JP6536403B2 - Composition for film formation and single layer coating type horizontal alignment film - Google Patents

Description

  The present invention relates to a film forming composition and a single-layer coating type horizontal alignment film. Specifically, a film-forming composition which provides a film having a suitable optical property for applications such as display devices and recording materials, particularly an optical compensation film such as a polarizing plate for liquid crystal display and a retardation plate And a single layer coating type horizontally oriented film obtained from the composition.

  From the demand for improvement in display quality and weight reduction of liquid crystal display devices, there is an increasing demand for polymer films in which the molecular orientation structure inside is controlled as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, development of a film utilizing the optical anisotropy of a polymerizable liquid crystal compound has been made. The polymerizable liquid crystal compound used herein is generally a liquid crystal compound having a polymerizable group and a liquid crystal structural site (a structural site having a spacer portion and a mesogenic portion), and an acryl group is widely used as this polymerizable group. ing.

  Such a polymerizable liquid crystal compound is generally converted to a polymer (film) by a method of irradiation by irradiation with radiation such as ultraviolet light. For example, there is a method of supporting a specific polymerizable liquid crystal compound having an acrylic group between supports and irradiating the radiation while maintaining the compound in a liquid crystal state to obtain a polymer (Patent Document 1), or having an acrylic group There is known a method (Patent Document 2) in which a photopolymerization initiator is added to a mixture of two kinds of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with this mixture, and irradiating ultraviolet light.

  In addition, polymerizable liquid crystal compounds that do not require a liquid crystal alignment film, alignment films using polymers (patent documents 3 and 4), alignment films using polymers containing photocrosslinking sites (patent documents 5 and 6), etc. A variety of single layer coated oriented films have been reported. However, since the polymers used for these films have low solubility and it is necessary to use a solvent having excellent solubility such as N-methyl-2-pyrrolidone, chloroform, chlorobenzene as a solvent, they can be obtained from these solutions. There is a problem that the characteristics such as refractive index anisotropy (.DELTA.n) and haze value of the film may be deteriorated. Also, no material has been found so far that can obtain an oriented film exhibiting a low haze value by a simple process.

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

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

  As a result of intensive studies to solve the above problems, the present inventor has found that a polymer having a cinnamic acid ester structure on the side chain extending from the γ position of the lactone ring while containing the γ-butyrolactone skeleton in the main chain. The reason is that a horizontal alignment film having refractive index anisotropy (Δn) can be obtained without using a liquid crystal alignment film, because a stable network structure is formed after exposure to polarized ultraviolet light. The present invention has been completed by finding that a horizontally-oriented film exhibiting the following can be produced under low temperature conditions.

［式中、Ｘは式［２］又は［３］で表される基であり、

（式中、Ｒ¹は水素原子又はメチル基である。破線は結合手である。）
Ｍ¹は式［４］で表される基であり、Ｍ²は式［５］で表される基であり、

（式中、ｓ１〜ｓ４はそれぞれ独立に１又は２であり、Ｇ¹は単結合、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ²は水素原子、ハロゲン原子、シアノ基、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基であり、Ｒ³は炭素数１〜３のアルキル基である。破線は結合手である。）
ｍ及びｎはそれぞれ０＜ｍ＜１００、０＜ｎ＜１００、かつ、ｍ＋ｎ≦１００を満たす数であり、
ｑ及びｒはそれぞれ独立に２〜９の整数である。］
２．上記重合体の重量平均分子量が、３,０００〜２００,０００である１の膜形成用組成物。
３．ｍ及びｎが、２０≦ｍ≦９０、１０≦ｎ≦８０、かつ、ｍ＋ｎ≦１００を満たす数である１又は２の膜形成用組成物。
４．上記有機溶媒が、組成物中６０〜９５質量％含まれる１〜３のいずれかの膜形成用組成物。
５．１〜４のいずれかの膜形成用組成物から得られる単層塗布型水平配向フィルム。
６．５の単層塗布型水平配向フィルムを備える光学部材。
That is, the present invention provides the following composition for film formation and a single-layer coating type horizontal alignment film.
1. What is claimed is: 1. A composition for forming a film, which comprises at least one polymer containing repeating units represented by the formulas [1a] and [1b] and an organic solvent.

