KR20160046829A - Composition for forming film, and single-layer-coated horizontally oriented film - Google Patents

Abstract

식 [1a] 및 [1b]로 표시되는 반복단위를 포함하는 적어도 1종의 중합체와 유기 용매를 함유하는 것을 특징으로 하는 막 형성용 조성물.

A composition for forming a film, which comprises at least one polymer containing a repeating unit represented by the formula [1a] and [1b] and an organic solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for film formation and a single-layer coating type horizontally oriented film,

The present invention relates to a film-forming composition and a single layer-applied horizontally oriented film. More specifically, the present invention relates to a film forming composition which provides a film which can be suitably used for a material having optical characteristics suitable for use in a display device or a recording material, particularly, an optical compensation film such as a polarizing plate and a retarder for a liquid crystal monitor, To a single-layer application type horizontally oriented film obtained from a composition.

There has been an increasing demand for a polymer film whose internal molecular alignment structure is controlled as an optical compensation film such as a polarizing plate or a retardation plate due to demands for improvement in display quality and light weight of a liquid crystal display device. In order to meet this demand, development of a film using optical anisotropy of a polymerizable liquid crystal compound has been carried out. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

Such a polymerizable liquid crystal compound generally becomes a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays. For example, there is a method (Patent Document 1) in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and irradiated with radiation while keeping the compound in a liquid crystal state (Patent Document 1) A method of adding a photopolymerization initiator to a composition of a liquid crystal compound or a mixture of the mixture with a chiral liquid crystal and irradiating ultraviolet rays to obtain a polymer (Patent Document 2) is known.

(Patent Documents 3 and 4) using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film, and an orientation film (Patent Documents 5 and 6) using a polymer containing a photo- Oriented films have been reported. However, polymers used for these films are required to use a solvent having a low solubility and excellent solubility such as N-methyl-2-pyrrolidone, chloroform, and chlorobenzene as a solvent. Therefore, The refractive index anisotropy (? N), the haze value, and the like are deteriorated. Further, no material capable of obtaining an orientation film showing a low haze value by a simple process has been found so far.

Japanese Patent Laid-Open No. 62-70407 Japanese Patent Application Laid-Open No. 9-208957 European Patent Application Publication No. 1090325 International Publication No. 2008/031243 Japanese Patent Application Laid-Open No. 2008-164925 Japanese Patent Application Laid-Open No. 11-189665

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a film-forming composition capable of producing a single-layer coating type horizontally oriented film exhibiting a low haze value by a simpler process and a single- The purpose.

As a result of intensive investigations to solve the above problems, the present inventors have found that by using a polymer having a? -Butyrolactone skeleton in its main chain and having a acid ester structure on the side chain extending from the? -Position of the lactone ring A horizontal orientation film having a refractive index anisotropy (? N) can be obtained without using a liquid crystal alignment film, and a horizontally oriented film exhibiting a low haze value can be produced under a low temperature condition because a stable network structure is formed after the polarized UV exposure And completed the present invention.

That is, the present invention provides a film-forming composition and a single layer-applied horizontally oriented film.

1. A film-forming composition comprising at least one polymer containing repeating units represented by the formulas [1a] and [1b] and an organic solvent.

[In the formula, X is a group represented by the formula [2] or [3]

(Wherein R < ¹ > is a hydrogen atom or a methyl group.

M ¹ is a group represented by the formula [4], M ² is a group represented by the formula [5]

(Wherein, s1~s4 are each independently 1 or 2, G ¹ represents a single bond, -COO- or -OCO-, and, R ² is a cyano group halogen atom, hydrogen atom, having 1 to 10 carbon atoms An alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to ³ carbon atoms.

m and n are numbers satisfying 0 <m <100, 0 <n <100, and m + n≤100,

q and r each independently represent an integer of 2 to 9.]

2. A single-layer coating type horizontally oriented film obtained by applying a film-forming composition of 2.1 to a substrate, and then irradiating with polarized light to cure.

3. The single-layer applied horizontally oriented film of 2 wherein the polarized light is a linearly polarized ultraviolet ray.

4. An optical member comprising a two-layer or three-layer coated horizontally oriented film.

The polymer of the present invention contains a? -Butyrolactone skeleton in the main chain. Therefore, it is possible to produce a single-layer coating type horizontally oriented film exhibiting a low haze value by applying a film-forming composition containing the polymer, irradiating linearly polarized light at room temperature, and performing post-baking.

