KR102497981B1 - Viewing angle compensation film, manufacturing method for the viewing angle compensation film, polarizing plate, liquid crystal display device, and organic el element - Google Patents

Abstract

To provide a polymer composition for a viewing angle compensation film capable of obtaining a viewing angle compensation film having a high effect of improving display quality of a liquid crystal display device, as an optically anisotropic layer, a first optically anisotropic layer (12) and a first optically anisotropic layer ( Liquid crystal in the viewing angle compensation film (10) provided with a second optically anisotropic layer (13) different from 12), wherein the first optically anisotropic layer (12) has a liquid crystal alignment film (14) and a liquid crystal layer (15) In the polymer composition for a viewing angle compensation film for forming the alignment film 14, polyorganosiloxane is contained in the composition as a polymer component.

Description

Viewing angle compensation film, manufacturing method of viewing angle compensation film, polarizing plate, liquid crystal display element and organic EL element

The present invention relates to a polymer composition for a viewing angle compensation film, a viewing angle compensation film, a method for producing a viewing angle compensation film, a polarizing plate, a liquid crystal display element, and an organic EL element.

Conventionally, as a liquid crystal display element, various types of drive methods having different electrode structures, physical properties of liquid crystal molecules used, manufacturing processes, etc. have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA BACKGROUND ART Various types of liquid crystal display elements, such as a (vertical alignment) type, an in-plane switching (IPS) type, and a fringe field switching (FFS) type, are known.

Various optical materials are used for display devices such as liquid crystal displays. For example, a viewing angle compensation film (retardation film) is used for the purpose of eliminating coloration of display or eliminating viewing angle dependence that display color and contrast ratio change depending on viewing direction. In recent years, in order to further improve the display quality in liquid crystal displays and the like, various viewing angle compensation films have been proposed (for example, see Patent Document 1).

Patent Literature 1 discloses a viewing angle compensation film comprising a first optically anisotropic layer and a second optically anisotropic layer formed on the surface of the first optically anisotropic layer. The first optically anisotropic layer in the film has a structure in which the liquid crystal compound is fixed in a homogeneous alignment state, and the second optically anisotropic layer has a configuration in which the liquid crystal compound is fixed in a homeotropic alignment state. Further, Patent Literature 1 describes that a first optically anisotropic layer may be formed on the surface of an alignment film formed on a support. Patent Literature 1 describes that it is preferable to use denatured or unmodified polyvinyl alcohol as a material for the alignment film.

International Publication No. 2015/008773

"UV curable liquid crystal and its applications", Liquid Crystal, Vol. 3, No. 1 (1999), pp34-42

When the orientation of liquid crystal molecules is controlled using a liquid crystal alignment film made of polyvinyl alcohol, and thus optical anisotropy is expressed, the controllability of orientation of the liquid crystal molecules is low, and the effect of expanding the viewing angle of the liquid crystal display and the improvement of display color I am concerned about not being able to fully obtain the effect.

One object of the present invention is to provide a polymer composition for a viewing angle compensation film capable of obtaining a viewing angle compensation film having a high effect of improving the display quality of a liquid crystal display device.

In order to achieve the subject of the prior art as described above, the inventors of the present invention intensively examined and found that the subject could be solved by forming a liquid crystal alignment film included in a viewing angle compensation film using a specific polymer. Specifically, the following means are provided.

[1] A viewing angle compensation film comprising a first optically anisotropic layer and a second optically anisotropic layer different from the first optically anisotropic layer as the optically anisotropic layer, wherein the first optically anisotropic layer includes a liquid crystal alignment film and a liquid crystal layer. A polymer composition for a viewing angle compensation film for forming the liquid crystal alignment film in the above, containing a polyorganosiloxane as a polymer component.

[2] A viewing angle compensation film comprising a first optically anisotropic layer as an optically anisotropic layer and a second optically anisotropic layer different from the first optically anisotropic layer, wherein the first optically anisotropic layer comprises a liquid crystal alignment film and a liquid crystal layer and wherein the liquid crystal alignment layer contains polyorganosiloxane.

[3] A method for producing a viewing angle compensation film comprising a first optically anisotropic layer as an optically anisotropic layer and a second optically anisotropic layer different from the first optically anisotropic layer, wherein the polymer composition for a viewing angle compensation film according to [1] above A step of forming a liquid crystal alignment film of the first optically anisotropic layer by forming a coating film and irradiating the coating film with light, and applying a polymerizable liquid crystal to the surface of the liquid crystal alignment film and curing the first optically anisotropic layer. A method for producing a viewing angle compensation film comprising a step of forming a liquid crystal layer of a layer.

[4] A polarizing plate provided with the viewing angle compensation film of said [2] and a polarizer.

[5] A liquid crystal display element provided with the viewing angle compensation film of the above [2].

[6] An organic EL device provided with the viewing angle compensation film of [2] above.

By containing polyorganosiloxane as a polymer component in a polymer composition for forming a liquid crystal alignment film for a viewing angle compensation film having a first optically anisotropic layer and a second optically anisotropic layer, the liquid crystal orientation of the optically anisotropic layer is good, In addition, a viewing angle compensation film having excellent contrast can be obtained. Therefore, the viewing angle compensation film of the present invention has a high effect of improving the display quality of liquid crystal display elements and organic EL elements, and therefore can be suitably used in image display fields and the like.

1 is a schematic configuration diagram showing an example of a viewing angle compensation film.
Figure 2 is a schematic configuration diagram showing another example of a viewing angle compensation film.
3 is a schematic configuration diagram showing an example of a polarizing plate.
4 is a schematic configuration diagram showing another example of a polarizing plate.
5 is a schematic configuration diagram showing an example of a liquid crystal display element;
6 is a schematic configuration diagram showing another example of a viewing angle compensation film.
7 is a schematic configuration diagram showing another example of a viewing angle compensation film.
8 is a schematic configuration diagram showing another example of a viewing angle compensation film.

《Viewing Angle Compensation Film》

(First Embodiment)

Hereinafter, the viewing angle compensation film of the present disclosure will be described with appropriate reference to drawings. In addition, in each embodiment below, the same code|symbol is attached|subjected to the mutually same or equivalent part in drawing, and about the part of the same code|symbol, the description is used. As shown in FIG. 1 , the viewing angle compensation film of the present disclosure includes a first optically anisotropic layer 12 and a second optically anisotropic layer 13 different from the first optically anisotropic layer 12 as the optically anisotropic layer. are equipped In the first embodiment, in the viewing angle compensation film 10 of FIG. 1 , a first optically anisotropic layer 12 and a second optically anisotropic layer 13 are laminated on one surface of a substrate 11 .

As the base material 11, a film made of a material that is transparent and has low optical anisotropy can be preferably used. Specifically, for example, cellulose acylate, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyethersulfone, polyamide, polyimide, poly(meth)acrylate, polymethyl methacrylate, polycarbonate and films made of synthetic resins such as cyclic polyolefins. Among these materials, cellulose acylate is preferred, and cellulose acetate is more preferred. In addition, in the aspect in which the base material 11 also serves as a polarizer, you may use polyvinyl alcohol. Regarding the substrate 11 to be used, in order to improve the adhesion between the substrate surface and the optically anisotropic layer (first optically anisotropic layer 12 in FIG. 1 ), the surface on which the optically anisotropic layer is formed is subjected to saponification treatment or the like. A conventionally known preprocessing may be performed.

The first optically anisotropic layer 12 is provided on one surface of the substrate 11 and includes a liquid crystal alignment film 14 and a liquid crystal layer 15 . The liquid crystal alignment film 14 is formed on the substrate 11 using a polymer composition for viewing angle compensation films. In addition, a polymer composition for a viewing angle compensation film will be described later. The film thickness of the liquid crystal aligning film 14 formed on the base material 11 is preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

The liquid crystal layer 15 is a coating film containing liquid crystal molecules, and is provided adjacent to the liquid crystal alignment film 14 . This liquid crystal layer 15 is formed using a liquid crystal composition containing polymerizable liquid crystal. As a polymerizable liquid crystal, a conventionally well-known thing can be used. Specifically, for example, the nematic liquid crystal compounds described in Non-Patent Document 1 (“UV curable liquid crystal and its application”, liquid crystal, Vol. 3, No. 1 (1999), pp 34 to 42) are exemplified. there is. Further, cholesteric liquid crystals; discotic liquid crystals; twisted nematic orientation type liquid crystals to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds, or may be a composition containing a known polymerization initiator, suitable solvent, or the like. The thickness of the liquid crystal layer 15 is appropriately set depending on the desired optical properties and the optical properties of the polymerizable liquid crystal to be used, but is set within a range of, for example, 0.1 to 1.5 μm.

The second optically anisotropic layer 13 is laminated on the first optically anisotropic layer 12, and in FIG. 1 , the first optically anisotropic layer 12 is sandwiched between the liquid crystals on the side opposite to the substrate 11 It is provided adjacent to the layer 15. The aspect of the second optically anisotropic layer 13 is not particularly limited as long as it has optical anisotropy. Specifically, it may be formed using a composition containing a liquid crystal compound, may be formed using a composition containing a polymer, or may be formed by sticking a stretched film. Moreover, a polarizer may be sufficient and the structure which consists of a liquid crystal aligning film and a liquid crystal layer may be sufficient.

In the aspect in which the second optically anisotropic layer 13 is formed using a composition containing a liquid crystal compound, the liquid crystal compound contained in the composition may be a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound. Moreover, as a liquid crystal phase of a liquid crystal compound, a smectic phase, a nematic phase, etc. are mentioned. The liquid crystal compound for forming the second optically anisotropic layer may be appropriately selected according to the liquid crystal compound used for forming the first optically anisotropic layer 12 . Specifically, for example, the liquid crystal compound used for forming the second optically anisotropic layer 13 may be in the same liquid crystal phase as the liquid crystal compound used for forming the first optically anisotropic layer 12, or It is good also as a liquid crystal phase different from the liquid crystal compound used for formation of the optically anisotropic layer 12. Moreover, you may use a polymeric liquid crystal as a liquid crystal compound. As a liquid crystal compound, only 1 type may be used and you may use in combination of 2 or more type. The composition for forming the second optically anisotropic layer may further contain a polymerization initiator, a polymerizable compound, a solvent, a vertical alignment agent and the like as needed.

In the aspect in which the second optically anisotropic layer 13 is formed of a stretched film, as a material for the stretched film, a polymer exhibiting birefringence when stretched can be used, and examples thereof include poly(meth)acrylate, polycarbonate, Polystyrene, polyester, polyolefin, cellulose derivative, polyurethane, etc. are mentioned. These materials can be used individually by 1 type or in combination of 2 or more types. The weight average molecular weight of the polymer forming the second optically anisotropic layer 13 is, for example, preferably 1,000 to 300,000, more preferably 5,000 to 250,000, still more preferably 10,000 to 200,000. The stretching treatment may be uniaxial stretching or biaxial stretching. Arbitrary appropriate methods can be employed for the stretching method. The stretching ratio may be appropriately set according to the desired retardation value and the thickness of the film, but may be, for example, 1.1 to 3.0 times. The thickness of the second optically anisotropic layer 13 may be appropriately set according to the intended retardation, but is preferably 0.3 to 3.0 µm, and more preferably 0.5 to 2.8 µm.

In the aspect where the second optically anisotropic layer 13 is a polarizer, a conventionally known polarizer can be used. For example, a polarizing film in which iodine is absorbed while polyvinyl alcohol is stretched orientated, and the polarizing film is a cellulose acetate protective film A polarizing film sandwiched therebetween is exemplified. In addition, when the second optically anisotropic layer 13 is used as a polarizer, the viewing angle compensation film 10 has a configuration in which the base material 11 is not provided by forming the first optically anisotropic layer 12 on one side of the polarizer. You may (see FIG. 6).

