KR20170122644A - Methods for Producing Optically Anisotropic Polymer Films, Organic EL Display Devices and Liquid Crystal Display Devices - Google Patents

Abstract

Provided is a method for producing an optical anisotropy polymeric films which is capable of conducting photopolymerization in the air without being affected by surrounding atmosphere, while uncured state and white turbidity can hardly take place. The method for producing the optical anisotropy polymeric film comprises the following processes: forming a coating film by applying, to a base material, a photopolymerizable composition consisting of a surfactant, a bifunctional oxetane compound, and/or and a monofunctional oxetane compound having a mesogen group; and emitting light while continuously altering an exposure part with respect to the coating film.

Description

TECHNICAL FIELD [0001] The present invention relates to an optically anisotropic polymer film, an organic EL display device, and a manufacturing method of a liquid crystal display device,

The present invention relates to a method of manufacturing an optically anisotropic polymer membrane used in a display device such as an organic EL display device or a liquid crystal display device, and an organic EL display device using the optically anisotropic polymer film and a method of manufacturing the liquid crystal display device.

BACKGROUND ART In display devices such as an organic EL display device and a liquid crystal display device, an optically anisotropic polymer film (also referred to as an " optically anisotropic film ") such as a polarizing film, a retardation film, a viewing angle improving film and a luminance improving film is used. Conventionally, various orientational control methods such as a stretching method, a rubbing method, and a photo alignment method have been generally used as a method for producing such an optically anisotropic polymer film.

In the stretching method, a polymer material such as a polycarbonate resin is stretched to obtain a polymer film in which the polymer chains are oriented in the stretching direction. Although the stretching method is easy to manufacture, there are cases where the orientation direction of the polymer chains and the stretching direction do not coincide with each other.

In the rubbing method, a polymer film in which polymer chains are oriented in one direction can be obtained by rubbing an orientation film such as polyimide and then polymerizing the polymerizable liquid crystal compound on the alignment film. However, the rubbing method requires a rubbed orientation film, and it also causes a problem caused by the rubbing process (for example, dust may be generated, foreign matter tends to adhere to the polymer film due to static electricity, or alignment defects may occur) easy to do.

In the photo alignment method, a photo alignment layer is formed using a photoreactive compound (a compound causing photoisomerization, optical duplication, photodecomposition or the like by light irradiation), and then a polymerizable liquid crystal composition is coated on the photo alignment layer and polymerized to polymerize the polymer chain in one direction Can be obtained. The photo alignment method does not cause a problem due to the rubbing treatment, but it is necessary to use a photo alignment film.

Therefore, as a method for solving the problem of the orientation control method, a technique of controlling the orientation of the polymer chain (hereinafter referred to as "dynamic photopolymerization") by performing dynamic photopolymerization in recent years has been proposed (for example, Patent Document 1). In the dynamic photopolymerization method, since it is not necessary to use an orientation film, a polymer film in which the polymer film is oriented in one direction can be manufactured simply and efficiently as compared with the rubbing method and the photo alignment method.

Patent Document 1: International Publication No. 2014/038260

However, since the material (photopolymerizable composition) used in the dynamic photopolymerization method is susceptible to oxygen in ambient air during the photopolymerization reaction, it has been necessary to perform a photopolymerization reaction in the cell or a photopolymerization reaction under an inert atmosphere. In addition, the dynamic photopolymerization method is performed while continuously changing the exposure part, so that the curing (photopolymerization reaction) of the photopolymerizable composition may be insufficient, and the polymer film may be clouded in some cases.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing an optically anisotropic polymer membrane capable of performing a photopolymerization reaction in the air without being affected by the ambient atmosphere, And an object of the present invention is to provide an organic EL display device using an optically anisotropic polymer film and a manufacturing method of the liquid crystal display device.

As a result of diligent studies to solve the above problems, the present inventors have found that a photopolymerizable composition containing a mesogenic group-containing monofunctional oxetane compound and a bifunctional oxetane compound and / or a surfactant is used for dynamic photopolymerization The present invention has been completed.

That is, the present invention provides a process for producing a photocurable composition, comprising the steps of: applying a photopolymerizable composition comprising a monofunctional oxetane compound having a mesogen group and a bifunctional oxetane compound and / or a surfactant to a substrate to form a coating film; And irradiating the optically anisotropic polymer film with light.

Further, the present invention relates to an organic EL display device characterized by using the optically anisotropic polymer film obtained by the above production method as at least one film selected from the group consisting of a polarizing film, a retardation film, a viewing angle improving film and a luminance improving film Lt; / RTI >

Furthermore, the present invention relates to a liquid crystal display device characterized by using the optically anisotropic polymer film obtained by the above-mentioned production method as at least one film selected from the group consisting of a polarizing film, a retardation film, a viewing angle improving film and a luminance improving film Method.