Fig. 1 is a diagram showing the retardation value angle dependency at a wavelength of 550 nm of the film obtained in Example 1. Fig.
Fig. 2 is a diagram showing the retardation value angle dependency at a wavelength of 550 nm of the film obtained in Example 2. Fig.
3 is a diagram showing the retardation value angle dependence at a wavelength of 550 nm of the film obtained in Example 3. Fig.
4 is a diagram showing the retardation value angle dependency of the film obtained in Comparative Example 1 at a wavelength of 550 nm.

[Composition for forming a film]

The film-forming composition of the present invention contains at least one kind of the following polymer and an organic solvent.

[polymer]

The polymer contained in the film forming composition of the present invention includes the repeating units represented by the formulas [1a] and [1b].

In the formula [1a], X is a group represented by the formula [2] or [3].

(Wherein R &lt; ¹ &gt; is a hydrogen atom or a methyl group.

In the formula [1a], M ¹ is a group represented by the formula [4], and M ² in the formula [1b] is a group represented by the formula [5].

(Wherein, s1~s4 are each independently 1 or 2, G ¹ represents a single bond, -COO- or -OCO-, and, R ² is a cyano group halogen atom, a hydrogen atom, having 1 to 10 carbon atoms An alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to ³ carbon atoms.

Here, the halogen atom includes fluorine, chlorine, bromine and iodine atoms, but in the present invention, a fluorine atom is preferable.

The alkyl group may be any of linear, branched and cyclic, and the carbon number thereof is not particularly limited. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec- N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Of these, R ² is preferably a straight-chain alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group. R ³ is preferably an alkyl group having 1 to ³ carbon atoms, particularly preferably a methyl group or an ethyl group.

The alkoxy group may be any of linear, branched and cyclic, and the carbon number thereof is not particularly limited. In the present invention, a straight chain alkoxy group having 1 to 10 carbon atoms is preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a s-butoxy group, Hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, and n-decyloxy group. Among them, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

In the above alkyl group and alkoxy group, a part or all of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

R ² is more preferably a hydrogen atom, a fluorine atom, a cyano group, a methyl group, or a methoxy group. R ³ is more preferably a methyl group.

G ¹ is preferably -COO- or -OCO-.

M and n are numbers satisfying 0 <m <100, 0 <n <100, and m + n≤100, respectively, representing the content (mol%) of each repeating unit in the formulas [1a] and [ M, 90 and 10? N? 80 in view of improvement of? N and improvement of solubility of the polymer, and it is preferable that the number satisfies 50? M? 80 and 20? N? Is more preferable.

Among the formulas [1a] and [1b], q and r each independently represent an integer of 2 to 9, preferably 3 to 6, more preferably 5 or 6 as q.

The polymer preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. When the weight average molecular weight is more than 200,000, the solubility in a solvent is lowered and the handling property is lowered. On the other hand, if the weight average molecular weight is less than 3,000, the curing becomes insufficient at the time of thermosetting and the solvent resistance and heat resistance are lowered have.

The weight average molecular weight is a polystyrene reduced value measured by gel permeation chromatography (GPC).

The polymer may contain other repeating units other than the formula [1a] and [1b], so long as the effect of the present invention is not impaired. Examples of the polymerizable compound which provides the above other repeating unit include an acrylate ester compound, a methacrylate ester compound, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, and a styrene compound.

The content of the other repeating units is preferably 0 to 10 mol% of the total repeating units. If the content of the other repeating units is too large, the properties of the polymer of the present invention, such as the liquid crystallinity, may be deteriorated.

Further, the polymer of the present invention may be any of a random copolymer, an alternating copolymer and a block copolymer.

[Polymerizable compound]

The polymerizable compound which is a raw material of the polymer used in the present invention is represented by the formulas [6] and [7].

Wherein R ² , R ³ , G ¹ , q, r and s ^{1 to s} 4 are as defined above. X 'is a polymerizable group represented by the formula [8] or [9].

(Wherein R &lt; ¹ &gt; is as defined above)]

[Synthesis of polymerizable compound]

The polymerizable compound can be synthesized by combining the techniques in organic synthesis chemistry, and the synthesis method thereof is not particularly limited.