In the aspect in which the second optically anisotropic layer 13 is composed of a liquid crystal alignment film and a liquid crystal layer, the description of the first optically anisotropic layer is applied to the liquid crystal alignment film, and the second optically anisotropic layer 13 is applied to the liquid crystal layer. The description of the case of formation using a composition containing a compound applies.

In addition to optical anisotropy, the second optically anisotropic layer 13 may further have physical properties of A), B) or C) below.

A) It has positive birefringence.

B) The moisture permeability at 40°C and 90% relative humidity according to JIS Z-0208 is 200 g/m 2 /day or less.

C) The modulus of elasticity is 4.2 GPa or more.

In order to express the physical properties of A) in the second optically anisotropic layer 13, for example, (A1) a method of forming a layer so that the liquid crystal compound has a predetermined tilt angle using a composition containing a liquid crystal compound; (A2) Positive A stretching treatment may be applied to a film formed using a polymer exhibiting intrinsic birefringence, and the film may be bonded together.

Specifically, as (A1), a method for controlling the alignment state of a liquid crystal compound by blending a tilt angle control agent in a composition containing the liquid crystal compound; a liquid crystal compound by the influence of the interface with the first optically anisotropic layer 12 A method of controlling the orientation state of As a tilt angle control agent, the polymer etc. which have a fluoro aliphatic group are mentioned, for example. As a specific example of such a tilt angle control agent, the compound of Unexamined-Japanese-Patent No. 2008-257205 and Unexamined-Japanese-Patent No. 2006-91732 etc. are mentioned, for example. Tilt angle control agents can be used individually by 1 type or in combination of 2 or more types.

Examples of the "polymer exhibiting positive intrinsic birefringence" in (A2) include cycloolefin-based polymers, cellulose derivatives, and (meth)acrylic-based polymers having a ring structure in the main chain.

In the case where the second optically anisotropic layer 13 has positive birefringence, the first optically anisotropic layer 12 only needs to be capable of obtaining desired optical characteristics in combination with the second optically anisotropic layer 13. , may have positive birefringence or may have negative birefringence.

When the second optically anisotropic layer 13 has the physical property of B) above, it is preferable in that penetration of moisture into the liquid crystal cell can be suppressed and display unevenness can be reduced. Moreover, it is preferable also from the point which can improve the reliability and durability of a liquid crystal cell, and the point which can suppress the curvature of a liquid crystal cell. The water vapor transmission rate of the second optically anisotropic layer 13 is preferably 100 g/m 2 /day or less, more preferably 90 g/m 2 /day or less, still more preferably 50 g/m 2 /day or less.

As one aspect for expressing the physical properties of B) in the second optically anisotropic layer 13, (B1) the second optically anisotropic layer 13 is formed by using a composition containing a polymerizable compound having an alicyclic hydrocarbon group. The method of forming, or the method of forming using the composition containing (B2) cyclic olefin type-resin, etc. are mentioned. In addition, the composition used for forming the second optically anisotropic layer 13 may further contain a polymerization initiator, light-transmitting particles, a fluorine-containing or silicone compound, a solvent, and the like as needed.

Here, in the case of the above (B1), examples of the alicyclic hydrocarbon group of the polymerizable compound include a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, a pentacyclopentadecanyl group, an adamantyl group, and a diamantyl group. A damantanyl group etc. are mentioned. Examples of the polymerizable group in the polymerizable compound include a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group, and among these, a (meth)acryloyl group is preferable.

As cyclic olefin resin in the case of said (B2), the polymer of Unexamined-Japanese-Patent No. 2008-58473 etc. can be used, for example.

In the above (B1) and (B2), a composition containing a polymeric compound or a cyclic olefin polymer is applied to the surface of the first optically anisotropic layer 12, preferably dried, and then light or heat is used. It is preferable to form the target second optically anisotropic layer 13 by curing the layer.

When the second optically anisotropic layer 13 has physical properties of C), the obtained viewing angle compensation film 10 has a high elastic modulus and excellent rigidity. Therefore, when the viewing angle compensation film is stored in a roll shape, it is suitable from the viewpoint that deformation of the roll surface into an irregular shape can be suppressed. In addition, since the obtained viewing angle compensation film 10 exhibits low birefringence, it has excellent optical performance.

The modulus of elasticity of the second optically anisotropic layer 13 is preferably 4.3 GPa or more, more preferably 4.5 GPa or more, from the viewpoint of sufficiently obtaining the above effects. In addition, the modulus of elasticity is measured by measuring the stress at 0.5% elongation at a tensile rate of 10%/min in an atmosphere of 23°C and 60% relative humidity using a tensile tester (STM T50BP, manufactured by Toyo Baldwin Co., Ltd.), MD. and a value measured as an average value of tensile modulus of TD.

One aspect for expressing the physical properties of C) in the second optically anisotropic layer 13 is a composition comprising a polyester having an alicyclic backbone and having a hydroxyl group having a hydrogen atom substituted with an acyl group derived from monocarboxylic acid. to form the second optically anisotropic layer 13. As such an acyl group-substituted polyester, the polymer of Unexamined-Japanese-Patent No. 2015-18162 etc. can be used, for example.

(Second Embodiment)

Next, the viewing angle compensation film of the second embodiment will be mainly described with respect to differences from the first embodiment. As shown in FIG. 2 , in the viewing angle compensation film 10 of the second embodiment, the second optically anisotropic layer 13 is disposed on the contact surface with the first optically anisotropic layer 12, and , and a functional layer 13A exhibiting optical anisotropy by orientation of liquid crystal molecules, and thereby the second optically anisotropic layer 13 has reverse wavelength dispersion. With such a structure, when applied to a liquid crystal display element or an organic EL element, it becomes possible to realize a higher contrast.

In the viewing angle compensation film 10 of FIG. 2 , the first optically anisotropic layer 12, the intermediate layer 16, and the functional layer 13A are disposed adjacent to each other in this order on one surface of the substrate 11. The middle layer 16 is typically a layer containing a polymer. The polymer is not particularly limited, but from the viewpoint of increasing adhesion to the functional layer 13A and forming a thin and smooth film capable of realizing homogeneous orientation of the functional layer 13A, a (meth)acrylic polymer, A bromine-containing polymer, a styrene-acrylonitrile-(N-phenylmaleimide) terpolymer, a modified styrene polymer composed of p-hydrostyrene or the like is preferred, and a (meth)acrylic polymer is particularly preferred. It is preferable to set it as 30 weight% or more with respect to the total amount of components contained in a layer, and, as for the content rate of these preferable polymers, it is more preferable to set it as 40 weight% or more. In addition, the intermediate layer 16 is preferably not subjected to orientation treatment.

The intermediate layer 16 preferably contains a component having at least one of a polar group and a polymerizable group, and more preferably contains a polar group and a polymerizable group in the same or different components, and the polymer constituting the intermediate layer 16 Those having a polar group and a polymerizable group are particularly preferred. From the viewpoint of high adhesion to the optically anisotropic layer, the polar group is preferably a hydroxyl group, and the polymerizable group is preferably a (meth)acryloyl group. The thickness of the intermediate layer 16 is preferably 0.3 to 3.0 μm, and more preferably 0.5 to 2.8 μm, from the viewpoint of making the viewing angle compensation film express reverse wavelength dispersion.

When the second optically anisotropic layer 13 exhibits reverse wavelength dispersion, the second optically anisotropic layer 13 preferably satisfies Equation (1) below.

Re(450)/Re(650)<1　　　... (One)

(In Formula (1), Re (450) represents in-plane retardation at a wavelength of 450 nm, and Re (650) represents in-plane retardation at a wavelength of 650 nm.)

In addition, in-plane retardation in wavelength (gamma) is a value computed according to the method described in Unexamined-Japanese-Patent No. 2015-43073.

(another embodiment)

1, a first optically anisotropic layer 12 is disposed on a substrate 11, and a second optically anisotropic layer 13 is formed on the surface of the first optically anisotropic layer 12 opposite to the substrate 11 Although the structure of disposing is shown, the lamination order of the 1st optically anisotropic layer 12 and the 2nd optically anisotropic layer 13 is not limited to this. For example, the second optically anisotropic layer 13 is disposed on the substrate 11, and the first optically anisotropic layer 12 is formed on the surface of the second optically anisotropic layer 13 opposite to the substrate 11. It is good also as an arrangement structure (refer FIG. 8).

<<Polymer composition for viewing angle compensation film>>

Next, components to be blended in the polymer composition for a viewing angle compensation film (hereinafter also simply referred to as "polymer composition") for forming the liquid crystal alignment film for a viewing angle compensation film of the present disclosure, and other components optionally blended as needed explain about.

<Polymer component>

(Polyorganosiloxane)

The polymer composition of the present disclosure contains polyorganosiloxane as a polymer component. The said polyorganosiloxane can be obtained by hydrolyzing and condensing a hydrolysable silane compound, for example.

Specific examples of the silane compound are not particularly limited as long as they exhibit hydrolysis, and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and phenyltrie. alkoxysilanes such as oxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane;

3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- nitrogen/sulfur containing alkoxysilanes such as (3-cyclohexylamino)propyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane;

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, etc. silane;

3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 3-(meth) Alkoxysilanes containing unsaturated bonds such as acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane; In addition, trimethoxysilylpropyl succinic acid anhydride etc. are mentioned. A silane compound can be used individually by these 1 type or in combination of 2 or more types.

The hydrolysis/condensation reaction of the silane compound is carried out by reacting one or more of the above silane compounds and water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis/condensation reaction, the proportion of water used is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, relative to 1 mole of the silane compound (total amount). As a catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. are mentioned, for example. The amount of catalyst used differs depending on the type of catalyst, reaction conditions such as temperature, etc., and should be set appropriately. ~1 fold mole.

Examples of the organic solvent include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use a water-insoluble or sparingly water-soluble organic solvent. The proportion of the organic solvent used is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight in total of the silane compounds used in the reaction.

It is preferable to carry out the above hydrolysis/condensation reaction by heating, for example, in an oil bath or the like. In the case of a hydrolysis/condensation reaction, it is preferable to set heating temperature to 130 degreeC or less, and it is more preferable to set it as 40-100 degreeC. It is preferable to set it as 0.5 to 12 hours, and, as for heating time, it is more preferable to set it as 1 to 8 hours. During heating, the liquid mixture may be stirred or may be placed under reflux. After completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction solution with water. In this washing, washing with water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight, etc.) is preferred in view of facilitating the washing operation. Washing is performed until the water layer after washing becomes neutral, and thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to obtain the target poly Organosiloxanes can be obtained. In addition, the synthesis method of polyorganosiloxane is not limited to the said hydrolysis/condensation reaction, You may carry out, for example, the method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

It is preferable that the polyorganosiloxane to be contained in the polymer composition of the present disclosure is a polymer having an optical orientation group. The alignment of the liquid crystal molecules in the first optically anisotropic layer 12 is precisely controlled by using such an optical orientation group-containing polyorganosiloxane as at least a part of the polymer components in the polymer composition for the viewing angle compensation film. can do.

The photo-orientable group of the polyorganosiloxane is a functional group that imparts anisotropy to the film by a photo-isomerization reaction, a photo-dimerization reaction, or a photolysis reaction by light irradiation. Specific examples of the photo-alignable group include, for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof as a basic skeleton, and a chalcone or derivative thereof as a basic skeleton. a chalcone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, a polyimide-containing structure containing polyimide or a derivative thereof as a basic skeleton etc. can be mentioned. Among these, the photo-orientable group possessed by the polyorganosiloxane is preferably a group containing a cinnamic acid structure composed of cinnamic acid or a derivative thereof from the viewpoint of having high orientation ability and being easily introduced into a polymer.