According to the present invention, there is provided a method of producing an optically anisotropic polymer membrane capable of performing a photopolymerization reaction in the air without being influenced by the ambient atmosphere, and further preventing occurrence of uncured or cloudy white matters, and an organic EL display device using the optically anisotropic polymer membrane A manufacturing method of a liquid crystal display device can be provided.

1 is a schematic vertical sectional view for explaining a dynamic photopolymerization method used in the present invention.
2 is a schematic vertical sectional view of an organic EL display device using an optically anisotropic polymer film as a retardation film.
3 is a schematic vertical sectional view of a liquid crystal display device using an optically anisotropic polymer film as a retardation film.

The method for producing an optically anisotropic polymer film of the present invention includes a step of forming a coating film by applying a photopolymerizable composition to a base material and a step of irradiating the coating film with light while continuously changing the exposure part.

The photopolymerizable composition comprises a monofunctional oxetane compound having a mesogen group and a bifunctional oxetane chemical and / or a surfactant. In the present specification, the term "monofunctional oxetane compound" means a compound having one oxetane group in the molecule and "bifunctional oxetane compound" means a compound having two oxetane groups in the molecule.

The monofunctional oxetane compound having a mesogen group is not particularly limited and those known in the art can be used. In the present specification, the term "mesogen group" means a functional group having rigidity to exhibit liquid crystallinity, and generally has a cyclic structure such as a cyclohexane skeleton and a benzene skeleton. Examples of mesogens include, but are not limited to, phenyl benzoate, biphenyl, cyanobiphenyl, terphenyl, cyanoterphenyl, azobenzene, diazobenzene, aniline benzylidene, azomethine, azoxybenzene, stilbene, phenylcyclohexyl, Biphenylcyclohexyl, phenoxyphenyl, benzylidene aniline, benzoyl benzoate, phenylpyrimidine, phenyl dioxane, benzoyl aniline, tolan and derivatives thereof.

The monofunctional oxetane compound having a mesogen group preferably has a structure in which an oxetane group and a mesogen group are connected via a spacer such as an alkylene chain. Among them, the monofunctional oxetane compound having a mesogen group is preferably a compound represented by the following general formula (1).

R ¹ in formula is a hydrogen, methyl or ethyl, L ¹ is (CH ₂₎ n- represents an (n is an integer of ¹ ~ 12), X 1 is a single bond, -O-, -S-, OCH _{2 -, -CH 2 O-, -CO-,} -CH 2 CH 2 -, -CF 2 CF 2 -, -OCO-, COO-, CH = CH-, CF = CF-, -CH = CH-COO- , -OCO-CH = CH- or C? C-, and M ¹ represents a group selected from the formula (2). L ² is a single bond, -O-, -S-, OCH ₂ -, -CH ₂ O-, -CO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -OCO-, COO-, CH -CH═CH-, CF═CF-, -CH═CH-COO-, -OCO-CH═CH- or C≡C-, and M ² represents a group selected from the formula (3).

Me, Et, nPr, iPr, nBu and tBu in the formulas (2) and (3) represent a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a n-butyl group and a tert-butyl group.

The monofunctional oxetane compound having such a structure can be produced by a method known in the art. Further, since such a monofunctional oxetane compound is commercially available, a commercial product may be used.

The bifunctional oxetane compound is not particularly limited and those known in the art can be used. It is preferable that the bifunctional oxetane compound exhibits liquid crystallinity from the viewpoint of orientation control property like the monofunctional oxetane compound. Therefore, the bifunctional oxetane compound also preferably has a mesogen group. The bifunctional oxetane compound having a mesogen group preferably has a structure in which an oxetane group and a mesogen group are connected via a spacer such as an alkylene chain. Among them, the bifunctional oxetane compound having a mesogen group is preferably a compound represented by the following general formula (4).

In the formula, R ¹ , L ¹ , L ² , X ¹ , M ¹ and M ² are as defined above, and M ³ represents a group selected from the formula (5).

The bifunctional oxetane compound having such a structure can be prepared by a method known in the art. Such a bifunctional oxetane compound is commercially available, and a commercially available product may be used.

The mass ratio of the monofunctional oxetane compound and the bifunctional oxetane compound in the photopolymerizable composition is not particularly limited, but is preferably 100: 0 to 85:15, more preferably 99: 1 to 86:14, Is 98: 2 to 87:13, particularly preferably 97: 3 to 88:12. When the proportion of the monofunctional oxetane compound is too small, the orientation controllability may be deteriorated.