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

(In the formula, R ¹ is a hydrogen atom or a methyl group. The 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, 1 to 10 carbon atoms Or an alkoxy group having 1 to 10 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, and the broken line indicates a bond.
m and n are numbers satisfying 0 <m <100, 0 <n <100, and m + n ≦ 100, respectively
q and r are each independently an integer of 2-9. ]
2. The composition for film formation of 1, wherein the weight average molecular weight of the polymer is 3,000 to 200,000.
3. The composition for film formation of 1 or 2 whose m and n are numbers which satisfy | fill 20 <= m <= 90, 10 <= n <= 80, and m + n <= 100.
4. The composition for film formation in any one of 1-3 in which the said organic solvent is contained 60 to 95 mass% in a composition.
The single layer coating type horizontal alignment film obtained from the composition for film formation in any one of 5.1-4.
6 . An optical member provided with the single layer coating type horizontal alignment film of 5 .

  The polymer of the present invention contains a γ-butyrolactone skeleton in the main chain. Therefore, a film-forming composition containing this polymer is applied, linearly polarized light is irradiated at room temperature, and post-baking is performed to produce a single layer coating type horizontally oriented film exhibiting a low haze value. It is possible.

It is a figure which shows the retardation value angle dependence in wavelength 550nm of the film obtained in Example 1. FIG. It is a figure which shows the retardation value angle dependence in wavelength 550 nm of the film obtained in Example 2. FIG. It is a figure which shows the retardation value angle dependence in wavelength 550nm of the film obtained in Example 3. FIG. It is a figure which shows the retardation value angle dependence in wavelength 550nm of the film obtained by the comparative example 1. FIG.

[Composition for film formation]
The composition for film formation of the present invention contains at least one of the following polymers and an organic solvent.

[Polymer]
The polymer contained in the composition for film formation of the present invention contains repeating units represented by the formulas [1a] and [1b].

（式中、Ｒ¹は水素原子又はメチル基である。破線は結合手である。）In formula [1a], X is a group represented by formula [2] or [3].

(In the formula, R ¹ is a hydrogen atom or a methyl group. The broken line is a bond.)

（式中、ｓ１〜ｓ４はそれぞれ独立に１又は２であり、Ｇ¹は単結合、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ²は水素原子、ハロゲン原子、シアノ基、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基であり、Ｒ³は炭素数１〜３のアルキル基である。破線は結合手である。）In Formula [1a], M ¹ is a group represented by Formula [4], and in Formula [1b], M ² is a group represented by 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, 1 to 10 carbon atoms Or an alkoxy group having 1 to 10 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, and the broken line indicates a bond.

  Here, as a halogen atom, although a fluorine, chlorine, a bromine, and an iodine atom are mentioned, a fluorine atom is preferable in this invention.

The alkyl group may be linear, branched or cyclic, and the carbon number is also not particularly limited. Specific examples of the above alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n- A pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like can be mentioned. Among these, as R ² , a linear alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group, an ethyl group and the like are particularly preferable. As R ³ , an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group and the like are particularly preferable.

  The alkoxy group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but in the present invention, a linear alkoxy group having 1 to 10 carbon atoms is preferable. Specific examples of the above alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n- A hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group etc. are mentioned. Among these, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group, an ethoxy group and the like are particularly preferable.

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

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

As G ¹ , -COO- or -OCO- is preferable.

  In the formulas [1a] and [1b], m and n each represent the content (mol%) of each repeating unit, and in a number satisfying 0 <m <100, 0 <n <100, and m + n ≦ 100, respectively. However, it is preferable that the numbers satisfy 20 ≦ m ≦ 90 and 10 ≦ n ≦ 80, respectively, and 50 ≦ m ≦ 80 and 20 ≦ n ≦ from the viewpoint of improvement of Δn and improvement of the solubility of the polymer. It is more preferable that the number is 50.