As a group containing a cinnamic acid structure, for example, a monovalent group obtained by removing a hydrogen atom from a carboxyl group of cinnamic acid or a group in which a substituent is introduced into the benzene ring of the monovalent group (hereinafter, these are referred to as “pure” groups). Also referred to as "cinnamate group"), a monovalent group in which the carboxyl group of cinnamic acid is esterified and a divalent organic group is bonded to a benzene ring, or a group in which a substituent is introduced into the benzene ring of the monovalent group (hereinafter , these are also referred to as "inverse cinnamate groups"). A forward cinnamate group can be represented by, for example, the following formula (cn-1), and a reverse cinnamate group can be represented by, for example, the following formula (cn-2).

(In formula (cn-1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R ² is a phenylene group, a biphenylene group, a ter A phenylene group or a cyclohexylene group, or at least a part of the hydrogen atoms of these groups are substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or at least a part of the hydrogen atoms of the alkoxy group is substituted with a halogen atom A ¹ is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, -CH=CH-, -NH-, * ¹ -COO, * ¹ -OCO-, * ¹ -NH-CO-, * ¹ -CO-NH-, * ¹ -CH ₂ -O- or * ¹ -O-CH ₂ - (“* ¹ ” indicates a bond with R ² R ³ is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group, a is 0 or 1, and b is an integer of 0 to 4. Here, b When is 2 or more, a plurality of R ³ 's may be the same or different, and "*" indicates a bond.

In formula (cn-2), R ⁴ is an alkyl group having 1 to 3 carbon atoms. R ⁵ is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. A ² is an oxygen atom, * ¹ -COO-, * ¹ -OCO-, * ¹ -NH-CO-, or * ¹ -CO-NH- (“* ¹ ” represents a bond with R ⁶ ). . R ⁶ is an alkanediyl group having 1 to 6 carbon atoms. c is 0 or 1, and d is an integer from 0 to 4. However, when d is 2 or more, a plurality of R ⁵ may be the same or different. "*" indicates that it is a bonding hand.)

As a specific example of the group represented by the said formula (cn-1), for example, the following formula

(In the above formula, "*" indicates a bond);

As a specific example of the group represented by the said formula (cn-2), for example, the following formula

(In the above formula, "*" indicates a bonding hand)

Groups represented by each of;

The method of synthesizing the polyorganosiloxane having an optical orientation group is not particularly limited. For example, the method by the following [1a] or [2a], etc. are mentioned.

[1a] An epoxy group-containing polyorganosiloxane is synthesized by hydrolytic condensation of an epoxy group-containing alkoxysilane or a mixture of an epoxy group-containing alkoxysilane and other silane compounds, and then, the resulting epoxy group-containing polyorganosiloxane and light A method of reacting a carboxylic acid (hereinafter also referred to as "specific carboxylic acid") having an orientation group.

[2a] A hydrolytic condensation of a hydrolyzable silane compound having an optical orientation group or a mixture of the silane compound and other silane compounds.

Among these, the [1a] method is convenient and preferable from the viewpoint of being able to increase the introduction rate of the photo-alignable group in the polyorganosiloxane.

Regarding the method of [1a], the epoxy equivalent of the epoxy group-containing polyorganosiloxane is from 100 to 100, from the viewpoint of suppressing side reactions caused by excessive amounts of epoxy groups while enabling sufficient introduction of photo-alignable groups into the polymer. It is preferably 10,000 g/mol, and more preferably 150 to 1,000 g/mol. Therefore, in synthesizing the epoxy group-containing polysiloxane, it is preferable to adjust the use ratio of the epoxy group-containing alkoxysilane so that the epoxy equivalent of the obtained polymer falls within the above range.

In the method of [1a], the obtained epoxy group-containing polyorganosiloxane is then reacted with a specific carbonic acid. In this way, the epoxy group of the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain a polyorganosiloxane having an optical orientation group.

Although a specific carboxylic acid is not specifically limited if it has a photoreactive group, It is preferable that it is a carboxylic acid which has a group containing a cinnamic acid structure as a photo-alignment group. Examples of such a specific carboxylic acid include carboxylic acids in which a hydrogen atom is bonded to a portion of a bond in a group represented by each of the formulas (cn-1) and (cn-2). More specifically, for example, each group listed as a specific example of the group represented by the formula (cn-1) and the bond in each group listed as a specific example of the group represented by the formula (cn-2) carbonic acid having a hydrogen atom bonded thereto; and the like. A specific carbonic acid can be used individually by 1 type or in combination of 2 or more types.

In addition, for the compound in which a hydrogen atom is bonded to the bond of the group represented by each of the formulas (cn-1) and (cn-2), the synthesis method is not particularly limited, and conventionally known methods are combined. can be synthesized. As a typical synthetic method, for example, a method in which a compound having a benzene ring skeleton substituted with a halogen atom is reacted with (meth)acrylic acid or a derivative thereof in the presence of a transition metal catalyst under basic conditions; A method of reacting a cinnamic acid substituted with a halogen atom and a compound having a benzene ring skeleton substituted with a halogen atom in the presence of a transition metal catalyst; and the like.

In the reaction between the epoxy group-containing polyorganosiloxane and the specific carboxylic acid, a carboxylic acid having no photo-alignment group (other carboxylic acids) may be used. The other carboxylic acids to be used are not particularly limited, but examples thereof include carboxylic acids having a polymerizable group (hereinafter, also referred to as “polymerizable group-containing carboxylic acids”). In the reaction between the epoxy group-containing polyorganosiloxane and the specific carboxylic acid, polyorganosiloxane having a polymerizable group and an optical orientation group is obtained by using a polymerizable group-containing carboxylic acid in combination. In addition, using such a polyorganosiloxane for at least a part of the polymer components of the polymer composition is preferable from the viewpoint that optical performance (particularly, contrast characteristics) of the obtained viewing angle compensation film can be improved.

Examples of the polymerizable group include (meth)acryloyl group, styryl group, vinyl group, vinylidene group, vinyloxy group (CH ₂ =CH-O-), maleimide group, allyl group, ethynyl group and the like. can Among these, a (meth)acryloyl group is preferable from the viewpoint of high reactivity to light. In addition, a (meth)acryloyl group is the meaning containing an acryloyl group and a methacryloyl group.

Specific examples of the polymerizable-containing carboxylic acid include (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and phthalic acid monohydroxy. unsaturated carboxylic acids such as ethyl (meth)acrylate; unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride; there is. As a polymerizable group containing carboxylic acid, it can use individually by 1 type or in combination of 2 or more types.

As other carboxylic acids, compounds other than unsaturated bond-containing carboxylic acids can also be used as needed. Examples of such other carboxylic acids include propionic acid, benzoic acid, methylbenzoic acid, and carboxylic acids having a group capable of imparting liquid crystal orientation ability to a coating film regardless of light (hereinafter also referred to as a "pretilt angle imparting group"). can be heard Examples of the pretilt angle imparting group include, for example, an alkyl group of 4 to 20 carbon atoms, a fluoroalkyl group of 4 to 20 carbon atoms, an alkoxy group of 4 to 20 carbon atoms, a group having a steroid skeleton of 17 to 51 carbon atoms, and two and groups having a structure in which the above rings are linked directly or via a linking group. In addition, other carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

In the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid, the ratio of the carboxylic acid used is 1 mole of the total number of epoxy groups of the polyorganosiloxane from the viewpoint of reducing the amount of unreacted carboxylic acid while sufficiently performing the reaction. It is preferably 0.001 to 1.5 mol, more preferably 0.01 mol or more and less than 1.0 mol, and even more preferably 0.1 to 0.8 mol.

Moreover, it is preferable to use the polyorganosiloxane made to contain in a polymer composition as a polymer which has an epoxy group in a side chain. For example, by setting the proportion of the total amount of the specific carboxylic acid and other carboxylic acids used in the reaction with the epoxy group-containing polyorganosiloxane to be less than 1.0 mol with respect to 1 mol of the total epoxy groups of the polyorganosiloxane, A polyorganosiloxane having an epoxy group and an optical orientation group can be obtained.

The proportion of specific carboxylic acids used (the total amount when two or more kinds are used) is 10 mol with respect to the total amount of carboxylic acids used in the reaction, from the viewpoint of improving the liquid-crystal orientation and contrast ratio of the obtained viewing angle compensation film. It is preferably set to % or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.

In the case of using a polymerizable group-containing carboxylic acid, the proportion thereof is preferably 1 mol% or more, more preferably 3 to 50 mol%, based on the total amount of the carboxylic acid used for the reaction. , It is more preferable to set it as 5-30 mol%.

The reaction between the epoxy group-containing polyorganosiloxane and carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, for example, a compound known as a so-called curing accelerator that promotes the reaction of an organic base or an epoxy compound can be used. Especially, a tertiary organic amine or a quaternary organic amine is preferable. The proportion of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing polyorganosiloxane.

As an organic solvent used for the said reaction, hydrocarbon, ether, ester, ketone, amide, alcohol etc. are mentioned, for example. Among these, from the viewpoint of the solubility of raw materials and products and the ease of purification of products, it is preferable to use at least one selected from the group consisting of ethers, esters and ketones, and as specific examples of particularly preferable solvents, 2- butanone, 2-hexanone, methyl isobutyl ketone, butyl acetate, and the like. The organic solvent is preferably used in such a proportion that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, and 5 to 50% by weight. It is more preferable to use it in a ratio that becomes The reaction temperature is preferably 0 to 200°C, more preferably 50 to 150°C. In addition, the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. After completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction solution with water.

The reaction solution containing the polyorganosiloxane may be used as it is for preparation of the polymer composition, or may be used for preparation of the polymer composition after isolating the polyorganosiloxane contained in the reaction solution, or the isolated polyorganosiloxane After purifying, you may use for preparation of a polymer composition. Isolation and purification of polyorganosiloxane can be performed according to known methods.

With respect to the polyorganosiloxane to be contained in the polymer composition, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably in the range of 100 to 50,000, and preferably in the range of 200 to 10,000. It is more desirable to have When the weight average molecular weight of the polyorganosiloxane is within the above range, it is easy to handle when producing the viewing angle compensation film, and the obtained film has sufficient material strength and characteristics. By using polyorganosiloxane as a polymer component of the viewing angle compensation film, the heating temperature at the time of film formation can be set to a relatively low temperature (for example, 150°C or lower). Therefore, there are few restrictions on the substrates that can be used, and it is also suitable from the viewpoint of energy saving.

(other polymers)

The polymer composition of the present disclosure may contain only polyorganosiloxane as a polymer component, but may also contain other polymers other than polyorganosiloxane. Examples of such other polymers include, but are not particularly limited to, polyamic acid, polyamic acid esters, polyimides, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, Polymers having poly(meth)acrylate or the like as the main skeleton are exemplified. In addition, (meth)acrylate means containing an acrylate and a methacrylate.

When blending other polymers, the ratio of their use is appropriately selected depending on the type of polyorganosiloxane, but it is preferably 90 parts by weight or less with respect to 100 parts by weight of the total of polyorganosiloxane and other polymers. , more preferably 80 parts by weight or less.

The polymer composition of the present disclosure preferably contains a component having an optical orientation group and a polymerizable group in the same or different molecules. When a polymer composition contains the component which has these groups, liquid-crystal orientation ability can be provided to a coating film by radiation irradiation. Also, a viewing angle compensation film having high optical performance can be obtained.

It is preferable that the component which has an optical orientation group and a polymeric group is a polymer component. As a preferable specific example in the polymer composition of this indication, the following (1) and (2) are mentioned.

(1) As a polymer component, a polymer (hereinafter also referred to as "polymer (P1)") having an optical orientation group and a polymerizable group in one molecule is included.

(2) As the polymer component, a polymer having an optical alignment group (hereinafter also referred to as "polymer (P2)") and a polymer having a polymerizable group (hereinafter also referred to as "polymer (P3)") are included.