The surfactant is not particularly limited, but those known in the art can be used. Among them, the surfactant is preferably a fluorine-based surfactant. In the present specification, the term "fluorinated surfactant" means a surfactant in which a hydrogen atom in the alkyl chain is substituted with a fluorine atom, and generally refers to a surfactant having a perfluoroalkyl group. Since a fluorinated surfactant is commercially available, a commercially available product such as MEGAFACE series (for example, MEGAFACE R40, F-554, F-563) of DIC Co., Ltd. can be used as a fluorine surfactant.

When the photopolymerizable compound contains a surfactant, the content of the surfactant is not particularly limited, but is preferably 0.01 part by mass to 1 part by mass, more preferably 0.02 part by mass to 0.9 part by mass with respect to 100 parts by mass of the monofunctional oxetane compound More preferably 0.03 mass parts to 0.8 mass parts, and particularly preferably 0.04 mass parts to 0.7 mass parts. If the content of the surfactant is less than 0.01 part by mass, the effect of the surfactant may not be sufficiently obtained. On the other hand, if the content of the surfactant exceeds 1 part by mass, the orientation controllability may be deteriorated.

The photopolymerizable composition may contain a photopolymerization initiator from the viewpoint of efficiently proceeding the photopolymerization. The photopolymerization initiator is not particularly limited and those known in the art may be used. Examples of the photopolymerization initiator include CPI-100P, CPI-101A and CPI-200K of San-Apro Co., Ltd., CYRACURE photo-curing initiator UVI-6990 of Japan Dow Chemical Co., CYRACURE photo-curing initiator UVI- 6992, CYRACURE photo- 6976 and Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172 and Adeka Optomer SP-300 of ADEKA Co., Ltd., and san- aid SI-60L, san of SANSHIN CHEMICAL INDUSTRY Co., San-aid SI-110L, san-aid SI-110L, san-aid SI-110L, san-aid SI-110L, san-aid SI-110L and san Jiemu Resins Co. Esakyua1064, Esakyua1187 , Omni Cat 550, and Irgacure 250 from Ciba Specialty Chemicals, Inc.). Of these, CPI-100P and CPI-101A, which are triacylsulfonium salt photoacid generators (Photo Acid Generator, photo cationic polymerization initiator), are preferred.

When the photopolymerizable composition contains a photopolymerization initiator, the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the total amount of the monofunctional oxetane compound and the optional bifunctional oxetane compound More preferably 0.3 part by mass to 22 parts by mass, still more preferably 0.5 part by mass to 20 parts by mass, and particularly preferably 1.0 part by mass to 18 parts by mass. If the content of the photopolymerization initiator is less than 0.1 part by mass, the effect of the photopolymerization initiator may not be sufficiently obtained. On the other hand, if the content of the photopolymerization initiator exceeds 25 parts by mass, the orientation controllability may be deteriorated.

The photopolymerizable composition may contain, in addition to the above components, components known in the art such as a solvent, a viscosity modifier, a plasticizer, a polymerization inhibitor, and so forth so long as the effect of the present invention is not lost.

The photopolymerizable composition containing the above components can be prepared according to a method well known in the art. Specifically, the photopolymerizable composition may be prepared by mixing the above components.

The photopolymerizable composition thus obtained is not susceptible to oxygen in the air during the photopolymerization reaction, so that the photopolymerizable composition can be carried out in air. Therefore, there is no need to perform a photopolymerization reaction in a cell or a photopolymerization reaction under an inert atmosphere.

In the method for producing an optically anisotropic polymer film of the present invention, the photopolymerizable composition is first applied to a substrate to form a coating film.

The substrate is not particularly limited and those known in the art can be used. Examples of the substrate include a glass substrate, a plastic substrate, and the like. In particular, in the present invention, since the alignment control is performed by the dynamic photopolymerization method described below, it is not necessary to perform a pre-treatment (for example, formation of an orientation film, rubbing of an orientation film, etc.) for imparting an alignment restraining force.

The method of applying the photopolymerizable composition is not particularly limited, but any method known in the art can be used. Examples of the application method include screen printing, roll coating or coating with a curtain coater, spray coating, spin coating, and the like.

The thickness of the coating film formed on the substrate is not particularly limited and may be suitably set according to the intended design. The typical thickness of the coating film is 0.1 to 200 탆.

After the coating film is formed, the coating film may be heated and dried as necessary. The drying conditions are not particularly limited and may be suitably adjusted according to the kind of the photopolymerizable composition to be used.

Next, the photopolymerization reaction is carried out by irradiating the coating film while continuously changing the exposure part. The light irradiation method is a method called a dynamic light polymerization method and can be carried out according to the method described in Patent Document 1 (International Publication No. 2014-038260). However, in the method for producing an optically anisotropic polymer film of the present invention, since a photopolymerizable composition capable of performing a photopolymerization reaction in air is used without being influenced by an ambient atmosphere, a photopolymerization reaction is performed in a cell as in Patent Document 1, It is not necessary to carry out a photopolymerization reaction. By using the dynamic photopolymerization method, an optically anisotropic polymer film having an orientation region formed in a large area can be efficiently formed.

