TW201527393A - Film forming composition and monolayer coating type horizontal alignment film - Google Patents

Abstract

The present invention relates to a film forming composition, characterized by containing the following polymer and organic solvent; the polymer contains at least one kind of repeating units expressed by formula [1a] and [1b], wherein, X is a group expressed by formula [2] or [3] (wherein, R 1 is hydrogen or methyl. The dotted line is a bond), M1 is a group expressed by formula [4], M2 a group expressed by formula [5] (wherein, s1 ~ s4 independently is 1 or 2, G 1 is a single bond, -COO- or -OCO-, R 2 is hydrogen, halogen, cyano, alkyl or alkoxy, R 3 is an alkyl group; the dotted line is a bond) m and n are integers and respectively satisfy 0 < m < 100, 0 < n < 100, and m + n ≤ 100, and q and r are each independently an integer of 2 to 9.

Description

Film forming composition and single layer coating type horizontal alignment film

The present invention relates to a film forming composition and a single layer coating type horizontal alignment film. In particular, a material for forming a film having an optical property suitable for use in a display device or a recording material, and the like, and a film forming composition for forming a film suitable for use in an optical compensation film such as a polarizing plate for a liquid crystal display or a phase difference plate, And a single layer coating type horizontal alignment film obtained from the composition.

In the optical compensation film such as a polarizing plate or a phase difference plate, the requirements for the polymer film having a controlled molecular alignment structure are increasing as the display quality of the liquid crystal display device is increased or reduced. In order to achieve this, development of a film using optical anisotropy of a polymerizable liquid crystal compound is underway. The polymerizable liquid crystal compound to be used is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure site (having a structure portion of a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

The polymerizable liquid crystal compound is generally a polymer (film) by a method of performing polymerization by irradiation with radiation such as ultraviolet rays. example For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports, a compound is held in a liquid crystal state, and a polymer is irradiated with radiation is known (Patent Document 1), or an acrylic group is known. A method in which a mixture of a polymerizable liquid crystal compound or a mixture of a chiral liquid crystal is added to the mixture to form a photopolymerization initiator, and ultraviolet rays are irradiated to obtain a polymer (Patent Document 2).

In addition, an alignment film (Patent Documents 3 and 4) using a polymerizable liquid crystal compound or a polymer which does not require a liquid crystal alignment film, and an alignment film (Patent Documents 5 and 6) using a polymer containing a photocrosslinking site have been used. Layer coating type alignment film. However, the solubility of the polymer used for these films is low, and it is necessary to use a solvent having excellent solubility such as N-methyl-2-pyrrolidone, chloroform or chlorobenzene as a solvent, and thus the film obtained from these solutions is used. Characteristics such as refractive index anisotropy (Δn) and haze value may deteriorate. Further, a material for obtaining an alignment film exhibiting a low haze value by a simple process has not been found yet.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP-A-62-70407

[Patent Document 2] Japanese Patent Publication No. 9-208957

[Patent Document 3] European Patent Application Publication No. 1090325

[Patent Document 4] International Publication No. 2008/031243

[Patent Document 5] JP-A-2008-164925

[Patent Document 6] JP-A-11-189665

The present invention has been made in view of the above problems, and the present invention is a film forming composition capable of producing a single-layer coating type horizontal alignment film which exhibits a low haze value in a simple process, and a composition obtained from the composition. The single layer coating type horizontal alignment film is for the purpose.

The inventors of the present invention have made it possible to solve the above problems and repeat the detailed review. It has been found that the γ-butyrolactone skeleton has a cinnamate structure on the side chain extending from the γ position of the lactone ring while being contained in the main chain. The polymer has a stable network structure after exposure to polarized ultraviolet light, and a horizontal alignment film having refractive index anisotropy (Δn) can be obtained without using a liquid crystal alignment film, and a horizontal alignment film exhibiting a low haze value can be obtained. The present invention was completed by being produced under low temperature conditions.

That is, the present invention provides the following film-forming composition and single-layer coating type horizontal alignment film.