In said (1), a polyorganosiloxane may be sufficient as polymer (P1), and other polymers other than polyorganosiloxane may be sufficient as it. Preferably, it is a polyorganosiloxane. Moreover, as polyorganosiloxane which has an optical orientation group and a polymeric group, the thing of the example demonstrated above is applicable.

When the polymer (P1) is a polyorganosiloxane, the blending ratio of the polymer (P1) is preferably 10 parts by weight or more, relative to 100 parts by weight in total of the polymer components contained in the polymer composition, and is 20 to 99 parts by weight. It is more preferable to set it as a weight part, and it is more preferable to set it as 30-90 weight part.

When the polymer (P1) is a polyorganosiloxane, the polymer composition of the present disclosure preferably further contains a polymer (P3) having a polymerizable group as other polymers. In this case, even if the usage-amount of polyorganosiloxane is reduced, the improvement effect of the contrast characteristic of the obtained viewing angle compensation film is high, and it is suitable.

The main skeleton of the polymer (P3) is not particularly limited, but is particularly preferably a polymer obtained by polymerization of a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "polymer [Pac]"). By using the polymer [Pac] together with the polyorganosiloxane, even if the amount of polyorganosiloxane used is reduced, a film having good optical properties and sufficiently high adhesion to the base material can be obtained, and the productivity is excellent. Further, by using the polymer [Pac] together, lowering of the firing temperature at the time of production and shortening of the firing time become possible, and reduction of the process load becomes possible.

The blending ratio of the polymer [Pac] in the above (1) is preferably 5 to 90 parts by weight based on 100 parts by weight of the total polymer components contained in the polymer composition from the viewpoint of improving the optical performance, It is more preferably 10 to 85 parts by weight, and even more preferably 20 to 80 parts by weight.

In the case of said (2), it is preferable that polymer (P2) is polyorganosiloxane. The above description is applicable to the polyorganosiloxane having an optical orientation group. The polymer (P3) may be polyorganosiloxane or other polymers other than polyorganosiloxane, but is preferably other polymers. Especially, the polymer (P3) is a polymer [Pac], and it is preferable that the polymer [Pac] has a polymerizable group in the side chain.

In the above (2), the content of the polymer (P2) is preferably 10 to 99 parts by weight, more preferably 20 to 90 parts by weight, based on 100 parts by weight of the total polymer components contained in the polymer composition. do. The content of the polymer (P3) is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the total polymer components contained in the polymer composition.

(Polymer [Pac])

Next, the polymer [Pac] is explained in detail. The monomer used in the synthesis of the polymer [Pac] is not particularly limited as long as it is a compound having a polymerizable carbon-carbon unsaturated bond, and examples thereof include (meth)acrylic compounds, aromatic vinyl compounds, conjugated diene compounds, and maleimide group-containing compounds. A compound etc. are mentioned. Among these, it is preferable that polymer [Pac] is a polymer obtained using a (meth)acrylic compound, ie, poly(meth)acrylate, from viewpoints of transparency, material strength, etc.

The poly(meth)acrylate having a polymerizable group is, for example, a (meth)acrylic monomer (ma-1) having an epoxy group, or the (meth)acrylic monomer (ma-1) and other materials not having an epoxy group. By a method of polymerizing a mixture of monomers (ma-2) in the presence of a polymerization initiator, and then reacting the obtained polymer (hereinafter, also referred to as "epoxy group-containing poly(meth)acrylate") with a polymerizable group-containing carboxylic acid. You can get it.

Examples of the (meth)acrylic monomer (ma-1) include unsaturated carboxylic acid esters having an epoxy group. Specific examples thereof include glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4 (meth)acrylate. -Epoxybutyl, α-ethylacrylate 3,4-epoxybutyl, (meth)acrylate 3,4-epoxycyclohexylmethyl, (meth)acrylate 6,7-epoxyheptyl, α-ethylacrylate 6,7-epoxyheptyl, Acrylic acid 4-hydroxybutyl glycidyl ether, (meth)acrylic acid (3-ethyloxetan-3-yl) methyl, etc. are mentioned. In addition, (meth)acrylic monomer (ma-1) can be used individually by 1 type or in combination of 2 or more types among the above.

Other monomers are not particularly limited as long as they have a polymerizable carbon-carbon unsaturated bond. Specific examples thereof include unsaturated carbon acids such as (meth)acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, and vinyl benzoic acid: methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid Propyl, (meth)acrylate aryl, (meth)acrylate cyclohexyl, (meth)acrylate benzyl, (meth)acrylate-2-ethylhexyl, (meth)acrylate lauryl, (meth)acrylate trimethoxysilylpropyl, (meth)acrylate (Methoxyethyl acrylate, (meth)acrylate-N,N-dimethylaminoethyl, (meth)acrylate methoxypolyethylene glycol, (meth)acrylate tetrahydrofurfuryl, (meth)acrylate 2-hydroxyethyl, etc. ) Acrylic compound;

Aromatic vinyl compounds, such as styrene, methylstyrene, and divinylbenzene;

Conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;

and maleimide group-containing compounds such as N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. Other monomers can be used individually by these 1 type or in combination of 2 or more types.

In the synthesis of epoxy group-containing poly(meth)acrylate, the total amount (number of moles) of epoxy groups per 1 g of polymer is preferably 5.0 × 10 ^-5 mol/g or more, from the viewpoint of sufficiently reacting with carboxylic acid, and 1.0 × It is more preferably 10 ^{−4 to} 1.0×10 ⁻² mol/g, and still more preferably 5.0×10 ^{−4 to} 5.0×10 ⁻³ mol/g. Therefore, the proportion of the (meth)acrylic monomer (ma-1) used is preferably adjusted so that the total number of moles of epoxy groups per 1 g of the epoxy group-containing poly(meth)acrylate falls within the above range.

In the above synthesis, the proportion of monomers (aromatic vinyl compounds, etc.) other than the (meth)acrylic compound is 30 mol% or less based on the total amount of monomers used in the synthesis of the epoxy group-containing poly(meth)acrylate. It is preferable, and it is more preferable to set it as 20 mol% or less.

It is preferable to carry out the said polymerization reaction by radical polymerization. Examples of the polymerization initiator used in the reaction include initiators usually used in radical polymerization, such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2,4 -Azo compounds such as dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); Benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate , organic peroxides such as 1,1'-bis(t-butylperoxy)cyclohexane; hydrogen peroxide; redox type initiators composed of these peroxides and reducing agents; and the like. Among these, an azo compound can be used preferably. As a polymerization initiator, these can be used individually by 1 type or in combination of 2 or more types. The proportion of the polymerization initiator used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the total monomers used for the reaction.

The polymerization reaction is preferably conducted in an organic solvent. As an organic solvent used for reaction, alcohol, ether, ketone, amide, ester, hydrocarbon compound etc. are mentioned, for example. Among these, it is preferable to use at least one selected from the group consisting of alcohols and ethers, and it is more preferable to use partial ethers of polyhydric alcohols. Preferred specific examples thereof include diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate and the like. In addition, as an organic solvent, these 1 type can be used individually or in combination of 2 or more types.

It is preferable to set it as 30-120 degreeC, and, as for the reaction temperature in the said polymerization reaction, it is more preferable to set it as 60-110 degreeC. It is preferable to set reaction time as 1 to 36 hours, and it is more preferable to set it as 2 to 24 hours. The amount (x) of the organic solvent used is preferably such that the total amount (y) of the monomers used in the reaction is 0.1 to 50% by weight with respect to the total amount (x+y) of the reaction solution.

Next, a polymerizable group-containing carboxylic acid is reacted with the epoxy group-containing poly(meth)acrylate obtained by the above reaction. As the polymerizable group-containing carboxylic acid to be used, the examples of the polymerizable group-containing carboxylic acid described in the synthesis of polyorganosiloxane can be applied. In the reaction, the polymerizable group-containing carboxylic acid may be used alone, or other carboxylic acids other than the polymerizable group-containing carboxylic acid may be used in combination. For specific examples of other carboxylic acids that may be used, the description of polyorganosiloxanes can be applied.

In the reaction between the epoxy group-containing poly(meth)acrylate and the polymerizable group-containing carboxylic acid, the use ratio of the polymerizable group-containing carboxylic acid (the total amount when two or more types are used) improves the contrast characteristics of the resulting viewing angle compensation film. From the point of view, it is preferably 0.001 to 1.0 mol, more preferably 0.01 to 0.8 mol, still more preferably 0.1 to 0.5 mol, based on 1 mol of the total number of epoxy groups of the epoxy group-containing poly(meth)acrylate. do.

In addition, in said (2), it is preferable that the polymer which has a polymeric group does not substantially have a photo-alignment group. Specifically, the proportion of the specific carboxylic acid used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid is preferably 1 mol% or less, and 0.5 mol based on the total amount of the carboxylic acid used in the reaction. It is more preferable to set it as % or less.

The reaction between epoxy group-containing poly(meth)acrylate and carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. Here, as a catalyst used for reaction, the catalyst etc. which were illustrated in the description of the synthesis|combination of polyorganosiloxane are mentioned. Especially, a quaternary ammonium salt can be used preferably. The amount of the catalyst used is preferably 100 parts by weight or less, more preferably 0.01 to 80 parts by weight, still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy group-containing poly(meth)acrylate.

As the organic solvent used for the reaction, examples of organic solvents that can be used in the polymerization of (meth)acrylic monomers can be applied, and among these, esters are preferable. The organic solvent is preferably used in such a proportion that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, and 5 to 50% by weight. It is more preferable to use it in a ratio that becomes The reaction temperature is preferably 0 to 200°C, and more preferably 50 to 150°C. The reaction time is preferably 0.1 to 50 hours, and more preferably 0.5 to 20 hours.

In this way, a solution containing poly(meth)acrylate having a polymerizable group can be obtained. This reaction solution may be used for preparation of the polymer composition as it is, may be used for preparation of the polymer composition after isolating the polymer contained in the reaction solution, or may be used for preparation of the polymer composition after purifying the isolated polymer. . Isolation and purification of poly(meth)acrylate can be performed according to known methods.

Regarding the poly(meth)acrylate having a polymerizable group, the number average molecular weight (Mn) in terms of polystyrene measured by GPC improves the liquid-crystal orientation of the formed film and ensures the temporal stability of the liquid-crystal orientation. From the viewpoint of doing, it is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<other ingredients>

The polymer composition of this indication may contain other components other than a polymer component as needed. As said other component, a metal chelate compound, a hardening accelerator, surfactant etc. are mentioned, for example.

[Metal chelate compound]

The metal chelate compound is a component having a catalytic action for the crosslinking reaction between epoxy structures, and is contained in the polymer composition for the purpose of accelerating the crosslinking reaction and enabling formation of a film of high hardness by heat treatment at low temperature and short time. .

As the metal chelate compound, an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium is preferable. Specifically, as an aluminum chelate compound, for example, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis(ethylacetoacetate) aluminum, isopropoxybis(acetylacetonate) aluminum, ) Aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetate bis (ethylacetoacetate) aluminum, etc.; As a chelate compound of titanium, for example, diisopropoxybis (ethylacetoacetate) Acetate) titanium, diisopropoxybis (acetylacetate) titanium, etc.; as a chelate compound of zirconium, for example, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris(ethylacetoacetate)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonate)zirconium, tetrakis(ethylacetoacetate)zirconium, and the like, respectively. As a metal chelate compound, 1 type selected from these can be used individually or in combination of 2 or more types.

As the metal chelate compound, among these, it is preferable to use an aluminum chelate compound, and 1 selected from the group consisting of diisopropoxyethylacetoacetate aluminum, tris(acetylacetonate) aluminum, and tris(ethylacetoacetate)aluminum. It is more preferable to use more than one species.

The proportion of the metal chelate compound used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, still more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total polymer components in the polymer composition. am.