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

The weight average molecular weight of the polymer is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight exceeds 200,000, the solubility in solvents may decrease and the handling properties may decrease, and if the weight average molecular weight is less than 3,000, the curing becomes insufficient at the time of heat curing, and the solvent resistance and heat resistance Gender may decrease.
In addition, a weight average molecular weight is a polystyrene conversion measurement value by gel permeation chromatography (GPC).

  Moreover, the said polymer may also contain other repeating units other than Formula [1a] and [1b], unless the effect of this invention is impaired. Examples of the polymerizable compound giving the other repeating unit include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and the like.

  As for the content rate of the said other repeating unit, 0-10 mol% is preferable in all the repeating units. When the content of the other repeating unit is too large, properties of the polymer of the present invention, for example, properties such as liquid crystallinity may be deteriorated.

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

［式中、Ｒ²、Ｒ³、Ｇ¹、ｑ、ｒ及びｓ１〜ｓ４は上記と同じ。Ｘ'は式［８］又は［９］で表される重合性基である。

（式中、Ｒ¹は上記と同じ。）］[Polymerizable compound]
The polymerizable compound used as the raw material of the polymer used by this invention is represented by Formula [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 Formula [8] or [9].

(Wherein, R ¹ is the same as the above.)]

[Synthesis of Polymerizable Compound]
The above polymerizable compounds can be synthesized by combining the methods in organic synthetic chemistry, and the synthesis method is not particularly limited.

（式中、Ｒ²、Ｘ'、ｑ、ｓ１及びｓ２は上記と同じ。ＤＣＣはＮ,Ｎ'−ジシクロヘキシルカルボジイミドを、ＤＭＡＰはＮ,Ｎ−ジメチル−４−アミノピリジンを表す。）For example, the polymerizable compound represented by the formula [6] is produced by the following method.
When G ¹ is —COO—, it is produced by condensing a benzoic acid derivative represented by the formula [10] and a phenol derivative in a solvent in the presence of a condensing agent as represented by the following scheme: Ru.

(Wherein R ² , X ′, q, s 1 and s ² are the same as above. DCC represents N, N′-dicyclohexylcarbodiimide, and DMAP represents N, N-dimethyl-4-aminopyridine.)

（式中、Ｒ²、Ｘ'、ｑ、ｓ１及びｓ２は上記と同じ。）When G ¹ is —OCO—, it is produced by condensing a phenol derivative represented by the formula [11] and a benzoic acid derivative in a solvent in the presence of a condensing agent as represented by the following scheme: Ru.

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

（式中、Ｒ³、ｒ、ｓ３及びｓ４は上記と同じ。）In addition, as the compound represented by the formula [7] is represented by the following synthesis scheme, the compound represented by the formula [12] and a phenol derivative are condensed in the presence of a condensing agent in a solvent Manufactured by

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

The compounds represented by the formulas [10] and [11] are commercially available from SYNTHON Chemicals or Green Chemical Co., Ltd. when X ′ is a group represented by the formula [8].
In addition, compounds represented by the formulas [10] and [11], wherein X ′ is a group represented by the formula [9], and a compound represented by the formula [12] are, for example, Talaga et al. It can synthesize | combine using the method which (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)) proposes. This method is a method in which 2- (bromomethyl) acrylic acid is reacted with an aldehyde or a ketone using SnCl ₂ as represented by the following synthesis scheme A1. 2- (bromomethyl) acrylic acid can be obtained by the method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, pp. 56- 59 (1983)).

（式中、Ｒ'は一価の有機基を表す。Ａｍｂｅｒｌｙｓｔ（登録商標）１５は、ロームアンドハース社製イオン交換樹脂である。ＴＨＦはテトラヒドロフランを表す。Ｅｔはエチル基を表す。）

(In the formula, R ′ represents a monovalent organic group. Amberlyst (registered trademark) 15 is a Rohm and Haas ion exchange resin. THF represents tetrahydrofuran. Et represents an ethyl group.)