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

Wherein X is a group of the formula [2] or [3], (wherein R ¹ is a hydrogen atom or a methyl group. The dotted line is a bond)

M ¹ is a group represented by the formula [4], and M ² is a group represented by the formula [5]. (wherein, s1 to s4 are each independently 1 or 2, G ¹ is a single bond, -COO- or -OCO-, and R ² is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or carbon An alkoxy group having 1 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 3 carbon atoms. The broken line is a bonding bond).

m and n are each 0<m<100, 0<n<100, and satisfy the number of m+n≦100, q and r are each an integer of 2 to 9].

2. A single-layer coating type horizontal alignment film which is obtained by applying a composition for forming a film on a substrate to a substrate, followed by irradiation with a polarized light and curing.

3. The single layer coating type horizontal alignment film of 2. wherein the polarized light is linear polarized ultraviolet light.

4. An optical member which is a single layer coating type horizontal alignment film having 2. or 3.

The polymer of the present invention contains a γ-butyrolactone skeleton in the main chain. Therefore, by applying a composition for forming a film containing the polymer, and irradiating linearly polarized light at room temperature to perform a post-baking process, a single-layer coating type horizontal alignment film exhibiting a low haze value can be produced.

Fig. 1 is a graph showing the dependence of the retardation angle in the wavelength of 550 nm of the film obtained in Example 1.

Fig. 2 is a graph showing the dependence of the retardation angle in the wavelength of 550 nm of the film obtained in Example 2.

Fig. 3 is a graph showing the dependence of the retardation angle in the wavelength of 550 nm of the film obtained in Example 3.

Fig. 4 is a graph showing the dependence of the retardation angle in the wavelength of 550 nm of the film obtained in Comparative Example 1.

[Formation to implement the invention] [Composition for film formation]

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

〔polymer〕

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

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

(wherein R ¹ is a hydrogen atom or a methyl group. The dotted line is a bond).

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

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

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. However, in the present invention, a fluorine atom is preferred.

The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain, and the carbon number 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, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a ring. Butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl and the like. In the above, R ^{2 is} preferably a linear 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 a linear form, a branched form, and a cyclic form, and the carbon number is not particularly limited. In the present invention, a linear alkoxy group having 1 to 10 carbon atoms is preferred. 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, an s-butoxy group, and a t- Butoxy, n-pentyloxy, n-hexyloxy A group, an n-heptyloxy group, an n-octyloxy group, an n-fluorenyloxy group, an n-fluorenyloxy group or the like. Among them, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.

Further, in the above alkyl group or alkoxy group, part or all of the hydrogen atom 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. As R ³ , a methyl group is more preferable.

As G ¹ , -COO- or -OCO- is preferred.

In the formulae [1a] and [1b], m and n represent the content ratio (mol%) of each repeating unit, and each of them satisfies 0 < m < 100, 0 < n < 100, and m + n ≦ 100, but From the viewpoint of increasing Δn or increasing the solubility of the polymer, it is preferable to satisfy the number of 20≦m≦90, 10≦n≦80, and satisfy the number of 50≦m≦80, 20≦n≦50. The better.

In the formulae [1a] and [1b], q and r are each independently an integer of 2 to 9, but preferably 3 to 6, particularly preferably q is 5 or 6.

The weight average molecular weight of the above polymer is preferably 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 exceeds 200,000, the solubility in a solvent is lowered, and the handleability is lowered. When the weight average molecular weight is less than 3,000, the hardening at the time of thermosetting is insufficient to reduce the solvent resistance and heat resistance. produce.

Further, the weight average molecular weight is a polystyrene-converted value measured by gel permeation chromatography (GPC).

Further, the above polymer is limited to the extent that the effect of the present invention is not impaired The system may contain other repeating units than the formulas [1a] and [1b]. Examples of the polymerizable compound to which the other repeating unit is added include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylonitrile compound, acrylonitrile, maleic anhydride, and a styrene compound.

The content of the above other repeating units is preferably from 0 to 10 mol% in the total repeating unit. When the content ratio of the other repeating unit is too large, the properties of the polymer of the present invention, such as liquid crystal properties, may be deteriorated.

Further, the polymer of the present invention may be any of a random copolymer, an interactive 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 s1 to s4 are the same as described above. X' is a polymerizable group represented by the formula [8] or [9].

(wherein R ¹ is the same as above)].

[Synthesis of Polymerizable Compounds]

The above polymerizable compound can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited.