Hereinafter, the dynamic photopolymerization method will be described with reference to the drawings.

1 is a schematic vertical sectional view for explaining a dynamic photopolymerization method. In the dynamic photopolymerization method, a light source 3 for irradiating light (L) onto a coating film (2) of a photopolymerizable composition formed on a substrate (1) and a light source On the other hand, a photomask (4) capable of moving in the movement direction (D) is arranged above the coating film (2) of the photopolymerizable composition. Thereafter, the photomask 4 is continuously moved in the moving direction D, and the coating film 2 of the photopolymerizable composition is irradiated with light to change the exposure unit A1 continuously. When the light L is irradiated as described above, the polymerization reaction does not proceed in the light-shielding portion A2 shielded by the photomask 4, and the polymerization reaction proceeds in the exposed portion A1, though it is not in the uncopolymerized state. In the exposed portion A1, the monofunctional oxetane compound proceeds in the photopolymerization and the monofunctional oxetane compound is consumed. Therefore, the amount of the monofunctional oxetane compound in the coating film 2 between the exposed portion A1 and the light- There is a bias in concentration. When the concentration of the monofunctional oxetane compound in the coating film (2) is deviated, the diffusion of the substance occurs in the direction of dissolving the concentration gradient due to the diffusion phenomenon of the substance. Diffusion of the monofunctional oxetane compound is caused in the boundary S between the exposed portion A1 and the shielding portion A2 to cause diffusion of the monofunctional oxetane compound from the light shielding portion A2 to the exposed portion A1, A flow of the cetane compound occurs. When a flow of the monofunctional oxetane compound is generated from the light-shielding portion A2 to the exposed portion A1 as described above, a shear stress is applied to the monofunctional oxetane compound by the flow, so that the monofunctional oxetane compound is exposed to the light- ) And the light-shielding portion A2. The direction in which the flow due to the movement of the monofunctional oxetane compound is generated is substantially perpendicular to the boundary S between the exposed portion A1 and the light-shielding portion A2. Therefore, the monofunctional oxetane compound and its polymeric compound The alignment direction of the molecular chains 5 is substantially perpendicular to the boundary S between the exposed portion A1 and the shielding portion A2.

In the dynamic photopolymerization method, by irradiating light onto the coating film 2 of the photopolymerizable composition while continuously moving the photomask 4 in the movement direction D, the boundary S, which continuously moves in the movement direction D, The orientation and the photopolymerization of the monofunctional oxetane compound by diffusion can be continuously generated. Once the alignment of the monofunctional oxetane compound is initiated, alignment is promoted in the liquid crystal due to a unique self-organization force, so that it becomes possible to perform the alignment control efficiently. Therefore, by using the dynamic photopolymerization method, the regions where alignment and photopolymerization have been performed can be continuously increased, so that an optically anisotropic polymer membrane can be efficiently produced. Further, since the alignment direction is determined by the flow of the monofunctional oxetane compound, the optically anisotropic polymer film in which alignment is controlled in a desired direction by controlling the shape of the photomask 4 can be produced.

The light source used for light irradiation is not particularly limited, and a known light source usable for light polymerization can be used. Examples of the light source include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and an LED lamp.

The irradiation intensity at the time of light irradiation may be set according to conditions such as the type and thickness of the coating film 2 and is not particularly limited, but is preferably more than 5 mW / cm 2, more preferably 10 mW / cm 2 to 500 mW / Preferably 30 mW / cm 2 to 400 mW / cm 2, particularly preferably 60 mW / cm 2 to 300 mW / cm 2. If the irradiation intensity is less than 5 mW / cm < 2 >, the reaction rate may become slow and the productivity may be lowered.

The shape of the photomask 4 is not particularly limited, but it is preferable to have a plurality of substantially rectangular slits (openings). In this specification, the term "substantially rectangular shape" is a concept including a shape in which four corners of a rectangle are formed in an arc shape in addition to a rectangular shape, a shape in which a portion corresponding to a long side or a short side of a rectangle is formed in an arc- .

The slit width of the photomask 4 is not particularly limited, but is preferably 0.1 mm to 3 mm, more preferably 0.15 mm to 2.5 mm, and still more preferably 0.2 mm to 2 mm.