For example, the polymerizable compound represented by the formula [6] is prepared in the following manner.

When G ¹ is -COO-, as shown in the following reaction formula, the benzoic acid derivative represented by the formula [10] and the phenol derivative are condensed in a solvent in the presence of a condensing agent.

DCC is N, N'-dicyclohexylcarbodiimide, DMAP is N, N-dimethyl-4-aminopyridine, R &lt; ² &gt;, X & .

When G ¹ is -OCO-, a phenol derivative represented by the formula [11] and a benzoic acid derivative are condensed in a solvent in the presence of a condensing agent as shown by the following scheme (reaction formula).

(Wherein R ² , X ', q, s 1 and s 2 are as defined above)

The compound represented by the formula [7] is produced by condensing a compound represented by the formula [12] and a phenol derivative in a solvent in the presence of a condensing agent, as shown by the following synthesis scheme.

(Wherein R ³ , r, s 3 and s 4 are as defined above).

The compounds represented by the formulas [10] and [11] are available as commercial products from SYNTHON Chemicals or Midorikaku Co., Ltd. when X 'is a group represented by the formula [8].

Examples of compounds represented by the formulas [10] and [11], wherein X 'is a group represented by the formula [9] and compounds represented by the formula [12] are described in, for example, Talaga et al. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)). This method is a method in which 2- (bromomethyl) acrylic acid is reacted with an aldehyde or ketone using SnCl ₂ , as shown by synthesis scheme A1 below. In addition, 2- (bromomethyl) acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol.61, pp. 56-59 (1983)).

(Wherein R 'represents a monovalent organic group, Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm and Haas, THF represents tetrahydrofuran, Et represents ethyl group).

Further, in the reaction of 2- (bromomethyl) acrylic acid using SnCl ₂ , an α-methylene-γ-butyrolactone structure can be obtained by reaction with a corresponding acetal or ketal instead of aldehyde or ketone. Examples of the acetal or ketal include compounds having a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxolane group, a 1,3-dioxolane group, and the like. The synthesis method and the protecting group in the case of using acetal or ketal in the following Synthesis Scheme A2 are shown.

(Wherein R 'is as defined above).

The compound represented by the formula [10], [11] or [12] can be synthesized by the following synthesis scheme B or C using the synthetic scheme A1 or A2.

(Wherein q and s1 are as defined above, Me represents a methyl group, and PCC represents pyridinium chlorochromate).

(Wherein q and s1 are as defined above.)

[Synthesis of Polymer]

The method for synthesizing the polymer is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, and the like can be employed. Of these, radical polymerization is particularly preferable. Specifically, the polymerization may be performed by heating the polymerizable compound in a solvent in the presence of a polymerization initiator.

As the polymerization initiator, conventionally known ones can be appropriately selected and used. Peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like; Persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; Azo compounds such as azobisisobutyronitrile (AIBN), azobismethylbutyronitrile and azobisisovaleronitrile, and the like can be given. These may be used singly or in combination of two or more.

The amount of the polymerization initiator to be used is preferably about 0.01 to 0.05 mol based on 1 mol of the polymerizable compound.

The reaction temperature may be appropriately set from 0 ° C to the boiling point of the solvent used, and is preferably about 20 to 100 ° C. The reaction time is preferably about 0.1 to 30 hours.

The solvent used in the polymerization reaction is not particularly limited and may be suitably selected from various solvents generally used in the polymerization reaction. Specifically, water; But are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, There may be mentioned alcohols such as t-butanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol Ryu; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and carbon tetrachloride; Ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve and diethylene glycol monobutyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonene, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene and anisole; Acetals such as methylal, diethyl acetal and the like; Fatty acids such as formic acid, acetic acid and propionic acid; (NMP), N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone And the like. These may be used alone or in combination of two or more.

When the polymer contains other repeating units other than the formulas [1a] and [1b], as a synthesizing method thereof, a polymerizable compound which provides the above other repeating unit may be co-polymerized during the polymerization.

[Organic solvents]

Examples of the organic solvent contained in the film-forming composition of the present invention include ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene, toluene and xylene; Polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as ethyl acetate, butyl acetate, and ethyl lactate; Alkoxy esters such as methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Dialkyl dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether; Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Diglycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; Glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; And ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-thionyl carbon. These organic solvents may be used singly or in combination of two or more.

Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, and cyclohexanone are preferred.

The amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.

[Other components]

A surfactant may be added to the film forming composition of the present invention for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include a fluorine surfactant, a silicone surfactant, and a nonionic surfactant. Of these, a fluorine-based surfactant having a high affinity for improving affinity with a substrate is preferable.

Specific examples of the fluorochemical surfactant include Fafto EF301, EF303 and EF352 (manufactured by Tohchem Products Corporation), Megafac F171, F173 and R-30 (manufactured by DIC Corporation), Florado FC430 and FC431 (Manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Garas Co., Ltd.) Do not. The surfactant may be used singly or in combination of two or more, and the addition amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the polymer.

An adhesion promoter may be added to the film forming composition of the present invention for the purpose of improving adhesion with a substrate.

Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane; Alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane and the like; Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole and the like; Vinyl trichlorosilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane , γ- (N-piperidinyl) propyltrimethoxysilane, and the like; Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thyouracil, Heterocyclic compounds such as mercaptopyrimidine; Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; Thio urea compounds, and the like.

The adhesion promoter may be used singly or in combination of two or more, and the addition amount thereof is preferably 1 part by mass or less based on 100 parts by mass of the polymer.

[Horizontal Orientation Film of Single Layer Coating Type]

The film forming composition of the present invention can be applied to a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, chromium or the like, A quartz substrate, an ITO substrate, or the like) or a film (e.g., a film of a resin such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) A film can be formed by applying a coating film by a coating method, a roll coating method, a slit coating method, a slit coating method, a spin coating method, an ink jet method, a printing method or the like to form a coating film and then heating and drying in a hot plate or oven.

As the heating and drying conditions, for example, heating temperature and heating time appropriately selected from the range of 40 to 100 占 폚 and 0.1 to 60 minutes are employed. The heating temperature and the heating time are preferably 40 to 80 DEG C for 0.1 to 2 minutes.

The thus formed film is subject to linear polarization irradiation and post baking to obtain a single layer coating type horizontally oriented film.

As a method of irradiating linearly polarized light, ultraviolet rays to visible rays having a wavelength of 150 to 450 nm are usually used and irradiated with linearly polarized light at room temperature or in a heated state. The irradiation dose varies depending on the light used, but is preferably about 100 to 2,000 mJ / cm ² .

The post bake may be heated by a hot plate or an oven, and the temperature and time are preferably 90 to 150 DEG C for 2 to 20 minutes, more preferably 95 to 120 DEG C for 5 to 20 minutes.

The film thickness of the single-layer coating type horizontally oriented film of the present invention can be appropriately selected in consideration of the step difference and the optical and electrical properties of the substrate to be used. For example, 0.1 to 3 탆 is suitable.

The thus obtained single-layer coating type horizontally oriented film of the present invention is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and a retarder for a liquid crystal monitor.

Example

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring method and the measuring condition of each physical property in the examples are as follows.

[1] &lt; ¹ &gt; H-NMR

The compound was dissolved in deuterated chloroform (CDCl ₃ ), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Zeol Co.).

[2] Average molecular weight measurement

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko K.K.

[3] Haze value

The haze value of the film was measured using Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku Co., Ltd.

[4] retardation value (?

The nd of a wavelength of 550 nm was measured using a retardation measurement apparatus (RETS-100, manufactured by Otsuka Denshi Co., Ltd.).

[5] polarizing microscope observation

Observation was carried out using a polarizing microscope E600-Pol manufactured by Nikon Corporation.

[Synthesis Example 1] Synthesis of polymerizable compound (M1)

[1] Synthesis of intermediate compound (A1)

7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate and 70 mL of acetone were added to a 200 mL eggplant- And the mixture was reacted at 64 DEG C for 24 hours with stirring. After completion of the reaction, the solvent was distilled off from the reaction solution under reduced pressure to obtain a yellow wet solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the obtained solution to obtain 11.3 g of a white solid. The result of ¹ H-NMR measurement of this solid is shown below. From this result, it was confirmed that the white solid was the desired intermediate compound (A1) (yield: 90%).