For example, the polymerizable compound represented by the formula [6] can be produced by the following method.

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

(wherein R ² , X', q, s1 and s2 are the same as above. DCC represents N,N'-dicyclohexylcarbodiimide, and DMAP represents N,N-dimethyl-4-aminopyridine) .

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

(wherein R ² , X', q, s1 and s2 are the same as described above).

Further, the compound of 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 in the following synthesis scheme.

(wherein R ³ , r, s3 and s4 are the same as described above).

When the compound represented by the formula [10] and [11] is a group represented by the formula [8], it can be obtained from a commercially available product of SYNTHON Chemicals Co., Ltd. or Green Chemical Co., Ltd.

Further, in the compounds of the formulae [10] and [11], X' is a group represented by the formula [9] and a compound of the formula [12], and for example, Talaga et al. (P. Talaga, M. Schaeffer, The synthesis was carried out by the method proposed by C. Benezra and JLStampf, Synthesis, 530 (1990). This method is a method of reacting 2-(bromomethyl)acrylic acid with an aldehyde or a ketone using SnCl ₂ as shown in the following Synthesis Scheme A1. Further, 2-(bromomethyl)acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJO 'Donnell and KDBerlin, 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 Company. THF represents tetrahydrofuran. Et represents an ethyl group).

Further, in the reaction using 2-(bromomethyl)acrylic acid of SnCl ₂ , an aldehyde or a ketone is substituted, and by reacting with the corresponding acetal or ketal, α-methyl-γ-butene can be obtained. Ester structure. Examples of the acetal or ketal include compounds having a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxanyl group, and a 1,3-dioxolyl group. The following synthesis scheme A2 shows a synthesis method and a protecting group in the case of using an acetal or a ketal.

(wherein R' is the same as above).

The compound of the formula [10], [11] or [12] can be synthesized by the following synthesis scheme B or C by the method of the above-mentioned synthesis scheme A1 or A2.

(wherein q and s1 are the same as above. Me represents a methyl group. PCC represents a pyridinium chlorochromate).

(wherein q and s1 are the same as above).

[Synthesis of Polymers]

The method for synthesizing the above polymer is not particularly limited, and radical polymerization, negative ion polymerization, cationic polymerization or the like can be employed. Among them, in particular, radical polymerization is preferred, and in particular, the polymerizable compound may be heated and polymerized in the presence of a polymerization initiator in a solvent.

As the polymerization initiator, it can be suitably selected from those used in the past. Examples thereof include peroxides such as benzammonium peroxide, cumene hydroperoxide, and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; and azodi An azo compound such as isobutyronitrile (AIBN), azodimethylbutyronitrile or azobisisovaleronitrile. These may be used alone or in combination of two or more.

The amount of the polymerization initiator to be used is preferably from 0.01 to 0.05 mol per 1 mol of the polymerizable compound.

The reaction temperature can be set to an appropriate temperature from 0 ° C to the boiling point of the solvent to be used, preferably from 20 to 100 ° C. The reaction time is preferably from 0.1 to 30 hours.

The solvent to be used in the polymerization reaction is not particularly limited, and can be suitably selected from various solvents generally used in the above polymerization reaction. Specific examples thereof include water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i-pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, An alcohol such as benzyl alcohol or cyclohexanol; an ether such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran or 1,4-dioxane; chloroform, Halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether Ether ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, and cellosolve acetate; N-pentane, n-hexane, n-heptane, n-octane, n-decane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and anisole; acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid, and propionic acid Nitropropane, nitrobenzene, dimethylamine, monoethanolamine, pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, dimethyl hydrazine, acetonitrile Wait. These can be used singly or in combination of two or more.

When the above-mentioned polymer is a repeating unit other than the formulas [1a] and [1b], the polymerization method may be carried out by coexisting a polymerizable compound imparting the other repeating unit in 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; and N,N-dimethylformamidine. Polar solvents such as amine and N-methyl-2-pyrrolidone; esters such as ethyl acetate, butyl acetate, ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate , alkoxy esters of 3-methoxypropionic acid ethyl, 2-methoxypropionic acid ethyl, 3-ethoxypropionic acid ethyl, 2-ethoxypropionic acid ethyl; ethylene glycol; Glycol dialkyl ethers such as dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol a diethylene glycol dialkyl ether such as methyl ether; a glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether; Diethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, card Alcohol acetate, ethyl cellosolve acetate Glycol monoalkyl ether; cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and other ketones. These organic solvents may be used singly or in combination of two or more.

Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and the like are preferred.

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

[Other ingredients]

In the film forming composition of the present invention, to improve affinity with the substrate A surfactant can be added for sexual purposes. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant. Among them, a fluorine-based surfactant having a high affinity improving effect with a substrate is preferred.

Specific examples of the fluorine-based surfactant include (hereinafter, the trade name), EFTOPEF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (made by DIC), and FLUORADFC430. , FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc., but are not limited thereto. Further, the surfactant may be used singly or in combination of two or more kinds, and the amount of the surfactant is preferably 5 parts by mass or less based on 100 parts by mass of the polymer.

Further, in the film-forming composition of the present invention, an adhesion promoter may be added for the purpose of improving the adhesion to the substrate.

Examples of the adhesion promoter include chlorodecanes such as trimethylchlorodecane, dimethylvinylchlorosilane, methyldiphenylchlorodecane, and chloromethyldimethylchloromethane; and trimethylmethoxy group; Alkoxydecane such as decane, dimethyldiethoxydecane, methyldimethoxydecane, dimethylvinylethoxysilane, diphenyldimethoxydecane, phenyltriethoxydecane Classes; hexamethyldioxane, N,N'-bis(trimethylmethyl)urea, dimethyltrimethyldecylamine, trimethyldecyl imidazole, etc.; Chlorodecane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ-glycidoxypropyl a decane such as methoxydecane or γ-(N-piperidinyl)propyltrimethoxydecane; benzotriazole, benzimidazole, oxazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzoene a heterocyclic compound such as thiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercapto imidazole or mercaptopyrimidine; urea compound such as 1,1-dimethylurea or 1,3-dimethylurea; sulfur Urea compounds and the like.

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

[Single layer coating type horizontal alignment film]

The film-forming composition of the present invention described above is applied to a substrate (for example, a ruthenium/yttrium oxide-coated substrate, a substrate coated with a tantalum nitride substrate, a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or the like). ITO substrate, etc. or film (for example, a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, a resin film such as an acrylic film), etc. Coating, flow coating, roll coating, slit coating, slit coating, and then coating by spin coating, inkjet method, printing method, etc., to form a coating film, and then in a heating plate or an oven, etc. A film can be formed after heating and drying.

As conditions for heat drying, for example, a suitable heating temperature and heating time selected from the range of 40 to 100 ° C and 0.1 to 60 minutes can be employed. The heating temperature and heating time are preferably 40 to 80 ° C for 0.1 to 2 minutes.

For the film thus formed, linear polarized light irradiation is performed, After the post-baking, a single-layer coating type horizontal alignment film can be obtained.

As a method of irradiating linearly polarized light, ultraviolet light to visible light of a wavelength of 150 to 450 nm is generally used, and irradiation with linear polarized light is performed at room temperature or in a heated state. The amount of illumination line varies depending on the light used, and is preferably about 100 to 2,000 mJ/cm ² .

Further, the post-baking may be performed only by heating on a hot plate or an oven, and the temperature and time are preferably 90 to 150 ° C, 2 to 20 minutes, more preferably 95 to 120 ° C, or 5 to 20 minutes.

The film thickness of the single-layer coating type horizontal alignment film of the present invention can be appropriately selected in consideration of the step difference or optical and electrical properties of the substrate to be used, and is preferably, for example, 0.1 to 3 μm.

The single-layer coating type horizontal alignment film of the present invention thus obtained can be used as a material having preferable optical characteristics in applications such as a display device or a recording material, and particularly as an optical compensation film such as a polarizing plate for liquid crystal display and a phase difference plate. It is better.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Further, the measurement methods and measurement conditions of the respective physical properties in the examples are as follows.

[1] ¹ H-NMR

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

[2] Determination of average molecular weight

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 Corporation.

[3] fog value

The haze value of the film was measured using a (limited) Tokyo Electric Color Spectral Haze Meter (TC-1800H).