The moving speed of the photomask 4 is not particularly limited as long as the speed at which the monofunctional oxetane compound is oriented is preferably 0.01 mm / s to 8 mm / s, more preferably 0.02 mm / s to 7 mm / s, More preferably 0.03 mm / s to 6 mm / s, and particularly preferably 0.05 mm / s to 5 mm / s. If the moving speed of the photomask 4 is less than 0.01 mm / s, desired productivity may not be obtained. On the other hand, when the moving speed of the photomask 4 exceeds 8 mm / s, the monofunctional oxetane compound may not be sufficiently aligned.

The light irradiation may be carried out under heating conditions from the viewpoint of efficiently performing alignment control and photopolymerization. The heating temperature may be suitably set in accordance with the type of the photopolymerizable composition to be used, but is preferably 50 ° C to 120 ° C, more preferably 60 ° C to 110 ° C, and still more preferably 70 ° C to 100 ° C. If the heating temperature is less than 50 캜, the effect of heating can not be sufficiently obtained. On the other hand, if the heating temperature exceeds 120 ° C, the polymerization due to heat may proceed before light irradiation, and the orientation control may become impossible.

Although a method of continuously changing the exposure unit A1 using the photomask 4 has been described above, the exposure unit A1 may be continuously changed by using a light source capable of irradiating only a part of the area.

Light irradiation may be performed on the entire surface of the coating film 2 from the viewpoint of sufficiently curing the coating film 2 after the dynamic photopolymerization. In this case, the light irradiation condition is not particularly limited as long as it is a condition that the coating film 2 is cured. For example, light irradiation may be performed under the same light irradiation conditions as the dynamic light polymerization method.

Since the optically anisotropic polymer film prepared as described above uses a photopolymerizable composition suitable for the dynamic photopolymerization method capable of performing the photopolymerization reaction in the air without being influenced by the ambient atmosphere, it is difficult to cause uncured or cloudy appearance, Do.

This optically anisotropic polymer film can be used as a polarizing film, a retardation film, a viewing angle improving film, a luminance improving film and the like in a display device such as an organic EL display device or a liquid crystal display device. For example, an example in which an optically anisotropic polymer film is used as a retardation film in an organic EL display device is shown in Fig. 2, and an example in which an optically anisotropic polymer film is used as a retardation film in a liquid crystal display device is shown in Fig. An organic EL display device having a structure in which an organic EL display element 12 is sandwiched between a pair of substrates 11 as shown in Fig. 2 and a polarizing film 13 is provided on one substrate 11 The optically anisotropic polymer film 10 is provided between the substrate 11 and the organic EL display element 12 or installed between the substrate 11 and the polarizing film 13 b. 3, a liquid crystal display element 14 is sandwiched between a pair of substrates 11 and a polarizing film 13 is provided on both substrates 11, In the apparatus, the optically anisotropic polymer film 10 is provided between the substrate 11 and the liquid crystal display element 14 or installed between the substrate 11 and the polarizing film 13 (b).

The optically anisotropic polymer film can be formed directly on a member (for example, the substrate 11) constituting each display device when manufacturing a display device such as an organic EL display device or a liquid crystal display device. Further, the optically anisotropic polymer film may be preliminarily manufactured and then adhered to a member (for example, the substrate 11) constituting each display device.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

<Materials Used>

1. Monofunctional oxetane compound

A monofunctional oxetane compound represented by the following formula (6) was used.

In the monofunctional oxetane compound, a monocomponent oxetane compound represented by the formula (6) was synthesized by first synthesizing a compound represented by the formula (iii) according to the following reaction formula and then using the compound as a raw material.

Namely, 51.8 g of 3-ethyl-3-hydroxymethyloxetane represented by the formula (i), 119.2 g of para toluenesulfonyl chloride (p-TsCl), 100 g of sodium hydroxide, 400 ml of tetrahydrofuran (THF) 400 ml of exchange water was added, and the mixture was stirred and mixed at 0 ° C for 4 hours, and the resulting solution was washed with saturated brine three times. To this solution were added 120.8 g of 1, 4-butanol, 43.8 g of potassium hydroxide and 116 ml of dimethylsulfoxide (DMSO), and the mixture was stirred and mixed at 30 DEG C for 15 hours. Then toluene and brine were added thereto and washed, &Lt; / RTI &gt; 65.3 g of methanesulfonyl chloride (MsCl), 65.3 g of toluene and 78.0 g of tolylethylamine (TEA) were added to the thus-obtained compound represented by the formula (ii), and the mixture was stirred at 0 ° C for 2 hours The obtained solution was washed with a saturated saline solution. 55.7 g of ethyl parahydroxybenzoate, 60.7 g of potassium carbonate and 420 g of N, N'-dimethylformamide (DMF) were added and mixed and stirred at 100 DEG C for 5 hours, washed with water, 116 g of a solid were obtained. 36 g of sodium hydroxide and 324 g of ion-exchanged water were added to this solid, and the reaction was carried out at 100 DEG C for 2 hours. The obtained solvent was diluted with water (450 ml), and hydrochloric acid (concentration 10 wt%) was added slowly until the pH reached 3. The obtained slurry solution was stirred at 0 캜 for 1 hour and then washed with water to obtain 121 g of a compound represented by the formula (iii).

