) attached to the liquid crystal layer and a Konica Minolta Op KC4UYSW film with a peelable protective film (PET) attached to one side. An alkali saponification treatment was performed. Further, after the alkali saponification treatment, the protective film was peeled off and bonded to the polarizing film as described below to produce a polarizing plate.

Saponification step 2.5M-NaOH 50 ° C. 90 seconds Water washing step Water 30 ° C. 45 seconds Neutralization step 10 parts HCl 30 ° C. 45 seconds Water washing step Water 30 ° C. 45 seconds Water treatment, neutralization, water washing in this order And then dried at 80 ° C.

(Preparation and bonding of polarizing film)
A 120 μm-thick long roll polyvinyl alcohol film was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 6 times at 50 ° C. in the film forming direction to prepare a polarizing film.

  Next, using a polyvinyl alcohol adhesive, a KC4UYSW film saponified on one side of the polarizing film so that the transmission axis of the polarizing film and the in-plane slow axis of the film are parallel to each other is optically separated on the opposite side. A polarizing film 1 was prepared by laminating an anisotropic film 1.

  Similarly, polarizing plates 2 to 13 were produced using the optical anisotropic films 2 to 13.

  The obtained polarizing plate was evaluated by the following method.

<Adhesion after saponification>
Evaluation was made according to the following criteria.

◎: Does not peel at all after drying ○: After drying, it can be peeled off if it is pulled strongly by hand △: After drying, it peels off with a weak force ×: After bonding, after a while, it peels off spontaneously XX: Unbonded Possible <Adhesion between liquid crystal layer and glass surface>
The adhesion of each optical anisotropic film to the glass surface was evaluated as follows.

  The liquid crystal layer surface of the polarizing plate prepared using the optically anisotropic film and the glass were bonded together with an adhesive tape (No. 31B manufactured by Nitto Denko Corporation) for 2 weeks in an environment of 80 ° C. and 90% RH. After leaving, the state of pasting was visually evaluated according to the following criteria.

○: No peeling can be confirmed Δ: Peeling can be confirmed in a part of the four sides ×: Peeling can be confirmed in the four sides

  As can be seen from Table 1, by using the fluorine-siloxane graft polymer according to the present invention, coating unevenness can be improved and alignment defects can be suppressed, adhesion with a pressure-sensitive adhesive is excellent, adhesion with a polarizer, glass surface It has been found that it is possible to provide an optically anisotropic film having no problem with the adhesive property.

Example 2
<Production of liquid crystal display devices 1 to 13>
(Production of liquid crystal cell and liquid crystal display devices 1 to 13)
A polyimide alignment film was provided on a glass substrate on which an ITO transparent electrode was provided, and a rubbing treatment was performed. Two glass substrates were stacked with a 4.3 μm spacer so that the alignment films face each other. The two glass substrates were arranged so that the rubbing directions of the alignment film were orthogonal. A rod-like liquid crystalline molecule (ZLI-4792, manufactured by Merck & Co., Inc.) is injected into the gap between the substrates, and the optically anisotropic films 1 to 13 are formed of the above-prepared polarizing plates on both sides of the TN liquid crystal cell produced as described above. TN type liquid crystal display devices 1 to 13 were prepared by using an adhesive so as to be on the cell side and pasting so that the transmission axes of the viewing side and the backlight side polarizing plate were orthogonal to each other.

  As a result of visual evaluation of the visibility as a liquid crystal display device, the polarizing plate produced from the optically anisotropic film of the present invention showed display properties excellent in viewing angle, gradation inversion, color shift, and blur. Thereby, it was confirmed that it is excellent as a polarizing plate for an image display device such as a liquid crystal display.

Example 3
In the same manner as in Example 1 except that the polymerizable liquid crystal compound A and polymerizable liquid crystal compound B used in Example 1 were dried at 120 ° C. for 30 seconds and then aligned for 30 seconds after using the following discotic compound. Thus, when an optically anisotropic film, a polarizing plate, and a liquid crystal display device were produced, it was found that a liquid crystal display device excellent in contrast in addition to viewing angle, gradation inversion, color shift, and blur was obtained.

Example 4
An optically anisotropic film was prepared in the same manner except that the cellulose ester of the cellulose ester film prepared in Example 1 was changed to diacetylcellulose (Eastman Chemical, CA-394-60S). As a result, it was found that the optically anisotropic film of the present invention has excellent adhesiveness because both of the polarizer adhesive properties are ◎.

DESCRIPTION OF SYMBOLS 10 Optical anisotropic film 11 Film base material 12 Functional layer 13 Liquid crystal aligning layer 14 Liquid crystal layer 15 1st intermediate layer 16 2nd intermediate layer 20 Optical anisotropic film manufacturing apparatus 21 Unwinding apparatus 22 Coating apparatus 23 1st temperature Adjustment device 24 Second temperature adjustment device 25 Curing device 26 Winding device 31, 41 Resin film manufacturing device 32 Endless belt support 33, 43 Casting die 34, 47 Peeling roller 35, 49 Stretching device 36 Drying device 37, 50 Winding device 38 Dope 42 First cooling roller 44 Touch roller 45 Second cooling roller 46 Third cooling roller 48 Conveying roller

Claims (7)

In an optically anisotropic film formed by laminating a liquid crystal alignment layer and a liquid crystal layer on a film substrate,
The liquid crystal layer contains a fluorine-siloxane graft polymer and a polymerizable liquid crystal compound, the polymerizable liquid crystal compound is inclined with respect to the thickness direction of the liquid crystal layer, and is fixed in an inclined state ; and
Optically anisotropic, characterized in that the fluorine-siloxane graft polymer is a copolymer obtained by reacting a fluorine resin having a radical polymerizable unsaturated bond moiety via a urethane bond and a one-terminal radical polymerizable polysiloxane. Sex film. 2. The optically anisotropic film according to claim 1, wherein the fluorine-siloxane graft polymer is contained in an amount of 0.01 to 1% by mass with respect to the polymerizable liquid crystal compound. The optically anisotropic film according to claim 1 or 2, wherein the polymerizable liquid crystal compound, characterized in that it comprises a discotic compound. The optically anisotropic film according to any one of claims 1 to 3 , wherein the liquid crystal layer contains a photopolymerization initiator in an amount of 0.1 to 30% by mass with respect to the polymerizable liquid crystal compound. The optically anisotropic film according to any one of claims 1 to 4 , wherein the film base material contains diacetylcellulose having an acetyl group substitution degree of 2.1 to 2.6. A polarizing plate comprising the optically anisotropic film according to any one of claims 1 to 5 on at least one surface of a polarizer. A twisted nematic liquid crystal display device comprising the polarizing plate according to claim 6 on at least one surface of a liquid crystal cell.

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