[Curing accelerator]

The curing accelerator is a component contained in the polymer composition for the purpose of enhancing the catalytic action of the curing catalyst and accelerating the crosslinking reaction between epoxy structures.

As the curing accelerator, a hydrogen donor such as a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group or the like can be used, for example. Among these, a compound having a phenol group, a silanol group or a carboxyl group is preferable, and a compound having a phenol group or a silanol group is more preferable.

Specific examples thereof include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, bis(4-hydroxyphenyl)sulfone, and bis(hydroxynaphthyl) as a curing accelerator having a phenol group. Sulfone, (3-hydroxyphenyl)(4-hydroxyphenyl)sulfone, phenyl(4-hydroxyphenyl)sulfone, (methoxyphenyl)(4-hydroxyphenyl)sulfone, 4-benzylphenol, 2,2 -Bis(4-hydroxyphenyl)propane, etc.;

As the curing accelerator having a silanol group, for example, trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis(hydroxydimethylsilyl) Benzene, triphenylsilanol, tri(p-tolyl)silanol, tri(m-trifluoromethylphenyl)silanol, tri(o-trifluoromethylphenyl)silanol, tri(m-fluorophenyl)silanol , tri(o-fluorophenyl)silanol, diphenylsilanediol, di(o-tril)silanediol, and the like, respectively. Moreover, as a hardening accelerator, 1 type selected from these can be used individually or in combination of 2 or more types.

The proportion of the curing accelerator used is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less with respect to 100 parts by weight of the total polymer components in the polymer composition.

In particular, in the polymer composition of the present disclosure, it is preferable that the compounding ratio of the hydrogen donor having a silanol group is 1 part by weight or less with respect to 100 parts by weight in total of the polymer components contained in the liquid crystal aligning agent. The liquid-crystal orientation and viewing angle compensation film 10 of the first optically anisotropic layer 12 are obtained by making the polymer composition not contain a hydrogen donor having a silanol group or, even when it contains, the blending ratio thereof within a predetermined range. The contrast of can be made more favorable. The compounding ratio of the hydrogen donor having a silanol group is more preferably 0.5 part by weight or less, and still more preferably 0.1 part by weight or less with respect to 100 parts by weight in total of the polymer components contained in the liquid crystal aligning agent. Moreover, as a specific example of the hydrogen donor which has a silanol group, the compound etc. which were illustrated as a hardening accelerator which has a silanol group are mentioned.

[Surfactants]

A surfactant can be contained in the polymer composition for the purpose of improving the coating properties of the polymer composition to a substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. Moreover, as surfactant, 1 type selected from these can be used individually or in combination of 2 or more types.

The proportion of the surfactant used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the total polymer components in the polymer composition.

Further, the polymer composition may contain components other than the above within a range not interfering with the objects and effects of the present invention. Examples of such components include compounds having at least one epoxy group in the molecule, functional silane compounds, silica particles, fillers, antifoaming agents, photosensitizers, dispersants, antioxidants, adhesion aids, antistatic agents, antibacterial agents, ultraviolet absorbers, etc. can be heard In addition, these blending ratios can be appropriately set according to each compound to be blended within a range that does not impede the effects of the present invention.

[menstruum]

The polymer composition of the present disclosure is prepared as a liquid composition in which the polyorganosiloxane and other components optionally used are preferably dispersed or dissolved in a suitable solvent.

The solvent used is preferably an organic solvent, and for example, alcohols, ethers, ketones, amides, esters, hydrocarbons and the like can be suitably used. Among them, it is preferable to use at least one selected from partial esters, ethers, ketones and esters of polyhydric alcohols. Specifically, as the partial ester of the polyhydric alcohol, propylene glycol monomethyl ether; As the ester, at least one selected from ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, ethyl acetoacetate, and propylene glycol monomethyl ether acetate can be preferably used.

The use ratio of the solvent depends on the solid content concentration of the polymer composition (the total weight of all components other than the solvent in the polymer composition is It is preferable to set it as the ratio which becomes 0.2 to 10 weight%, and it is more preferable to set it as the ratio which becomes 3 to 10 weight%.

<Method of manufacturing viewing angle compensation film>

The viewing angle compensation film 10 of the present disclosure can be manufactured by a method including the following steps 1 and 2, for example.

Process 1: The process of forming a coating film using the polymer composition for viewing angle compensation films, light-irradiating the said coating film, and forming the liquid crystal aligning film 14.

Process 2: The process of forming the liquid crystal layer 15 by apply|coating polymeric liquid crystal to one surface of the liquid crystal alignment film 14, and hardening it.

(Process 1; Formation of Liquid Crystal Alignment Film)

The polymer composition described above is applied to, for example, one surface of the substrate 11 to form a coating film serving as the liquid crystal alignment film 14 . Application of the polymer composition can be by an appropriate application method. For example, roll coater method, spinner method, printing method, inkjet method, bar coater method, extrusion die method, direct gravure coater method, chamber doctor coater method, offset gravure coater method, single roll kiss coater method, small diameter gravure roll Reverse kiss coater method, 3-axis reverse roll coater method, 4-axis reverse roll coater method, slot die method, air doctor coater method, forward roll coater method, blade coater method, knife coater method, impregnation coater method, MB coater method, MB A reverse coater method or the like can be employed.

After application, the coated surface is heated (baked) to form a coating film. It is preferable to set it as 40-150 degreeC, and, as for the heating temperature at this time, it is more preferable to set it as 80-140 degreeC. It is preferable to set it as 0.1 to 15 minutes, and, as for heating time, it is more preferable to set it as 1 to 10 minutes. The film thickness of the coating film formed by the polymer composition is preferably 0.001 to 1 μm, more preferably 0.05 to 0.5 μm.

Next, the coating film formed as described above is irradiated with polarized light radiation. As the radiation to be irradiated, for example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm are exemplified. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As polarization, it is preferable to use light containing linearly polarized light. Light irradiation may be performed from a direction perpendicular to the base material surface, from an oblique direction, or may be performed in a combination thereof.

As a light source used, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a mercury-xenon lamp (Hg-Xe lamp) etc. are mentioned, for example. Polarized light can be obtained by a means of using these light sources in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 0.1 to 1,000 mJ/cm 2 , more preferably 1 to 500 mJ/cm 2 , and still more preferably 2 to 200 mJ/cm 2 . The coating film may be irradiated with the polarized radiation only once in a predetermined polarization direction, but the coating film may be irradiated with radiation having different polarization directions (incident directions) a plurality of times.

(Process 2; formation of liquid crystal layer 15)

At this process, polymeric liquid crystal is apply|coated to one surface of the liquid crystal aligning film 14 obtained at the process 1. This makes it adjacent to the liquid crystal aligning film 14, and forms the coating film containing polymeric liquid crystal. In order to apply the polymerizable liquid crystal to one side of the formed liquid crystal alignment film 14, suitable coating methods such as bar coating, roll coating, spinner method, printing method, inkjet method, etc. can be employed, for example.

Next, the coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment selected from heating and light irradiation to cure the coating film and form the liquid crystal layer 15 . It is preferable to perform these treatments superimposedly because good orientation can be obtained. The heating temperature of the coating film must be appropriately selected according to the type of polymerizable liquid crystal to be used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80°C. The heating time is preferably 0.5 to 5 minutes.

As irradiation light, unpolarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation amount of light is preferably 50 to 10,000 mJ/cm 2 , and more preferably 100 to 5,000 mJ/cm 2 . The thickness of the liquid crystal layer 15 to be formed is appropriately set depending on the desired optical properties and the optical properties of the polymerizable liquid crystal to be used, and is set within a range of, for example, 0.1 to 1.5 μm.

(Process 3; formation of the second optically anisotropic layer 13)

This manufacturing method may include a step of forming the second optically anisotropic layer 13 on the liquid crystal layer 15 as step 3.

In step 3, the second optically anisotropic layer 13 is formed on the liquid crystal layer 15 . Here, “above the liquid crystal layer 15” means a configuration in which the second optically anisotropic layer 13 is directly laminated on the liquid crystal layer 15, and the second optically anisotropic layer 13 on the liquid crystal layer 15 ) is a concept including a configuration in which the second optically anisotropic layer 13 is laminated with a different layer interposed therebetween. Specifically, when the first optically anisotropic layer 12 and the second optically anisotropic layer 13 are adjacent to each other, a composition for forming the second optically anisotropic layer 13 on one surface of the liquid crystal layer 15 A method of coating and, if necessary, processing such as drying and curing; The second optically anisotropic layer 13 is formed by a method of adhering stretched films together using an adhesive or pressure-sensitive adhesive or the like. In the case where a layer different from the second optically anisotropic layer 13 is provided between the first optically anisotropic layer 12 and the second optically anisotropic layer 13, first, for example, the liquid crystal layer 15 ), a composition for forming a layer different from the second optically anisotropic layer 13 is applied to one surface of the obtained second optically anisotropic layer 13, and then, on one surface of the obtained layer different from the second optically anisotropic layer 13, the second optically anisotropic layer A composition for forming the layer 13 is applied, and processing such as drying and curing is performed as necessary. In addition, various conditions for layer formation, such as coating, drying, and curing, may be appropriately selected according to the composition to be used, and can be performed by the same method as for the first optically anisotropic layer 12, for example.

≪Polarizer≫

A polarizing plate of the present disclosure includes the viewing angle compensation film and a polarizer. In FIG. 3, one aspect of the polarizing plate of this indication is shown. In FIG. 3 , a polarizing plate 20 includes a viewing angle compensation film 10 including a substrate 11 , a first optical anisotropic layer 12 , and a second optical anisotropic layer 13 . In the substrate 11, a polarizer 17 and a protective film 18 are laminated in this order on the surface opposite to the surface on which the first optically anisotropic layer 12 is provided.

Examples of the polarizer 17 include a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while iodine is absorbed, a polyene type polarizing film, and a dye type polarizing film using a dichroic dye. The polarizer 17 is bonded to the substrate surface of the substrate 11 using, for example, a water-based adhesive in which polyvinyl alcohol is dissolved in water, an adhesive having a polar group, or the like. It is preferable to install the polarizer 17 so that the direction of the polarization axis in the polarizer 17 is orthogonal to the optical orientation direction of the liquid crystal alignment film 14 . As the protective film 18, a cellulose acetate film etc. are mentioned, for example.

Further, the polarizing plate of the present disclosure may have a configuration including a viewing angle compensation film (see FIG. 2 ) having an intermediate layer 16 . As another aspect, as shown in FIG. 4, a first optically anisotropic layer 12 composed of a liquid crystal alignment film 14 and a liquid crystal layer 15 on one surface of the polarizer 17 using the polarizer 17 as a base material , and the second optically anisotropic layer 13 may have a structure in which the liquid crystal alignment film 14, the liquid crystal layer 15, and the second optically anisotropic layer 13 are laminated in this order. In this case, the second optically anisotropic layer 13 is preferably an optically anisotropic layer utilizing orientation of liquid crystal molecules. In the polarizing plate 20 of FIG. 4 , a protective film 18 is provided on a surface opposite to the first optically anisotropic layer 12 in the polarizer 17 . In this case, the viewing angle compensation film 10 is constituted by the liquid crystal alignment film 14, the liquid crystal layer 15, and the second optically anisotropic layer 13. In the polarizing plate 20, a hard coat layer may be further provided on the surface of the protective film 18.

<<liquid crystal display element and organic EL element>>

The liquid crystal display element and the organic EL element of the present disclosure are provided with the viewing angle compensation film described above. The operation mode of the liquid crystal display element is not particularly limited, and for example, various operations such as TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS type, FFS type, OCB type, etc. Applicable to mods.