Next, 47.2 g of methanesulfonyl chloride (MsCl), 52.0 g of NN-diisopropylethylamine (DIPEA) and 400 ml of tetrahydrofuran (THF) were added to the compound represented by the formula (iii) After mixing and stirring, 270 g of 4- (trans-4-n-propylcyclohexyl) phenol from BOC Sciences, 11.2 g of 4-dimethylaminopyridine (DMAP) and 53.2 g of triethylamine (TEA) And the mixture was stirred for 1 hour. Thereafter, the mixture was further stirred under reflux for 3 hours to obtain a monofunctional oxetane compound represented by the formula (6).

2. Bifunctional oxetane compounds

A bifunctional oxetane compound represented by the following formula (7) was used.

The bifunctional oxetane compound represented by the formula (7) was synthesized by using the compound represented by the formula (iii) synthesized in the same manner as described above as a raw material.

47.2 g of methanesulfonyl chloride (MsCl), 52.0 g of NN-diisopropylethylamine (DIPEA) and 400 ml of tetrahydrofuran (THF) were added to the compound represented by the formula (iii) After mixing and stirring, 68 g of hydeoxyne, 11 g of 4-dimethylaminopyridine (DMAP) and 53 g of triethylamine (TEA) were further added, followed by mixing and stirring at 0 ° C for 1 hour. Thereafter, the mixture was further stirred under reflux for 3 hours to obtain a compound represented by formula (7).

3. Surfactants

A fluorine surfactant (MEGAFACE R40 manufactured by DIC Corporation) was used.

4. Photopolymerization initiator

(CPI-100P of San-Apro Co.) and an alkylphenon-based photopolymerization initiator (Irgacure 651 of BASF) were used.

5. Monofunctional acrylate (for comparative purposes)

4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl (A6CB) was used. This compound was synthesized according to the method described in Patent Document 1 (International Publication No. 2014/038260).

6. Bifunctional methacrylate (for comparison)

Ethylene glycol dimethacrylate (EGDMA, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1,6-hexanediol dimethacrylate (HDDMA, Tokyo Chemical Industry Co., Ltd.) were used.

&Lt; Example 1 >

A photopolymerizable composition was prepared by mixing a monofunctional oxetane compound, a surfactant, and a photo cationic polymerization initiator. In this photopolymerizable composition, the blending amount of the surfactant was set to 0.1 part by mass with respect to 100 parts by mass of the monofunctional oxetane compound, and the amount of the cationic photopolymerization initiator blended was changed to 15 parts by mass with respect to 100 parts by mass of the monofunctional oxetane compound.

Next, the photopolymerizable composition was applied to a glass substrate (10 cm x 10 cm) by spin coating (500 rpm for 4 seconds and 1200 rpm for 30 seconds) and dried at 120 캜 for 5 minutes to form a 2.0 탆 coating film Followed by dynamic photopolymerization using a photomask. In this dynamic photopolymerization method, a metal halide lamp (UVL-7000M-N) was used as a light source for light irradiation, and the irradiation intensity was set to 294 mW / I conducted an investigation. As the photomask, a photomask having a substantially rectangular slit (slit width of 0.25 mm) was used, and the moving speed of the photomask was set to 0.9 mm / s. Thereafter, the entire surface was irradiated with light for one minute under the same light irradiation conditions as in the dynamic light polymerization method to produce a polymer membrane.

&Lt; Example 2 >

A photopolymerizable composition was prepared in the same manner as in Example 1 except that the mixing amount of the photo cationic polymerization initiator was changed to 2.5 parts by mass based on 100 parts by mass of the monofunctional oxetane compound.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity was changed to 281 mW / cm 2 upon light irradiation.

&Lt; Example 3 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity was changed to 281 mW / cm 2 and the moving speed of the photomask was changed to 1.8 mm / s.

<Example 4>

A photopolymerizable composition was prepared in the same manner as in Example 1 except that the mixing amount of the photo cationic polymerization initiator was changed to 10 parts by mass with respect to 100 parts by mass of the monofunctional oxetane compound.

Next, a polymer membrane was prepared in the same manner as in Example 1 except that the thickness of the coating film was changed to 2.5 탆 and the irradiation intensity upon irradiation with light was changed to 281 mW / cm 2.

&Lt; Example 5 >

A photopolymerizable composition was prepared in the same manner as in Example 1 except that the amount of the surfactant was changed to 0.05 part by mass with respect to 100 parts by mass of the monofunctional oxetane compound.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity at the time of light irradiation was changed to 101 mW / cm 2 and the moving speed of the photomask was changed to 0.3 mm / s.