[4] Film retardation value (Δnd)

Δnd at a wavelength of 550 nm was measured using a retardation measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.).

[5] Observation by polarized light microscope

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

[Synthesis Example 1] Synthesis of Polymerizable Compound (M1) [1] Synthesis of intermediate compound (A1)

To a 200 mL eggplant type flask equipped with a cooling tube, 7.61 g (50.0 mmol) of 4-hydroxybenzoic acid methyl group, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, and 13.8 g (100 mmol) of potassium carbonate were added. 70 mL of acetone was used as a mixture, and the reaction was carried out while stirring at 64 ° C for 24 hours. After the completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure to give a yellow, wet solid. This solid was purified by a silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, solvent: hexane/ethyl acetate = 1/1). The solvent was evaporated from the obtained solution to give 11.3 g of white solid. The solid was measured by ¹ H-NMR and the results are shown below. From the result, the white solid was identified as the objective intermediate compound (A1) (yield: 90%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d) , 2H).

[2] Synthesis of intermediate compound (B1)

Next, in a 100 mL three-necked flask equipped with a cooling tube, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane were placed, and the mixed intermediate compound (A1) was added dropwise with 2.5 g (10.0 mmol). A solution of 15.0 mL of dichloromethane was stirred at room temperature for additional 6 hours. Thereafter, a solution of the oily substance adhering to the wall of the flask was removed, 90 mL of diethyl ether was added thereto, and the mixture was filtered under reduced pressure.

The solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, solvent: hexane/ethyl acetate = 2/1). The solvent was evaporated from the obtained solution to give a white solid. The results of measurement of the solid by ¹ H-NMR are shown below. From the result, it was confirmed that the colorless solid was the objective intermediate compound (B1) (yield 50%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d) , 2H), 9.78 (s, 1H).

[3] Synthesis of intermediate compound (C1)

Next, in a 50 mL eggplant type flask equipped with a cooling tube, 1.25 g (5.0 mmol) of an intermediate compound (B1), 0.83 g (5.0 mmol) of 2-(bromomethyl)acrylic acid, and Amberlyst (registered trademark) 15 (Solomon) were added. 0.8 g, THF 8.0 mL, tin chloride (II) 0.95 g (5.0 mmol), and pure water 2.0 mL were used as a mixture, and the mixture was stirred at 70 ° C for 5 hours to carry out a reaction. After the completion of the reaction, the reaction solution was filtered under reduced pressure, and then mixed with 40 mL of purified water, and 50 mL of diethyl ether was added thereto and extracted. The extraction was carried out 3 times.

Anhydrous magnesium sulfate was added to the organic layer after extraction and dried, and the solvent was filtered off from the filtrate under reduced pressure to give 1.5 g of colorless solid. The solid was measured by ¹ H-NMR and the results are shown below. From the result, the colorless solid was identified as the intermediate compound (C1) (yield: 94%).

¹ H-NMR (DMSO-d6) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 ( m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H).

[4] Synthesis of intermediate compound (D1)

Into a 100 mL eggplant type flask equipped with a cooling tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of an intermediate compound (C1), and 5 mL of a 10% by mass aqueous sodium hydroxide solution were added as a mixture, and the mixture was stirred at 85 ° C for 3 hours. While allowing it to react. After the reaction was completed, 300 mL of water and a reaction liquid were added to a 500 mL beaker, and the mixture was stirred at room temperature for 30 minutes, and then 5 mL of a 10% by mass aqueous HCl solution was added dropwise thereto, followed by filtration to obtain a white solid (1.3 g).

Next, in a 50 mL eggplant type flask equipped with a cooling tube, 1.1 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15 (manufactured by Rohm and Haas Company), and 20.0 mL of tetrahydrofuran were added as a mixture, and the mixture was subjected to a mixture at 70 ° C for 5 hours. Stir and allow to react. After the completion of the reaction, the solvent was filtered off from the reaction solution under reduced pressure to give a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1 / 1) to yield 0.9 g of white solid. The solid was measured by ¹ H-NMR and the results are shown below. From the result, the white solid was identified as the objective intermediate compound (D1) (yield: 71%).

¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H).