[2] Synthesis of intermediate compound (B1)

Next, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were added to a 100 mL three-necked flask equipped with a cooling tube and 2.5 g (10.0 mmol) of the intermediate compound (A1) was dissolved in dichloromethane 15.0 mL was added dropwise, and the mixture was further stirred at room temperature for 6 hours. Then, 90 ml of diethyl ether was added to the solution from which the oily substance adhered to the wall of the flask was removed, and the mixture was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a wet green solid. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the obtained solution to obtain 1.3 g of a colorless solid. The result of ¹ H-NMR measurement of this solid is shown below. From this result, it was confirmed that the colorless solid was the desired intermediate compound (B1) (yield: 50%).

[3] Synthesis of intermediate compound (C1)

Next, 1.25 g (5.0 mmol) of the intermediate compound (B1), 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, 1.5 g of Amberlyst (registered trademark) 15 (manufactured by Rohm and Haas) ), 8.09 mL of THF, 0.95 g (5.0 mmol) of tin (II) chloride and 2.0 mL of pure water were added to the mixture, and the mixture was reacted at 70 DEG C for 5 hours with stirring. After completion of the reaction, the reaction mixture was filtered under reduced pressure, mixed with 40 mL of pure water, and 50 mL of diethyl ether was added to the mixture. Extraction was carried out three times.

The organic layer after the extraction was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain 1.5 g of a colorless solid. The result of ¹ H-NMR measurement of this solid is shown below. From this result, it was confirmed that the colorless solid was the desired intermediate compound (C1) (yield: 94%).

[4] Synthesis of intermediate compound (D1)

35 ml of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (C1) and 5 ml of a 10 mass% sodium hydroxide aqueous solution were added to a 100 ml eggplant-shaped flask with a cooling tube, and the mixture was reacted at 85 ° C for 3 hours with stirring. After the completion of the reaction, 300 mL of water and a reaction solution were added to a 500 mL beaker, and the mixture was stirred at room temperature for 30 minutes. 5 mL of a 10% by mass aqueous HCl solution was then added dropwise and filtered to obtain 1.3 g of a white solid.

Next, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (manufactured by Rohm and Haas) and 20.0 mL of tetrahydrofuran were added to a 50 mL eggplant-shaped flask equipped with a cooling tube, followed by stirring at 70 캜 for 5 hours Lt; / RTI &gt; After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off from the solution to obtain a yellow solid. This yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1) to obtain 0.9 g of a white solid. The result of ¹ H-NMR measurement of this solid is shown below. From this result, it was confirmed that the white solid was the desired intermediate compound (D1) (yield: 71%).

[5] Synthesis of polymerizable compound (M1)

3.0 g (10.0 mmol) of the intermediate compound (D1), 1.8 g (10.0 mmol) of methyl 4-hydroxycinnamate, 0.05 g of DMAP and a small amount of butylhydroxytoluene (BHT) were stirred at room temperature with 45 mL , And a solution prepared by dissolving 2.7 g (13.0 mmol) of DCC in 15 mL of dichloromethane was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of a saturated sodium hydrogencarbonate aqueous solution and 100 mL of saturated brine successively, dried with magnesium sulfate, and then the solvent was distilled off under reduced pressure To give a yellow solid. This solid was purified by recrystallization with ethanol. 2.6 g of the target polymerizable compound (M1) was obtained (yield: 56%).

[Synthesis Example 2] Synthesis of polymerizable compound (M2)

[1] Synthesis of intermediate compound (A2)

(25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol and 7.0 g (50 mmol) of potassium carbonate were added to a 100- And acetone (50 mL) were added to the mixture, and the mixture was reacted at 64 DEG C for 24 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid was mixed with 70 mL of water and extracted with 50 mL of diethyl ether. Extraction was carried out three times.

The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck Co., eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the obtained solution to obtain 6.9 g of a white solid. The result of ¹ H-NMR measurement of this solid is shown below. From this result, it was confirmed that the white solid was the desired intermediate compound (A2) (yield: 91%).

[2] Synthesis of polymerizable compound (M2)

3.0 g (10.2 mmol) of Intermediate Compound (A2) was dissolved in 10 mL of THF together with 1.5 mL of triethylamine and a small amount of BHT, and the mixture was stirred at room temperature, and 0.9 mL of acryloyl chloride dissolved in 10 mL of THF The work was dripped over 15 minutes. After the dropwise addition, the reaction solution was stirred for 30 minutes, the water bath was removed, stirring was continued overnight while returning to room temperature, and the precipitated triethylamine hydrochloride was filtered. The organic layer was washed successively with 50 mL of a saturated aqueous solution of sodium hydrogencarbonate, 50 mL of 0.5 mol / L hydrochloric acid, and 50 mL of a saturated aqueous solution of sodium hydrogencarbonate, and the organic layer was washed successively with magnesium sulfate After drying, the solvent was distilled off to obtain a product. After recrystallization with methanol, 1.7 g of the intended polymerizable compound (M2) was obtained. The measurement results of ¹ H-NMR are shown below.