&Lt; Example 6 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1 except that the thickness of the coating film was changed to 1.5 탆, the irradiation intensity upon irradiation with light was changed to 101 mW / cm 2, and the moving speed of the photomask was changed to 0.1 ㎜ / s.

&Lt; Example 7 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity at the time of light irradiation was changed to 31 mW / cm 2 and the moving speed of the photomask was changed to 0.05 mm / s.

&Lt; Example 8 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity was changed to 31 mW / cm 2 and the moving speed of the photomask was changed to 0.1 mm / s.

&Lt; Example 9 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity at the time of light irradiation was changed to 31 mW / cm 2 and the moving speed of the photomask was changed to 0.3 mm / s.

&Lt; Example 10 >

The same photopolymerizable composition as in Example 1 was prepared.

Next, a polymer membrane was prepared in the same manner as in Example 1, except that the irradiation intensity at the time of light irradiation was changed to 31 mW / cm 2 and the moving speed of the photomask was changed to 0.5 mm / s.

&Lt; Example 11 >

A photopolymerizable composition was prepared by mixing a monofunctional oxetane compound, a bifunctional oxetane compound and a photo cationic polymerization initiator. In this photopolymerizable composition, the mass ratio of the monofunctional oxetane compound and the bifunctional oxetane compound was 85:15, and the mixing amount of the photo cationic polymerization initiator was 15.5 parts by mass based on 100 parts by mass of the monofunctional oxetane compound.

Next, the thickness of the coating film was changed to 3.0 탆, the irradiation intensity at the time of light irradiation was changed to 9 mW / cm 2, the heating temperature at the time of light irradiation was changed to 90 캜, the slit width of the photomask was changed to 0.5 mm and the moving speed of the photomask was changed to 0.02 mm / , A polymer membrane was prepared in the same manner as in Example 1. [

&Lt; Comparative Example 1 &

A photopolymerizable composition was prepared by mixing EGDMA, A6CB, and an alkylphenon-based photopolymerization initiator. In this photopolymerizable composition, the molar ratio of EGDMA to A6CB was set to 2:98, and the amount of alkylphenon-based photopolymerization initiator to be added was adjusted to 1 mol% with respect to the total of EGDMA and A6CB.

Next, in the same manner as in Example 1 except that a photomask without a slit was used and the irradiation intensity at the time of light irradiation was changed to 0.016 mW / cm 2, the heating temperature at the time of light irradiation was changed to 85 ° C and the moving speed of the photomask was changed to 0.025 mm / A polymer membrane was prepared in the same manner.

&Lt; Comparative Example 2 &

A photopolymerizable composition identical to that of Comparative Example 1 was prepared.

Next, using a photomask without a slit, the thickness of the coating film was changed to 3.0 탆, the irradiation intensity at the time of light irradiation was changed to 0.05 mW / cm 2, the heating temperature at the time of light irradiation was changed to 85 캜, and the moving speed of the photomask was changed to 0.0025 mm / , A polymer membrane was prepared in the same manner as in Example 1.

&Lt; Comparative Example 3 &

A photopolymerizable composition was prepared in the same manner as in Comparative Example 1 except that the molar ratio of EGDMA to A6CB was changed to 4:96.

Next, a photomask without a slit was used, and the thickness of the coating film was changed to 1.8 탆, the irradiation intensity at the time of light irradiation was changed to 0.001 mW / cm 2, the heating temperature at the time of light irradiation was changed to 120 캜, and the moving speed of the photomask was changed to 0.02 mm / , A polymer membrane was prepared in the same manner as in Example 1.

&Lt; Comparative Example 4 &

A photopolymerizable composition was prepared in the same manner as in Comparative Example 3.

The procedure of Example 1 was repeated except that the irradiation intensity at the time of light irradiation was changed to 0.001 mW / cm 2, the heating temperature at the time of light irradiation was changed to 120 ° C, the slit width of the photomask was changed to 0.1 mm, and the moving speed of the photomask was changed to 2 mm / A polymer membrane was produced.

&Lt; Comparative Example 5 &

A photopolymerizable composition was prepared in the same manner as in Comparative Example 3.

Next, the thickness of the coating film was changed to 1.7 μm, the irradiation intensity at the time of light irradiation was 0.001 mW / cm 2, the heating temperature at the time of light irradiation was 120 ° C., the slit width of the photomask was 0.1 mm and the moving speed of the photomask was changed to 0.002 mm / , A polymer membrane was prepared in the same manner as in Example 1. [

&Lt; Comparative Example 6 >

A photopolymerizable composition was prepared in the same manner as in Comparative Example 3.