[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 and suspended. To 45 mL of dichloromethane, a solution of dissolved 2.7 g (13.0 mmol) of DCC in 15 mL of dichloromethane was added thereto, and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 0.5 mL/L hydrochloric acid 50 mL, saturated sodium bicarbonate aqueous solution 50 mL, and saturated brine (100 mL), dried over magnesium sulfate, and evaporated under reduced pressure. Solvent gave a yellow solid. The solid was purified by recrystallization from ethanol. 2.6 g (yield 56%) of the objective polymerizable compound (M1) was obtained. The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.40-1.90 (m, 8H), 2.58 (m, 1H), 3.08 (m, 1H), 3.80 (s, 3H), 4.05 (t, 2H), 4.55 (m) , 1H), 5.64 (s, 1H), 6.22 (s, 1H), 6.42 (d, 1H), 6.97 (d, 2H), 7.22 (d, 2H), 7.60 (d, 2H), 7.70 (d, 1H), 8.15 (d, 2H).

[Synthesis Example 2] Synthesis of polymerizable compound (M2) [1] Synthesis of intermediate compound (A2)

To a 100 mL eggplant type flask equipped with a cooling tube, 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl group, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, and potassium carbonate 7.0 were added. g (50 mmol) and 50 mL of acetone were mixed as a mixture at 64 ° C for 24 hours while stirring. After the completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. Thereafter, 70 mL of the solid and water were mixed, and 50 mL of diethyl ether was added and extracted. The extraction was carried out 3 times.

After the organic layer was separated, anhydrous magnesium sulfate was added to dryness, and filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. This solid was dissolved in 3 mL of ethyl acetate, and purified by a silica gel column chromatography (column: yttrium 60, 0.063-0.200 mm, manufactured by Merck, solvent: hexane/ethyl acetate = 1/1). The solvent was evaporated from the obtained solution to give 6.9 g of white solid. The solid was measured by ¹ H-NMR and the results are shown below. From the result, the white solid was identified as the objective intermediate compound (A2) (yield: 91%).

¹ H-NMR (DMSO-d6) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d, 2H), 7.85 (m, 4H).

[2] Synthesis of polymerizable compound (M2)

3.0 g (10.2 mmol) of the intermediate compound (A2) and 1.5 mL of triethylamine and a small amount of BHT were simultaneously dissolved in 10 mL of THF, and stirred at room temperature, and dissolved in THF 10 mL of 0.9 mL by cooling in a water bath. The acrylonitrile chloride was added dropwise over 15 minutes. After the dropwise addition, the reaction solution was stirred for 30 minutes, and after removing the water bath, the mixture was returned to room temperature and stirred overnight, and the precipitated triethylamine hydrochloride was filtered. Approximately 3/4 of THF was distilled off from the obtained filtrate, and 50 mL of dichloromethane was added, and the organic layer was washed with 50 mL of a saturated aqueous sodium hydrogencarbonate solution, 50 mL of 0.5 mol/L hydrochloric acid, and 50 mL of a saturated saline solution, and then After drying over magnesium sulfate, the solvent was evaporated to give a product. After recrystallization by methanol, 1.7 g of the objective polymerizable compound (M2) was obtained. The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.50 (m, 4H), 1.73 (m, 2H), 1.85 (m, 2H), 4.05 (t, 2H), 4.20 (t, 2H), 5.82 (d, 1H) ), 6.15 (m, 1H), 6.41 (d, 1H), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H).

[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 group, 0.008 g of DMAP, and a small amount of BHT were stirred at room temperature, and suspended in two. In 10 mL of methyl chloride, a solution of 0.5 mL (2.5 mmol) of DCC dissolved in 5 mL of dichloromethane was added thereto, and stirred overnight. After the separated DCC urea was separated by filtration, the filtrate was washed twice with 0.5 mL/L hydrochloric acid 50 mL, saturated sodium bicarbonate aqueous solution 50 mL, and saturated brine (50 mL), dried over magnesium sulfate, and then evaporated. It was purified by recrystallization from ethanol to obtain 0.6 g (yield 62%) of the objective polymerizable compound (M3). The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4H), 1.75 (m, 2H), 1.85 (m, 2H), 2.61 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H) ), 4.54 (m, 1H), 5.63 (d, 1H), 6.24 (d, 1H), 6.97 (d, 2H), 7.29 (d, 2H), 7.35 (m, 1H), 7.45 (m, 2H) , 7.62 (m, 4H), 8.17 (d, 2H).