[Synthesis Example 3] Synthesis of polymerizable compound (M3)

0.6 g (2.0 mmol) of the intermediate compound (D1) obtained in Synthesis Example 1, 0.3 g (2.0 mmol) of 4-hydroxybiphenyl, 0.008 g of DMAP and a small amount of BHT were suspended in 10 mL of dichloromethane A solution of 0.5 g (2.5 mmol) of DCC in 5 mL of dichloromethane was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 ml of 0.5 mol / L hydrochloric acid, 50 ml of a saturated sodium hydrogencarbonate aqueous solution and 50 ml of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, To obtain 0.6 g of the intended polymerizable compound (M3) (yield: 62%). The measurement results of ¹ H-NMR are shown below.

[Synthesis Example 4] Synthesis of polymerizable compound (M4)

(100 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (SYNTHON Chemicals), 17.0 g (100 mmol) of 4-hydroxybiphenyl, 0.6 g of DMAP and a small amount of BHT Was suspended in 200 mL of dichloromethane under stirring, and a solution prepared by dissolving 24.0 g (116 mmol) of DCC in 100 mL of dichloromethane was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 150 mL of 0.5 mol / L hydrochloric acid, 150 mL of saturated sodium hydrogencarbonate aqueous solution and 150 mL of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, To obtain 39.6 g of the aimed polymerizable compound (M4) (yield: 89%). The measurement results of ¹ H-NMR are shown below.

[Synthesis Example 5] Synthesis of polymerizable compound (M5)

(10 mmol) of 4- (6-acryloyloxy-1-hexyl) benzoic acid (SYNTHON Chemicals), 1.8 g (10 mmol) of methyl 4-hydroxycinnamate, 0.06 g of DMAP and a small amount of BHT were stirred In 30 mL of dichloromethane, a solution of 2.4 g (12 mmol) of DCC dissolved in 10 mL of dichloromethane was added thereto, and the mixture was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed with 20 mL of 0.5 mol / L hydrochloric acid, 20 mL of a saturated sodium hydrogencarbonate aqueous solution and 30 mL of saturated brine successively twice, dried over magnesium sulfate, and then the solvent was distilled off To obtain a yellow solid. This solid was purified by recrystallization with ethanol. 3.4 g of a target polymerizable compound (M5) was obtained (yield: 72%). The measurement results of ¹ H-NMR are shown below.

[Synthesis Example 6] Synthesis of polymer (1)

0.98 g (2.1 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 1.7 g (4.9 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 2, 24 g of NMP and 57 mg of AIBN were charged in a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 300 mL of methanol to precipitate a white powder. This white powder was filtered and vacuum-dried at room temperature to obtain 2.6 g of polymer (1) (yield: 96%). The obtained polymer (1) had Mn of 20,643 and Mw of 64,612 (Mw / Mn = 3.13).

[Synthesis Example 7] Synthesis of polymer (2)

0.40 g (0.9 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.91 g (2.0 mmol) of the polymerizable compound (M3) obtained in Synthesis Example 3, 11.8 g of NMP and 25 mg of AIBN were placed in a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 300 mL of methanol, and a white powder was precipitated. The white powder was filtered and vacuum-dried at room temperature to obtain 0.95 g of polymer (2) (yield: 73%). The obtained polymer (1) had 23,432 Mn and 52,956 Mn (Mw / Mn = 2.26).

[Synthesis Example 8] Synthesis of polymer (3)

(0.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.44 g (1.0 mmol) of the polymerizable compound (M4) obtained in Synthesis Example 4, 5.8 g of NMP and 12 mg of AIBN were charged in a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 200 mL of methanol, and a white powder was precipitated. This white powder was filtered, and then vacuum-dried at room temperature to obtain 0.5 g of polymer (3) (yield: 78%). The obtained polymer (1) had Mn of 15,877 and Mw of 51,759 (Mw / Mn = 3.26).