5, one aspect of the liquid crystal display element 40 of this indication is shown. The liquid crystal display element 40 in FIG. 5 includes a liquid crystal cell 21, a polarizing plate 20 on the front side, and a polarizing plate 30 on the rear side. Although not shown, the liquid crystal cell 21 includes a pair of substrates and a liquid crystal alignment film formed on at least one substrate surface in the pair of substrates. The liquid crystal is charged between the pair of substrates, and the alignment of the liquid crystal is controlled by switching the application/release of the voltage between the pair of substrates. In the front-side polarizing plate 20, a viewing angle compensation film 10 composed of a first optically anisotropic layer 12 and a second optically anisotropic layer 13 is formed on the polarizer 17, and the second optically anisotropic layer (13) is arranged adjacent to the liquid crystal cell (21). Note that the description of FIGS. 1 to 3 can be applied to the polarizing plate 20 . In the liquid crystal display element 40 of FIG. 5 , a hard coat layer 22 is provided on the surface of the polarizing plate 20 on the front side.

The rear-side polarizing plate 30 is a laminate in which an optically anisotropic layer 31, a liquid crystal alignment film 32, a polarizer 33, and a protective film 34 are laminated in this order, and the optically anisotropic layer 31 is a liquid crystal It is arranged in a state adjacent to the cell 21. The polarizer 33 on the rear side is arranged so that its absorption axis is orthogonal to the axis of absorption of the polarizer 17 on the front side. The rear-side optically anisotropic layer 31 may be formed by providing a liquid crystal alignment film on the surface of the polarizer 33, applying a liquid crystal compound to the surface of the liquid crystal alignment film and curing the surface, or may be formed by a stretched film. .

The liquid crystal display device and organic EL device of the present disclosure can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, and mobile phones. , smart phones, various monitors, liquid crystal TVs, information displays, liquid crystal projectors and the like can be used in various display devices.

<Example>

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight (Mw) of the polymer, the number average molecular weight (Mn) and the epoxy equivalent, and the solution viscosity of the polymer solution were measured by the following methods. Required amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthesis scale shown in the following synthesis examples as necessary.

[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of Polymer]

Mw and Mn are polystyrene conversion values measured by GPC under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Co., Ltd.

Solvent: Tetrahydrofuran

Temperature: 40 degrees Celsius

Pressure: 68 kgf/cm2

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solution viscosity of polymer solution]

The solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer.

In addition, below, "the compound represented by formula (X)" may be simply abbreviated as "compound (X)".

<Synthesis of polyorganosiloxane having an epoxy group>

[Synthesis Example 1]

To a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 70.5 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and triethylamine 8.8 g was put in and mixed at room temperature. Next, 70.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then reacted at 80°C for 2 hours while stirring under reflux. By repeating the operation of concentrating the reaction solution and diluting it with butyl acetate twice, triethylamine and water were distilled off to obtain a polymer solution containing polyorganosiloxane (SEp-1). When ¹ H-NMR analysis was performed, it was confirmed that no side reaction of the epoxy group occurred during the reaction. The Mw of this polyorganosiloxane (SEp-1) was 11,000, and the epoxy equivalent was 182 g/mol.

<Synthesis of cinnamic acid derivatives>

The synthesis reaction of the cinnamic acid derivative was conducted in an inert atmosphere.

[Synthesis Example 2]

In a 500 mL three-necked flask equipped with a cooling tube, 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, dimethylacetamide 135 mL was mixed. To this mixed solution, 7 g of acrylic acid was added with a syringe and stirred. Further, the mixed solution was stirred while heating at 120°C for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. After filtering the precipitate, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution, and the precipitate was collected. The recovered precipitate was recrystallized from a 1:1 (weight ratio) solution of ethyl acetate and hexane to obtain 10.2 g of a compound (cinnamic acid derivative (M-1)) represented by the following formula (M-1).

<Synthesis of optical orientation polyorganosiloxane>

[Synthesis Example 3]

In a 100 mL three-necked flask, 11.3 g of polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, cinnamic acid derivative (M-1) 1.7 g obtained in Synthesis Example 2, 0.54 g of acryloyl group-containing carbonic acid (Aronix M-5300, manufactured by Toa Synthesis Co., Ltd.) and 0.9 g of tetrabutylammonium bromide were charged, and the mixture was stirred at 80°C for 12 hours. After completion of the reaction, an additional 20 g of n-butyl acetate was added, and the solution was washed with water three times, and then an additional 20 g of n-butyl acetate was added, and the solvent was distilled off so that the solid content concentration was 10% by weight. In this way, an n-butyl acetate solution having a solid content concentration of 10% by weight containing polymer (S-1), which is an optical orientation polyorganosiloxane, was obtained. The weight average molecular weight (Mw) of polymer (S-1) was 18,000.

[Synthesis Example 4]

In a 100 mL three-neck flask, 11.3 g of polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, 1.7 g of a cinnamic acid derivative (M-1) obtained in Synthesis Example 2, and 0.10 g of a quaternary amine salt (San Afro, Inc., UCAT18X) was put thereinto, and the mixture was stirred at 80°C for 12 hours. After completion of the reaction, an additional 20 g of n-butyl acetate was added, and the solution was washed with water three times, and then an additional 20 g of n-butyl acetate was added, and the solvent was distilled off so that the solid content concentration was 10% by weight. In this way, an n-butyl acetate solution having a solid content concentration of 10% by weight containing Polymer (S-2), which is an optical orientation polyorganosiloxane, was obtained. The weight average molecular weight (Mw) of polymer (S-2) was 17,000.

[Synthesis Example 5]

A polysiloxane having a cinnamic acid structure was obtained according to a formulation described in Japanese Patent Laid-Open No. 9-278890. Specifically, a mixture of 0.05 ml of an ester corresponding to 4-aryloxycinnamic acid, 0.1 ml of methylpolysiloxane, and a 100 ml solution of catalytic amount of platinum chloride in benzene was boiled for 10 hours, cooled, and then diluted with methanol. . The reaction product was filtered and washed with methanol. Thereafter, polysiloxane cinnamate was dried under vacuum at a temperature of 50 to 60° C. until a certain amount was obtained, and subsequently pulverized in a vibrating mill to obtain a polymer (S-3). In addition, when ¹ H-NMR analysis was conducted, it was found that there was no double bond of aryloxy molecule in the obtained compound.

[Synthesis Example 9]

Polysiloxane having a cinnamic acid structure was obtained according to the formulation described in paragraph 0228 of Japanese Patent Laid-Open No. 2012-155308. Specifically, as a monomer, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were charged and mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then reacted at 80°C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain polysiloxane containing an epoxy group as a viscous transparent liquid. . Next, to a 100 mL three-necked flask, 4.6 g of the obtained epoxy group-containing polysiloxane, 31 g of methyl isobutyl ketone, 3 g of a cinnamic acid derivative represented by the following formula (K-1), and a quaternary amine salt (manufactured by San Afro, UCAT 18X) 0.10 g was put in and stirred at 80 degreeC for 12 hours. After completion of the reaction, methanol was added to precipitate the reaction product, and then filtered. After dissolving the precipitate in ethyl acetate and washing the solution with water three times, the solvent was distilled off to obtain a polymer (S-4), which is an optical orientation polyorganosiloxane, as a white powder. The weight average molecular weight (Mw) of polymer (S-4) was 3,900.

<Synthesis of poly(meth)acrylate>

[Synthesis Example 6]

In a flask equipped with a cooling pipe and a stirrer, 1 part by weight of 2,2'-azobis (isobutyronitrile) as a polymerization initiator and 180 parts by weight of diethylene glycol methyl ethyl ether as a solvent were placed. Subsequently, after adding 70 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate and 30 parts by weight of 3-methyl-3-oxetanylmethyl methacrylate and substituting with nitrogen, stirring was gradually started. The solution temperature was raised to 80°C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a polymer (Pac-1) which is an epoxy group-containing polymethacrylate. The solid content concentration of the obtained polymer solution was 32.8% by weight. Mn of the obtained polymer was 16,000.

[Synthesis Example 7]

100 parts by weight of epoxy group-containing polymethacrylate (Pac-1) obtained in Synthesis Example 6, 20 parts by weight of acryloyl group-containing carbonic acid (Aronix M-5300, manufactured by Toa Synthesis Co., Ltd.), tetrabutylammonium bromide as a catalyst 10 parts by weight and 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent were added, and the mixture was stirred at 90°C in a nitrogen atmosphere for 12 hours. After completion of the reaction, it was diluted with 100 parts by weight of propylene glycol monomethyl ether acetate and washed with water three times. The operation of concentrating this solution and diluting with butyl acetate was repeated twice to obtain a polymer solution containing a polymer (Pac-2) which is an acryloyl group-containing polymethacrylate. Mn of the obtained polymer (Pac-2) was 20,000. In addition, the propylene glycol monomethyl ether acetate content of the obtained polymer solution was 20% by weight.

[Synthesis Example 10]

4'-(6-bromohexyloxy)vinyl-4-ol was synthesized by heating 4,4'-biphenyldiol and 1,6-dibromohexane under alkaline conditions. Lithium methacrylate was reacted with this product to obtain 2-(4'-hydroxyvinyl-4-yloxy)hexyloxymethacrylate. Then, 4-methoxycinnamoyl chloride was added under alkaline conditions to synthesize a compound represented by the following formula (M-2). Polymer (Pac-3) was obtained by dissolving this compound (M-2) in tetrahydrofuran and polymerizing with the addition of azobisisobutyronitrile as a polymerization initiator. This polymer (Pac-3) exhibited liquid crystallinity in the temperature range of 116 to 315°C.

<Synthesis of other polymers>

[Synthesis Example 8]

Polymer (Pva-1) was obtained by polymerizing polymer No. 4 (modified polyvinyl alcohol) described in paragraph [0073] of Patent No. 3907735 according to the description in paragraph [0101].

[Example 1]

1. Preparation of polymer composition for viewing angle compensation film

An amount equivalent to 30 parts by weight of the n-butyl acetate solution containing the polymer (S-1) obtained in Synthesis Example 3 as a polymer component in terms of the polymer (S-1), and the polymer (Pac obtained in Synthesis Example 7) -2), an amount equivalent to 70 parts by weight in terms of polymer (Pac-2), and tris(acetylacetonate)aluminum as a catalyst (aluminum chelate A(W), manufactured by Kawaken Fine Chemical Co., Ltd.) 3 parts by weight, and 1 part by weight of tri(p-tolyl)silanol as a curing accelerator were mixed, and as a solvent, n-butyl acetate (BA), methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA) and ethyl acetoacetate (EAA) were added to prepare a solid content concentration of 5% by weight and a weight ratio of each solvent to BA:MEK:PGMEA:EAA = 40:40:15:5. Subsequently, a polymer composition (A-1) was prepared by filtering this obtained solution with a filter having a pore diameter of 1 μm.

2. Production of viewing angle compensation film

(1) Surface treatment of substrate

According to the method described in International Publication No. 2015/008773, alkali saponification treatment was performed on one side of a cellulose film (Fuji Film Co., Ltd. product, zero retardation tag, ZRF25, thickness: 25 μm). Specifically, it was performed as follows.

After the film (ZRF25) was passed over a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C, an alkali solution (AL1) was applied using a rod coater at an application amount of 17 mL/m 2 , 110 It was made to stay for 10 seconds under a steam type far-infrared heater heated to °C. The composition of the alkali solution (AL1) is potassium hydroxide 8.6 parts by weight, water 24.1 parts by weight, isopropanol 56.3 parts by weight, surfactant (C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H) 1.0 parts by weight, and propylene glycol It was set as 10.0 weight part.

Subsequently, 2.8 mL/m 2 of distilled water was applied in the same way using a rod coater, and then water washing with a fountain coater and dehydration with an air knife were repeated three times, and dried by staying in a drying zone at 70°C for 5 seconds. Thus, a single-side saponified film was produced.