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

4-(6-Propyloxy-1-hexyloxy)benzoic acid (manufactured by SYNTHON Chemicals Co., Ltd.) 29.2 g (100 mmol), 4-hydroxybiphenyl 17.0 g (100 mmol), DMAP 0.6 g, and a small amount of BHT The mixture was suspended in 200 mL of dichloromethane under stirring at room temperature, and a solution of 24.0 g (116 mmol) of DCC dissolved in dichloromethane (100 mL) was added and stirred overnight. After the precipitated DCC urea was separated by filtration, the filtrate was washed twice with 150 mL of 0.5 mol/L hydrochloric acid, 150 mL of a saturated aqueous sodium hydrogencarbonate solution and 150 mL of a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and then evaporated. After ethanol was recrystallized and purified, 39.6 g (yield 89%) of the objective polymerizable compound (M4) was obtained. The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 4H), 1.70 (m, 2H), 1.86 (m, 2H), 4.40 (m, 2H), 4.19 (m, 2H), 5.82 (m, 1H) ), 6.12 (m, 1H), 6.39 (m, 1H), 6.97 (d, 2H), 7.29 (m, 2H), 7.36 (m, 1H), 7.47 (m, 2H), 7.62 (m, 4H) , 8.18 (m, 2H).

[Synthesis Example 5] Synthesis of Polymerizable Compound (M5)

4-(6-Acetoxy-1-hexyl)benzoic acid (manufactured by SYNTHON Chemicals Co., Ltd.) 2.9 g (10 mmol), methyl 4-hydroxycinnamate 1.8 g (10 mmol), DMAP 0.06 g, and a small amount of BHT After stirring at room temperature, it was suspended in 30 mL of dichloromethane, and a solution of dissolved DCC 2.4 g (12 mmol) in dichloromethane (10 mL) was added thereto, and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with a solution of 20 mL of 0.5 mol/L hydrochloric acid, 20 mL of a saturated aqueous sodium hydrogencarbonate solution and 30 mL of a saturated aqueous sodium chloride solution, and dried over magnesium sulfate. , a yellow solid was obtained. The solid was recrystallized from ethanol and purified. 3.4 g (yield 72%) of the objective polymerizable compound (M5) was obtained. The measurement results of ¹ H-NMR are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4H), 1.76 (m, 2H), 1.86 (m, 2H), 3.81 (s, 3H), 4.04 (m, 2H), 4.19 (m, 2H) ), 5.84 (d, 1H), 6.14 (m, 1H), 6.40 (m, 1H), 6.97 (d, 2H), 7.22 (m, 3H), 7.57 (d, 2H), 7.70 (d, 1H) , 8.17 (d, 2H).

[Synthesis Example 6] Synthesis of Polymer (1)

Into a flask equipped with a cooling tube, 0.98 g (2.1 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1 and 1.7 g (4.9 mmol) of the polymerizable compound (M2) obtained in Synthesis Example 2, NMP 24 g, And AIBN 57 mg, after replacing the inside of the flask with nitrogen, the mixture was stirred at 60 ° C for 20 hours and allowed to react. The obtained reaction solution was poured into 300 mL of methanol to precipitate a white powder. After filtering the white powder, it was vacuum dried at room temperature to obtain 2.6 g of a polymer (1) (yield 96%).

The obtained polymer (1) had an Mn of 20,643 and a Mw of 64,612 (Mw/Mn = 3.13).

[Synthesis Example 7] Synthesis of polymer (2)

In a flask equipped with a cooling tube, it was charged in Synthesis Example 1. 0.40 g (0.9 mmol) of the polymerizable compound (M1), 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, after the flask was replaced with nitrogen, The mixture was stirred at 60 ° C for 20 hours and allowed to react. The obtained reaction solution was poured into 300 mL of methanol to precipitate a white powder. After filtering the white powder, it was vacuum dried at room temperature to obtain 0.95 g of a polymer (2) (yield: 73%).

The obtained polymer (1) had an Mn of 23,432 and a Mw of 52,956 (Mw/Mn = 2.26).