Next, the thickness of the coating film was changed to 1.9 μm, the irradiation intensity at the time of light irradiation was 0.001 mW / cm 2, the heating temperature at the time of light irradiation was 120 ° C., the slit width of the photomask was 0.1 mm and the moving speed of the photomask was changed to 0.002 mm / , A polymer membrane was prepared in the same manner as in Example 1. [

&Lt; Comparative Example 7 &

A photopolymerizable composition was prepared in the same manner as in Comparative Example 3.

Next, in the same manner as in Example 1 except that a photomask without a slit was used and the irradiation intensity at the time of light irradiation was changed to 0.001 mW / cm 2, the heating temperature at the time of light irradiation was changed to 120 ° C and the moving speed of the photomask was changed to 0.002 mm / A polymer membrane was prepared in the same manner.

The composition of the photopolymerizable composition prepared in the above Examples and Comparative Examples is summarized in Table 1.

<Table 1>

The polymer membrane obtained in the above example was evaluated for the transmittance, haze value and retardation (? Nd) of 400 to 700 nm. In addition, the polymer membranes obtained in the above Comparative Examples were too cloudy to perform these evaluations.

The transmittance and haze value of 400 to 700 nm were measured in accordance with JIS K7361-1 and JIS K7136 using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.).

Measurement of the retardation (Δnd), which is the product of the refractive index difference (Δn) and the thickness (d) of the polymer membrane, was performed by disposing the polarizers for incident light and transmitted light so that their transmission axes were perpendicular to each other and a polymer membrane was disposed therebetween.

In addition, the polymer membranes obtained in the above Examples and Comparative Examples were hand-evaluated for stickiness.

The evaluation results are shown in Table 2.

<Table 2>

As shown in Table 2, the polymer membranes obtained in Examples had no stickiness, exhibited optical anisotropy, and had high transparency.

On the contrary, the polymer membrane obtained in the comparative example is cloudy and has a tackiness. This is presumably because the A6CB containing the photopolymerizable composition used in the comparative example was affected by oxygen in the ambient atmosphere and the photopolymerization reaction did not proceed sufficiently.

As can be seen from the above-mentioned results, according to the present invention, there can be provided a process for producing an optically anisotropic polymer membrane capable of performing a photopolymerization reaction in the air without being influenced by the ambient atmosphere and further preventing occurrence of uncured or cloudy white matters, and a process for producing an optically anisotropic polymer membrane It is possible to provide a used organic EL display device and a manufacturing method of a liquid crystal display device.

1: substrate 2: coated film
3: Light source 4: Photomask
5: Molecular chain 10: Optical anisotropic polymer membrane
11: substrate 12: organic EL display element
13: polarizing film 14: liquid crystal display element
A1: Exposure section A2:
S: Boundary L: Light
D: Direction of movement

Claims (12)

A step of coating a substrate with a photopolymerizable composition containing a monofunctional oxetane compound having a mesogen group and a bifunctional oxetane compound and / or a surfactant to form a coating film;
And irradiating the coating film with light while continuously changing an exposure unit.
The method of claim 1, wherein
Wherein the photopolymerizable composition further comprises a photo cationic polymerization initiator.
The method according to claim 1 or 2, wherein
Wherein the surfactant is a fluorine-based surfactant.
The method according to claim 1 or 2, wherein
Wherein the mass ratio of the monofunctional oxetane compound to the bifunctional oxetane compound in the photopolymerizable composition is 100: 0 to 85:15.
The method according to claim 1 or 2, wherein
Wherein said photopolymerizable composition comprises 0.01 to 1 part by mass of said surfactant based on 100 parts by mass of said monofunctional oxetane compound.
The method according to claim 1 or 2, wherein
Wherein the irradiation intensity during the light irradiation is more than 5 mW / cm &lt; 2 &gt;.
The method according to claim 1 or 2, wherein
Wherein the continuous change of the exposure unit is performed by continuously moving the photomask.
The method of claim 7, wherein
Wherein the photomask has a slit width of 0.1 to 3 mm.
The method of claim 7, wherein
Wherein the moving speed of the photomask is 0.01 to 8 mm / s.
The method according to claim 1 or 2, wherein
Wherein the coating film is heated at a temperature of 50 to 120 DEG C during the light irradiation.
An organic EL display device using an optically anisotropic polymer film obtained by the production method according to claim 1 or 2 as at least one film selected from the group consisting of a polarizing film, a retardation film, a viewing angle improving film and a luminance improving film Gt;
A liquid crystal display device using the optically anisotropic polymer film obtained by the production method according to claim 1 or 2 as at least one film selected from the group consisting of a polarizing film, a retardation film, a viewing angle improving film and a luminance improving film Way.

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