(2) Fabrication of the first optically anisotropic layer

On the saponified surface of the saponified film obtained in (1) above, the polymer composition (A-1) prepared above was applied using a bar coater, and baked in an oven at 120°C for 2 minutes to obtain a film thickness of 0.1 µm. formed a coating. Next, the surface of this coating film was irradiated with 10 mJ/cm 2 of polarized light ultraviolet light containing a bright line of 313 nm perpendicularly from the normal line of the base material surface using a Hg-Xe lamp and a Glan Taylor prism to prepare a liquid crystal alignment film.

Next, a polymerizable liquid crystal (RMS03-013C, manufactured by Merck Co., Ltd.) was filtered through a filter having a pore diameter of 0.2 μm, and applied to the surface of the liquid crystal alignment film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 50° C., the polymerizable liquid crystal was irradiated with 1,000 mJ/cm 2 of unpolarized ultraviolet rays including a bright line of 365 nm using an Hg-Xe lamp to cure the polymerizable liquid crystal. The film thickness of the obtained film was 1.0 µm.

(3) Fabrication of the second optically anisotropic layer

According to the method described in International Publication No. 2015/008773, the second optically anisotropic layer was produced. Specifically, first, the following composition was dissolved in a solution of methyl ethyl ketone:cyclohexanone = 86:14 (weight ratio) to prepare 30% by weight.

<Composition for the second optically anisotropic layer>

･Liquid crystal compound

A mixture of liquid crystal compound (B1) and liquid crystal compound (B2) 100 parts by weight

(B1:B2=80:20 (weight ratio))

Polymerization initiator compound (J1) 3 parts by weight

Compound (J2) 1 part by weight

Leveling agent compound (R1) 0.4 parts by weight

Compound (R2) 　　　　　　　　　 0.05 parts by weight

・Monomer compound (A1) 5 parts by weight

Vertical alignment component compound (S1) 1 part by weight

Compound (S2) 0.5 parts by weight

Next, the composition prepared above was applied on the first optically anisotropic layer with a wire bar coater, and heated in a thermostat at 100° C. for 2 minutes to align the liquid crystal compound. Then, after cooling to 40°C, under a nitrogen purge, at an oxygen concentration of about 0.1%, using a 160 W/cm 2 air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an illuminance of 190 mW/cm 2 and an irradiation amount of 300 mJ/cm 2 The coating layer was cured by irradiation with ultraviolet rays. After that, it was allowed to cool to room temperature to form a second optically anisotropic layer (film thickness: 0.9 µm) to obtain a viewing angle compensation film.

3. Fabrication of polarizing film

Using the viewing angle compensation film, which is a laminate comprising the first optically anisotropic layer and the second optically anisotropic layer obtained above, polyvinyl alcohol polarization using polyvinyl alcohol glue on the outer surface of the base material of the viewing angle compensation film. A film (film thickness of 17 μm) was bonded. At this time, the films were bonded so that the orientation direction of the liquid crystal aligning film was orthogonal to the longitudinal direction of the polarizing film.

Further, a cellulose acylate film (protective film, film thickness: 25 μm) was applied to the surface opposite to the substrate in the polarizing film, and a 3% aqueous solution of polyvinyl alcohol (polyvinyl alcohol-117H manufactured by Kuraray Co., Ltd.) was added. It was bonded using an adhesive. In addition, what was produced according to the method of international publication 2015/008773 was used for the cellulose acylate film.

4. Evaluation of liquid crystal orientation

About the polarizing film produced above, orientation was observed with the naked eye and a polarization microscope under Cross Nicols. “Good (A)” indicates a case in which the orientation is visually observed and no abnormal domain is observed with a polarizing microscope, and “possible (B)” indicates a case in which an abnormal domain is observed with a polarizing microscope although the orientation is observed with the naked eye. )”, the case where an abnormality in orientation was observed visually was evaluated as “defective (C)”. As a result, in this Example, it was evaluation of liquid-crystal orientation "possible (B)".

5. Evaluation of contrast

For the polarizing film obtained above, the luminance when transmitted light was irradiated from the opposite direction to the observation side was measured, and the luminance when the polarizing film was disposed under crossed nicol (black display) and the luminance when not disposed under crossed nicol ( The optical performance of the viewing angle compensation film was evaluated by the contrast ratio (=white display luminance/black display luminance) expressed as the ratio of white display). Also, the better the optical performance, the higher the contrast ratio. In the evaluation, the case where the contrast ratio was 1,000 or more was “good (A)”, the case where the contrast ratio was 500 or more and less than 1,000 was “possible (B)”, and the case where the contrast ratio was less than 500 was made “poor (C)”. In addition, the luminance was measured using a spectroscopic radiation luminance meter "CS-2000A" manufactured by Konica Minolta. As a result, in this Example, it was an evaluation of "good (A)".

[Examples 2 to 4]

Polymer compositions (A-2) to (A-4) were prepared in the same manner as in Polymer composition (A-1), except that the types and amounts of each component shown in Table 1 below were used. Moreover, using the obtained polymer composition, it carried out similarly to Example 1, the polarizing film was produced, and various evaluations were performed. These results are shown in Table 2 below.

[Comparative Example 1]

A polymer composition (A-5) was prepared in the same manner as in the polymer composition (A-1) except that each component of the type and compounding amount shown in Table 1 below was used. In addition, except that the polymer composition (A-5) was used instead of the polymer composition (A-1), and the rubbing treatment was performed in the direction orthogonal to the longitudinal direction of the film instead of the photo-alignment treatment, A polarizing film was produced in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2 below.

The numerical value of the compounding amount in Table 1 shows the compounding ratio (parts by weight) of each compound with respect to 100 parts by weight of the total of the polymer components used for preparing the polymer composition. In Table 1, the symbol of a compound is as follows.

B-1: Tris (acetylacetonate) aluminum (aluminum chelate A (W), manufactured by Kawaken Fine Chemical)

K-1: tri(p-tolyl)silanol

BA: n-butyl acetate

MEK: methyl ethyl ketone

PGMEA: Propylene glycol monomethyl ether acetate

EAA: Ethyl acetoacetate

EDM: Diethylene glycol ethyl methyl ether

CHN: Cyclohexanone

CPN: Cyclopentanone

PGME: Propylene glycol monomethyl ether

WT: distilled water

MEOH: methanol

As is clear from Table 2, in Examples 1-4, all evaluation of liquid-crystal orientation and contrast was "A" or "B" evaluation. On the other hand, in Comparative Example 1, the evaluation of liquid crystal orientation and contrast was "C", respectively, and was inferior to that of Examples.

[Example 5]

1. Production of viewing angle compensation film

In Example 1, except that the liquid crystal alignment film was produced using the polymer composition (A-2) and the second optically anisotropic layer was constituted with an intermediate layer, similarly to Example 1, and viewing angle compensation made the film. Specifically, first, by the same method as in 2.(2) of Example 1, using the polymer composition (A-2), on one side of a cellulose film subjected to alkali saponification treatment, a liquid crystal alignment film and a liquid crystal layer were formed. 1 An optically anisotropic layer (film thickness 1.1 μm) was formed. Next, an intermediate layer was formed on the first optically anisotropic layer. The middle layer was formed as follows.

First, 33 parts by weight of 2,3-dihydroxymethacrylate, 67 parts by weight of a mixture of 50/50 (weight ratio) of pentaerythritol triacrylate/pentaerythritol tetraacrylate, photopolymerization initiator (Irgacure 127, 4 parts by weight of Chiba Specialty Chemicals Co., Ltd.) and a solvent (methyl acetate/cyclohexanone = 50/50 (parts by weight)) are mixed, and the solid concentration is adjusted to 30% by weight to form an intermediate layer. composition was prepared. The obtained composition for forming an intermediate layer was applied to the surface of the first optically anisotropic layer with a wire bar coater, dried at 60° C. for 30 seconds, and then UV-irradiated at 30° C. for 30 seconds using a 120 W/cm 2 high-pressure mercury lamp and crosslinked. , to obtain an intermediate layer with a film thickness of 2.0 μm.

Next, on the intermediate layer, an optically anisotropic layer (film thickness: 0.9 μm) was formed in the same manner as in 2. (3) of Example 1, thereby producing a second optically anisotropic layer having an intermediate layer. A polarizing film and a protective film were bonded to the laminate provided with the first optically anisotropic layer and the second optically anisotropic layer obtained in this way in the same manner as in Example 1 to obtain a polarizing film. The obtained viewing angle compensation film exhibited reverse wavelength dispersion.

2. Evaluation of liquid crystal orientation and contrast

Using the polarizing film obtained in said 1., it carried out similarly to Example 1, and evaluated the liquid-crystal orientation and contrast. As a result, in Example 5, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "possible (B)".

[Example 6]

1. Production of viewing angle compensation film and polarizing film

Compensation for viewing angle in the same manner as in Example 1 except that the liquid crystal alignment film was produced using the polymer composition (A-3) and the composition for the second optically anisotropic layer was changed to that shown below in Example 1 A film and a polarizing film were produced. In addition, the second optically anisotropic layer exhibited positive birefringence.

<Composition for the second optically anisotropic layer (Example 6)>

･Liquid crystal compound

Mixture of liquid crystal compound (B3) and liquid crystal compound (B4) 　　　　　100 parts by weight

(B3:B4=90:10 (weight ratio))

・Photopolymerization initiator

(Irgacure 907, manufactured by Chiba Specialty Chemicals Co., Ltd.)

Sensitizer (Kayacure-DETX, Nippon Explosive Co., Ltd.) 　　　　　　　1 part by weight

Fluorine-containing compound (R3) 0.5 parts by weight

· Methyl ethyl ketone

2. Evaluation of liquid crystal orientation and contrast

Using the polarizing film obtained in said 1., it carried out similarly to Example 1, and evaluated the liquid-crystal orientation and contrast. As a result, in Example 6, it was evaluation of liquid-crystal orientation "good (A)" and contrast "good (A)."

[Example 7]

1. Production of viewing angle compensation film and polarizing film

In Example 1, the liquid crystal alignment film was produced using the polymer composition (A-4), and the composition for the second optically anisotropic layer was changed to that shown below, and the irradiation conditions of ultraviolet rays were 400 mW/cm 2 of illuminance, A viewing angle compensation film and a polarizing film were produced in the same manner as in Example 1 except that the irradiation amount was changed to 60 mJ/cm 2 . In addition, the water vapor transmission rate of the second optically anisotropic layer was 60 g/m 2 /day. In addition, the moisture permeability is a value measured at 40°C and 90% relative humidity based on JIS Z-0208.

<Composition for the second optically anisotropic layer (Example 7)>

Tricyclodecane dimethanol dimethacrylate 97 parts by weight

(A-DCP, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

3 parts by weight of photopolymerization initiator

(Irgacure 907, manufactured by Chiba Specialty Chemicals Co., Ltd.)

Fluorine-containing compound (R4) 0.04 parts by weight

(Mw=14,000)

Methyl ethyl ketone 　　 81.8 parts by weight

2. Evaluation of liquid crystal orientation and contrast

Using the polarizing film obtained in said 1., it carried out similarly to Example 1, and evaluated the liquid-crystal orientation and contrast. As a result, in Example 7, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "possible (B)".

[Example 8]

1. Production of viewing angle compensation film and polarizing film

In Example 1, a viewing angle compensation film and a polarizing film were produced in the same manner as in Example 1, except that the method for producing the second optically anisotropic layer was changed. The second optically anisotropic layer was produced as follows. First, with the composition A shown below, each component was put into a mixing tank and stirred, and each component was dissolved to prepare a core layer cellulose acylate dope.