[Synthesis Example 9] Synthesis of polymer (4)

0.54 g (1.2 mmol) of the polymerizable compound (M5) obtained in Synthesis Example 5, 1.3 g (2.8 mmol) of the polymerizable compound (M4) obtained in Synthesis Example 4, 16 g of NMP and 34 mg of AIBN were added to a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 300 mL of methanol to precipitate a white powder. This white powder was filtered, and then vacuum-dried at room temperature to obtain 1.6 g of polymer (4) (yield: 89%). The obtained polymer (1) had Mn of 12,678 and Mw of 22,313 (Mw / Mn = 1.76).

[Preparation of Film Forming Composition and Film Preparation and Evaluation]

A film-forming composition was prepared using the polymer obtained in Synthesis Example, and a film was produced in accordance with the following conditions, and the characteristics thereof were examined.

Film production conditions:

Spin coating: 300 rpm / 5 sec, 500-1000 rpm / 20 sec

Prebake: 50 캜 / 30 sec (hot plate)

Exposure: linear polarized ultraviolet ray, vertical irradiation, irradiation dose 1,000 mJ / cm ² (wavelength 313 nm)

Post bake: 100 占 폚 or 120 占 폚 / 20 minutes (hot plate)

[Example 1]

150 mg of the polymer (1) and 0.3 mg of R-30 (surfactant of DIC, the same applies hereinafter) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (1). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the film obtained on the substrate was transparent.

Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 1.4 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was aligned horizontally with respect to the substrate surface. The? Nd was 43 nm, and the haze value was 0.3%. Fig. 1 shows the angle dependency of DELTA nd of the film.

[Example 2]

150 mg of the polymer (2) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (2).

This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the film obtained on the substrate was transparent.

Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 1.6 탆 and it was observed with a polarizing microscope that the film was aligned horizontally with respect to the substrate surface. The? Nd was 53 nm, and the haze value was 0.0%. Fig. 2 shows the angle dependency of DELTA nd of the film.

[Example 3]

150 mg of the polymer (3) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (3).

This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the film obtained on the substrate was transparent.

Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 1.8 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was horizontally aligned with respect to the substrate surface. The? Nd was 79 nm, and the haze value was 0.4%. Fig. 3 shows the angle dependence of DELTA nd of the film.

[Comparative Example 1]

150 mg of the polymer (4) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (4).

This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the film obtained on the substrate was transparent.

Next, the coated film formed on the glass substrate was exposed, and then post-baked on a hot plate at 100 캜 for 20 minutes. The obtained film had a film thickness of 1.5 탆, which was observed by a polarizing microscope. As a result, a horizontally oriented film was not obtained. The nd was 25 nm and the haze value was 4.0%. Fig. 4 shows the angular dependence of DELTA nd of the film.

The above results are summarized in Table 1 below.

polymer Film thickness (占 퐉) Δnd (nm) Haze value (%) Example 1 (One) 1.4 43 0.3 Horizontally oriented film Example 2 (2) 1.6 53 0.0 Horizontally oriented film Example 3 (3) 1.8 79 0.4 Horizontally oriented film Comparative Example 1 (4) 1.5 25 4.0 Orientation disorder

Claims (4)

A composition for forming a film, which comprises at least one polymer containing a repeating unit represented by the formula [1a] and [1b] and an organic solvent.

[Wherein X is a group represented by the formula [2] or [3]

(Wherein R < ¹ &gt; is a hydrogen atom or a methyl group.
M ¹ is a group represented by the formula [4], M ² is a group represented by the formula [5]

(Wherein, s1~s4 are each independently 1 or 2, G ¹ represents a single bond, -COO- or -OCO-, and, R ² is a cyano group halogen atom, a hydrogen atom, having 1 to 10 carbon atoms An alkyl group or an alkoxy group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to ³ carbon atoms.
m and n are numbers satisfying 0 <m <100, 0 <n <100, and m + n≤100,
q and r each independently represent an integer of 2 to 9.] A single-layer coating type horizontally oriented film obtained by applying the film forming composition according to claim 1 to a substrate, and then irradiating and curing the polarizing film. The single-layer coating type horizontally oriented film according to claim 2, wherein the polarized light is linearly polarized ultraviolet light. An optical member comprising the single-layer coating type horizontally oriented film according to claim 2 or 3.

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