[Synthesis Example 8] Synthesis of polymer (3)

Into a flask equipped with a cooling tube, 0.20 g (0.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1 and 0.44 g (1.0 mmol) of the polymerizable compound (M4) obtained in Synthesis Example 4, NMP 5. 8 g and 12 ml of AIBN were substituted with nitrogen in the flask, and stirred at 60 ° C for 20 hours to cause a reaction. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. After filtering the white powder, it was vacuum dried at room temperature to obtain 0.5 g of a polymer (3) (yield 78%).

The obtained polymer (1) had an Mn of 15,877 and a Mw of 51,759 (Mw/Mn = 3.26).

[Synthesis Example 9] Synthesis of polymer (4)

Into a flask equipped with a cooling tube, 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, and NMP 16 g, And 34% of AIBN, after replacing the inside of the flask with nitrogen, the mixture was stirred at 60 ° C for 20 hours and allowed to react. The obtained reaction solution was poured into 300 mL of methanol to precipitate a white powder. After filtering the white powder, it was vacuum dried at room temperature to obtain 1.6 g of a polymer (4) (yield 89%).

The obtained polymer (1) had an Mn of 12,678 and a Mw of 22,313 (Mw/Mn = 1.76).

[Modulation of film forming composition and film production. Evaluation]

The film-forming composition was prepared by using the polymer obtained in the above Synthesis Example, and a film was produced under the following conditions, and the properties were examined.

Film production conditions:

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

Pre-baking: 50 ° C / 30 sec (heating plate)

Exposure: linear polarized ultraviolet light, vertical irradiation, irradiation line amount of 1,000mJ/cm ² (wavelength 313nm)

Post-baking: 100 ° C or 120 ° C / 20 minutes (heating plate)

[Example 1]

150 mg of the polymer (1) and R-30 (the surfactant of DIC (shares), the same applies hereinafter). 0.3 mg was dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (1).

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

Next, the coating film formed on the glass substrate is exposed and post-baked. The film thickness of the obtained film was 1.4 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned with respect to the substrate surface. The Δnd was 43 nm and the haze value was 0.3%. Fig. 1 shows the angular dependence of Δnd of the above 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).

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

Next, the coating film formed on the glass substrate is exposed and post-baked. The film thickness of the obtained film was 1.6 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned with respect to the substrate surface. And the △nd is 53 nm, the haze value was 0.0%. Fig. 2 shows the angular dependence of Δnd of the above 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).

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

Next, the coating film formed on the glass substrate is exposed and post-baked. The film thickness of the obtained film was 1.8 μm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned with respect to the substrate surface. The Δnd was 79 nm and the haze value was 0.4%. Fig. 3 shows the angular dependence of Δnd of the above 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).

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

Next, the coating film formed on the glass substrate was exposed, and then baked on a hot plate at 100 ° C for 20 minutes. The film thickness of the obtained film was 1.5 μm. When observed by a polarizing microscope, a horizontal alignment film was not obtained, and the ?nd was 25 nm, and the haze value was 4.0%. Fig. 4 shows the angular dependence of Δnd of the above film.

The above results are summarized in Table 1 below.

Claims (4)

A film forming composition comprising at least one polymer comprising a repeating unit represented by formula [1a] and [1b] and an organic solvent; Wherein X is a group of the formula [2] or [3], (wherein R ¹ is a hydrogen atom or a methyl group; a broken line is a bond; M ¹ is a group represented by the formula [4], and M ² is a group represented by the formula [5], (wherein, s1 to s4 are each independently 1 or 2, G ¹ is a single bond, -COO- or -OCO-, and R ² is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or carbon Alkoxy groups of 1 to 10, R ³ is an alkyl group having 1 to 3 carbon atoms; a broken line is a bonding bond) m and n are each 0 < m < 100, 0 < n < 100, and satisfy m + n ≦ 100 The number, q and r are each an integer of 2 to 9]. A single layer coating type horizontal alignment film which is obtained by applying a film forming composition according to claim 1 to a substrate, and then irradiating the polarized light to harden it. The single layer coating type horizontal alignment film of claim 2, wherein the polarized light is linearly polarized ultraviolet light. An optical member characterized by comprising a single-layer coating type horizontal alignment film according to claim 2 or 3.