In addition, in the reaction of 2- (bromomethyl) acrylic acid using SnCl ₂ , an α-methylene-γ-butyrolactone structure can also be obtained by reaction with the corresponding acetal or ketal instead of aldehyde or ketone. Examples of the acetal or ketal include compounds having a dimethylacetal group, a diethylacetal group, a 1,3-dioxane group, a 1,3-dioxolane group and the like. The following synthesis scheme A2 shows a synthesis method and a protecting group when using an acetal or ketal.

（式中、Ｒ'は上記と同じ。）

(In the formula, R 'is the same as above.)

  The compound represented by the formula [10], [11] or [12] can be synthesized by the method of the following synthesis scheme B or C to which the method of the above synthesis scheme A1 or A2 is applied.

（式中、ｑ及びｓ１は上記と同じ。Ｍｅはメチル基を表す。ＰＣＣはピリジニウムクロロクロマートを表す。）

(Wherein, q and s1 are the same as above. Me is a methyl group. PCC is pyridinium chlorochromate.)

（式中、ｑ及びｓ１は上記と同じ。）

(Wherein, q and s1 are the same as above)

[Synthesis of polymer]
It does not specifically limit as method to synthesize | combine the said polymer, Radical polymerization, anion polymerization, cationic polymerization etc. are employable. Among these, radical polymerization is particularly preferable, and specifically, the above-mentioned polymerizable compound may be heated and polymerized in the presence of a polymerization initiator in a solvent.

  The polymerization initiator can be appropriately selected and used from conventionally known ones. For example, peroxides such as benzoyl peroxide, cumene hydroperoxide and t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; azobisisobutyronitrile (AIBN), azo Examples include azo compounds such as bismethyl butyronitrile and azobisisovaleronitrile. These can be used singly or in combination of two or more.

The amount of the polymerization initiator used is preferably about 0.01 to 0.05 mol with respect to 1 mol of the polymerizable compound.
The reaction temperature may be appropriately set from 0 ° C. to the boiling point of the solvent used, but about 20 to 100 ° C. is preferable. The reaction time is preferably about 0.1 to 30 hours.

  It does not specifically limit as a solvent used for a polymerization reaction, What is necessary is just to select suitably from various solvents generally used by the said polymerization reaction, and just to use. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, Alcohols such as i-pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether , Ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride; methyl cellosolve, ethyl cellosolve, Ether alcohols such as 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 -Aliphatic or aromatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, anisole, etc. Acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane, nitrobenzene, dimethylamine, monoethanolamide , Pyridine, N- methyl-2-pyrrolidone (NMP), N, N- dimethylformamide, dimethyl sulfoxide, acetonitrile and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  In the case where the above polymer contains other repeating units other than those of the formulas [1a] and [1b], as the synthesis method thereof, a polymerizing compound which gives the above other repeating unit is made to coexist in the above polymerization. do it.

[Organic solvent]
Examples of the organic solvent contained in the composition for film formation of the present invention include ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide, N-methyl- Polar solvents such as 2-pyrrolidone; esters such as ethyl acetate, butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Alkoxy esters such as ethyl ethoxypropionate and ethyl 2-ethoxypropionate; glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether Diglycol dialkyl ethers such as 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; diethylene glycol monomethyl Diglycol monoalkyl ethers such as ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether; glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate; The Rohekisanon, methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone. These organic solvents can be used singly or in combination of two or more.

Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and the like are preferable.
The amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.

[Other ingredients]
A surfactant may be added to the composition for film formation of the present invention for the purpose of improving the affinity to the substrate. Although it does not specifically limit as surfactant, A fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant etc. are mentioned. Among these, fluorine-based surfactants having a high effect of improving the affinity to the substrate are preferable.

  Specific examples of the fluorine-based surfactant (hereinafter, trade names): F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafac F171, F173, R-30 (manufactured by DIC Corporation) , Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc., but these are limited thereto I will not. The surfactant may be used singly or in combination of two or more, and the amount thereof is preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer.