<Composition A>

Cellulose acetate having an acetyl substitution degree of 2.88 100 parts by weight

Ester oligomers 　　　　　　　　　　　　　　　　　　13 parts by weight

(Monomer; 1,4-cyclohexyl dicarboxylic acid and ethylene glycol (reaction molar ratio 1: 1), end-capped with an acetyl group, Mn = 1,000)

・Methylene chloride 　　　　　 430 parts by weight

・Methanol 64 parts by weight

Next, 2 parts by weight of silica particles (AEROSIL R972, manufactured by Aellosil Co., Ltd., average particle diameter: 20 nm), 76 parts by weight of methylene chloride, 11 parts by weight of methanol, and 1 part by weight of core layer cellulose acylate dope were added. By mixing, a mat agent solution was prepared. Subsequently, 10 parts by weight of the mat agent solution was added to 90 parts by weight of the core layer cellulose acylate dope to prepare an outer layer cellulose acetate solution.

Three layers of the obtained core layer cellulose acylate dope and the outer layer cellulose acetate solution on both sides thereof were simultaneously casted on a drum at 20°C from a pouring hole. The film was peeled off with a solvent content of about 20% by weight, both ends in the width direction were fixed with tenter clips, and dried while stretching 1.2 times in the transverse direction with a residual solvent of 3 to 15% by weight. Thereafter, a cellulose acylate film having a thickness of 25 µm was produced by conveying between the rolls of the heat treatment apparatus. The elastic modulus of the obtained film was 4.7 GPa. In addition, the modulus of elasticity is measured by measuring the stress at 0.5% elongation at a tensile rate of 10%/min in an atmosphere of 23°C and 60% relative humidity using a tensile tester (STM 　T50BP, manufactured by Dongyang Baldwin Co., Ltd.), MD. and a value measured as an average value of tensile modulus of TD. Further, the obtained film was adhered to the surface of the first optically anisotropic layer using a 3% aqueous solution of polyvinyl alcohol (Polyvinyl Alcohol-117H manufactured by Kuraray Co., Ltd.) as an adhesive to prepare a second optically anisotropic layer. did.

2. Evaluation of liquid crystal orientation and contrast

Using the polarizing film obtained in said 1., it carried out similarly to Example 1, and evaluated the liquid-crystal orientation and contrast. As a result, in Example 8, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "good (A)."

The results of Examples 5 to 8 were collectively shown in Table 3 below.

[Example 9]

1. Production of viewing angle compensation film

A viewing angle compensation film 10 in which the second optically anisotropic layer 13 shown in FIG. 6 is a polarizer 13B was produced. First, as the second optically anisotropic layer, a polarizing film with a single-sided protective film described in Paragraph 0163 of Japanese Unexamined Patent Publication No. 2015-43073 was produced. On the surface where the protective film was not formed, the polymer composition (A-1) prepared above was applied using a bar coater, and baked in an oven at 120° C. for 2 minutes to form a coating film having a thickness of 0.1 μm. . Next, the surface of this coating film was irradiated with 10 mJ/cm 2 of polarized light ultraviolet light containing a bright line of 313 nm perpendicularly from the normal line of the base material surface using a Hg-Xe lamp and a Glan Taylor prism to prepare a liquid crystal alignment film.

Subsequently, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck Co., Ltd.) was filtered through a filter having a pore diameter of 0.2 μm, and applied to the surface of the liquid crystal alignment film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 50° C., the polymerizable liquid crystal was irradiated with 1,000 mJ/cm 2 of unpolarized ultraviolet rays including a bright line of 365 nm using an Hg-Xe lamp to cure the polymerizable liquid crystal. The film thickness of the obtained film was 1.0 µm.

2. Evaluation of liquid crystal orientation and contrast

While carrying out similarly to Example 1 using the viewing angle compensation film obtained in said 1. and producing a polarizing film, liquid-crystal orientation and contrast were evaluated about the obtained polarizing film. As a result, in Example 9, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "possible (B)".

[Example 10]

1. Production of viewing angle compensation film

The viewing angle compensation film 10 in which the second optically anisotropic layer 13 shown in FIG. 7 is composed of the second liquid crystal alignment film 13C and the second liquid crystal layer 13D was produced. First, a polymer composition (A-6) was prepared in the same manner as in Example 1 except that the polymer (S-4) obtained in Synthesis Example 9 was used instead of the polymer (S-1) in Example 1. . Next, in the same manner as in Example 1, the first optically anisotropic layer 12 was formed on the single-side saponified film using the polymer composition (A-1). Subsequently, the polymer composition (A-6) was applied on the first optically anisotropic layer 12 using a bar coater, and baked in an oven at 120° C. for 2 minutes to form a coating film having a thickness of 0.1 μm. Next, the surface of this coating film was irradiated with 10 mJ/cm 2 of polarized ultraviolet light containing a bright line of 313 nm perpendicularly from the normal line of the substrate surface using an Hg-Xe lamp and a Glan Taylor prism, thereby forming a second liquid crystal alignment film 13C. has produced On the obtained 2nd liquid crystal aligning film 13C, the 2nd liquid crystal layer 13D was formed using the composition described in Paragraph 0186 of Unexamined-Japanese-Patent No. 2015-43073 - 0191.

Specifically, first, the following composition was dissolved in a solution of methyl ethyl ketone:cyclohexanone = 86:14 (weight ratio) to prepare 30% by weight.

<Composition for the second optically anisotropic layer (Example 10)>

･Liquid crystal compound

A mixture of liquid crystal compound (B5) and liquid crystal compound (B6) 100 parts by weight

(B5:B6=80:20 (weight ratio))

Polymerization initiator compound (J1) 3 parts by weight

Compound (J2) 1 part by weight

Leveling agent compound (R1) 　　　 0.4 parts by weight

Compound (R2) 　　　 0.05 parts by weight

・Monomer compound (A1) 　　　　　　 5 parts by weight

Vertical alignment component compound (S1) = 1 part by weight

Compound (S2) = 0.5 parts by weight

Next, on the second liquid crystal alignment film 13C, the composition prepared above was applied with a wire bar coater, and heated in a constant temperature bath at 100°C for 2 minutes. Next, after cooling to 40°C, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W/cm 2 was used under a nitrogen purge at an oxygen concentration of about 0.1%, with an illuminance of 190 mW/cm 2 and an irradiation amount of 300 mJ/cm 2 . The coating layer was cured by irradiation of ultraviolet rays, and then allowed to cool to room temperature.

2. Evaluation of liquid crystal orientation and contrast

While carrying out similarly to Example 1 using the viewing angle compensation film obtained by said 1. and producing a polarizing film, liquid-crystal orientation and contrast were evaluated about the obtained polarizing film. As a result, in Example 10, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "good (A)."

[Example 11]

In Example 1, the second optically anisotropic layer 13 was formed on the saponified surface of the single-side saponified film, and then, on the second optically anisotropic layer 13, the first optically anisotropic layer 12 was formed. The viewing angle compensation film 10 was produced in the same manner as in Example 1, except that the liquid crystal alignment film 14 and the liquid crystal layer 15 were produced in this order. 8, the schematic structure of the viewing angle compensation film 10 of Example 11 is shown. Moreover, while carrying out similarly to Example 1 using the obtained viewing angle compensation film and producing a polarizing film, liquid-crystal orientation and contrast were evaluated about the obtained polarizing film. As a result, in Example 11, it was evaluation of liquid-crystal orientation "possible (B)" and contrast "good (A)."

[Example 12]

A viewing angle compensation film was produced in the same manner as in Example 5, except that the polymer composition (A-3) was used instead of the polymer composition (A-2). Moreover, while carrying out similarly to Example 1 using the obtained viewing angle compensation film and producing a polarizing film, liquid-crystal orientation and contrast were evaluated about the obtained polarizing film. As a result, in Example 12, it was evaluation of liquid-crystal orientation "good (A)" and contrast "good (A)."

[Comparative Example 2]

Except for using the polymer (Pac-3) obtained in the above Synthesis Example 10 instead of the polymer (S-1) of the polymer composition (A-3), the polymer composition was adjusted in the same manner as in the polymer composition (A-3). (A-7) was obtained. Further, in Example 1, instead of the polymer composition (A-1), except that the polymer composition (A-7) was used, the viewing angle compensation film was produced in the same manner as in Example 1, and a polarizing film was produced And, liquid-crystal orientation and contrast were evaluated about the obtained polarizing film. As a result, in Comparative Example 2, it was evaluation of liquid-crystal orientation "defect (C)" and contrast "defect (C)".

As described above, by forming the liquid crystal alignment film in the viewing angle compensation film provided with a plurality of optically anisotropic layers using polyorganosiloxane, it is possible to obtain a viewing angle compensation film with excellent orientation and contrast and excellent optical properties. I get it.

10: viewing angle compensation film

11: materials

12: first optically anisotropic layer

13: second optically anisotropic layer

14: liquid crystal alignment layer

15: liquid crystal layer

16: middle layer

17: polarizer

18: protective film

20: polarizer

21: liquid crystal cell

30: polarizer

40: liquid crystal display element

Claims (16)

A viewing angle compensation film comprising a first optically anisotropic layer as an optically anisotropic layer and a second optically anisotropic layer different from the first optically anisotropic layer,
The first optically anisotropic layer has a liquid crystal alignment film and a liquid crystal layer,
The second optically anisotropic layer is disposed on the contact surface with the first optically anisotropic layer and is a (meth)acrylic polymer, a bromine-containing polymer, a styrene-acrylonitrile-(N-phenylmaleimide) tertiary copolymer, or a modified It has an intermediate layer formed using a styrenic polymer,
The viewing angle compensation film wherein the liquid crystal alignment film is formed using a polymer composition containing polyorganosiloxane. According to claim 1,
The viewing angle compensation film in which the second optically anisotropic layer has the following physical properties of A), B), C) or D):
A) has positive birefringence;
B) water vapor permeability at 40° C. and 90% relative humidity in accordance with JIS Z-0208 is 200 g/m 2 /day or less;
C) an elastic modulus of at least 4.2 GPa;
D) has reverse wavelength dispersion. According to claim 1 or 2,
The viewing angle compensation film wherein the polymer composition has an optical alignment group and a polymerizable group in the same or different molecules. According to claim 1 or 2,
The polyorganosiloxane is a viewing angle compensation film having an optical orientation group. According to claim 1 or 2,
The polyorganosiloxane is a viewing angle compensation film having an epoxy group. According to claim 1 or 2,
The polyorganosiloxane is a viewing angle compensation film having a polymerizable group in a side chain. According to claim 1 or 2,
The viewing angle compensation film of claim 1 , wherein the polymer composition further contains a polymer of a monomer having a polymerizable carbon-carbon unsaturated bond. According to claim 7,
The viewing angle compensation film wherein the polymer of the monomer having a polymerizable carbon-carbon unsaturated bond has a polymerizable group in a side chain. According to claim 1 or 2,
In the polymer composition, the blending ratio of the hydrogen donor having a silanol group is 1 part by weight or less with respect to 100 parts by weight of the total amount of polymer components contained in the polymer composition. A method for producing a viewing angle compensation film comprising a first optically anisotropic layer as an optically anisotropic layer and a second optically anisotropic layer different from the first optically anisotropic layer,
The second optically anisotropic layer is disposed on the contact surface with the first optically anisotropic layer and is a (meth)acrylic polymer, a bromine-containing polymer, a styrene-acrylonitrile-(N-phenylmaleimide) tertiary copolymer, or a modified It has an intermediate layer formed using a styrenic polymer,
A step of forming a liquid crystal alignment film of the first optically anisotropic layer by forming a coating film using a polymer composition containing polyorganosiloxane and irradiating the coating film with light;
A method for producing a viewing angle compensation film comprising a step of forming a liquid crystal layer of the first optically anisotropic layer by applying and curing a polymerizable liquid crystal on the surface of the liquid crystal alignment layer. A polarizing plate comprising the viewing angle compensation film according to claim 1 or 2 and a polarizer. A liquid crystal display device comprising the viewing angle compensation film according to claim 1 or 2. An organic EL device comprising the viewing angle compensation film according to claim 1 or 2. delete delete delete

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