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

  As adhesion promoters, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, etc .; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltrimethylsilane Alkoxysilanes such as ethoxysilane; Hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole; Vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-amino Propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- ( -Piperidinyl) silanes such as propyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine etc. Heterocyclic compounds; urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; thiourea compounds and the like.

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

[Single-layer coating type horizontal alignment film]
The composition for film formation of the present invention described above can be used as a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum or chromium, a glass substrate, a quartz substrate, Bar coat, spin coat, flow coat, roll coat, etc. on ITO substrate etc. and films (eg, resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film etc) A film can be formed by coating by a method such as slit coating, spin coating following slit coating, an inkjet method, a printing method, etc. to form a coating film, and then heat drying in a hot plate or an oven etc. .

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

The film thus formed is irradiated with linearly polarized light and post-baked to obtain a single layer coating type horizontally oriented film.
As a method of irradiating linearly polarized light, ultraviolet to visible light having a wavelength of 150 to 450 nm is generally used, and irradiation is performed by irradiating 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 .

  Also, post-baking may be carried out by heating on a hot plate or an oven, and the temperature and time thereof are preferably 90 to 150 ° C. for 2 to 20 minutes, more preferably 95 to 120 ° C. for 5 to 20 minutes is there.

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

  The single-layer coating type horizontal alignment film of the present invention thus obtained is a material having optical properties suitable for applications such as display devices and recording materials, and in particular, a polarizing plate and a retardation plate for liquid crystal displays. Etc. are suitable as an optical compensation film.

Hereinafter, the present invention will be more specifically described by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, the measuring method and measuring conditions of each physical property in an Example are as follows.
[1] ¹ 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 Diol Co., Ltd.).
[2] Measurement of Average Molecular Weight A number average molecular weight (Mn) and a weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko KK.
[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 of film (Δnd)
(DELTA) nd of wavelength 550nm was measured using the retardation measurement apparatus (RETS-100, Otsuka Electronics Co., Ltd. product).
[5] Polarized light microscope observation It observed using polarized light microscope E600-Pol made from Nikon Corporation.

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

In a 200 mL recovery flask with a condenser, 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 acetone 70 mL was added to make a mixture, and reacted while stirring at 64 ° C. for 24 hours. After completion of the reaction, the solvent was distilled off from the reaction liquid under reduced pressure to obtain a yellow wet solid. The solid was purified by silica gel column chromatography (column: silica gel 60, 0.063 to 0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the resulting solution to obtain 11.3 g of a white solid. The results of measuring this solid by ¹ H-NMR are shown below. From this result, it was confirmed that this white solid is the target intermediate compound (A1) (yield 90%).
¹ H-NMR (CDCl ₃ ) δ: 1.3 to 1.7 (m, 8 H), 3.67 (m, 2 H), 3. 88 (s, 3 H), 4.03 (t, 2 H), 6. 91 (d, 2 H), 7.99 (d , 2H).

[2] Synthesis of Intermediate Compound (B1)

Next, 2.2 g (10.0 mmol) of PCC and 15.0 mL of dichloromethane are placed in a 100 mL three-necked flask with a condenser, and while stirring and mixing, 2.5 g (10.0 mmol) of the intermediate compound (A1) in dichloromethane 15 The solution dissolved in .0 mL was added dropwise and further stirred at room temperature for 6 hours. Thereafter, 90 mL of diethyl ether was added to a solution from which oil attached to the wall of the flask was removed, followed by filtration under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.
The solid was purified by silica gel column chromatography (column: silica gel 60, 0.063 to 0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1). The solvent was distilled off from the resulting solution to obtain 1.3 g of a colorless solid. The results of measuring this solid by ¹ H-NMR are shown below. From this result, it was confirmed that this colorless solid is the target intermediate compound (B1) (yield 50%).
¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6 H), 2. 49 (t, 2 H), 3. 88 (s, 3 H), 3.99 (t, 2 H), 6. 87 (d, 2 H), 7.99 (d , 2H), 9.78 (s, 1 H).

[3] Synthesis of Intermediate Compound (C1)

Next, in a 50 mL recovery flask equipped with a condenser, 1.25 g (5.0 mmol) of the intermediate compound (B1), 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, Amberlyst (registered trademark) 15 (Rome 0.8g, THF 8.0 mL, 0.95 g (5.0 mmol) of tin (II) chloride, and 2.0 mL of pure water were added to make a mixture, and the mixture was reacted by stirring at 70 ° C. for 5 hours. . After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 40 mL of pure water, and extracted with 50 mL of diethyl ether added thereto. Extraction was performed three times.
Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and 1.5 g of colorless solid was obtained. The results of measuring this solid by ¹ H-NMR are shown below. From this result, it was confirmed that this colorless solid is the target intermediate compound (C1) (yield: 94%).
¹ H-NMR (DMSO-d6) δ: 1.3 to 1.8 (m, 8 H), 2.62 (m, 1 H), 3.04 (s, 1 H), 3.81 (s, 3 H), 4.05 (t, 2 H), 4.54 ( m, 1 H), 5.70 (s, 1 H), 6.01 (s, 1 H), 7.03 (d, 2 H), 7. 89 (d, 2 H).

[4] Synthesis of Intermediate Compound (D1)

35 mL of ethanol, 1.5 g (4.7 mmol) of an intermediate compound (C1), and 5 mL of a 10% by mass aqueous solution of sodium hydroxide are added to a 100 mL eggplant flask with a condenser to form a mixture, and the mixture is reacted at 85 ° C. for 3 hours I did. After completion of the reaction, 300 mL of water and the reaction solution were added to a 500 mL beaker and stirred at room temperature for 30 minutes, then 5 mL of 10% by mass aqueous HCl solution was 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 Co., Ltd.), and 20.0 mL of tetrahydrofuran are added to a 50 mL eggplant flask with a condenser to obtain a mixture at 70 ° C. The reaction was allowed to stir for 5 hours. 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. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1) to obtain 0.9 g of a white solid. The results of measuring this solid by ¹ H-NMR are shown below. From this result, it was confirmed that this white solid is the target intermediate compound (D1) (yield 71%).
¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8 H), 2.60 (m, 1 H), 3.09 (m, 1 H), 4.04 (m, 2 H), 4.55 (m, 1 H), 5.69 ( s, 1 H), 6.02 (s, 1 H), 6.99 (d, 2 H), 7. 88 (d, 2 H), 12.5 (s, broad, 1 H).

[5] Synthesis of Polymerizable Compound (M1)

Under stirring at room temperature, 3.0 g (10.0 mmol) of intermediate compound (D1), 1.8 g (10.0 mmol) of methyl 4-hydroxycinamate, 0.05 g of DMAP, and a small amount of butylhydroxytoluene (BHT) The solution was suspended in 45 mL of dichloromethane, and a solution of 2.7 g (13.0 mmol) of DCC dissolved in 15 mL of dichloromethane was added thereto and stirred overnight. The precipitated DCC urea is filtered off, and the filtrate is washed successively twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated brine, dried over magnesium sulfate, and then dried under reduced pressure. The solvent was evaporated to give a yellow solid. The solid was purified by recrystallization from ethanol. 2.6g of target polymeric compounds (M1) were obtained (yield 56%). The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.40-1.90 (m, 8 H), 2.58 (m, 1 H), 3.08 (m, 1 H), 3.80 (s, 3 H), 4.05 (t, 2 H), 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)

In a 100 mL recovery type flask equipped with a condenser, 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, 7.0 g (50 mmol) of potassium carbonate And 50 mL of acetone were added to make a mixture, and reacted while stirring at 64 ° C. for 24 hours. After completion of the reaction, the solvent was evaporated under reduced pressure to obtain a yellow wet solid. Thereafter, the solid and 70 mL of water were mixed, and extracted by adding 50 mL of diethyl ether. Extraction was performed three times.
The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063 to 0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 1/1). The solvent was distilled off from the resulting solution to obtain 6.9 g of a white solid. The results of measuring this solid by ¹ H-NMR are shown below. From this result, it was confirmed that this white solid is the target 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)

Intermediate compound (A2) 3.0 g (10.2 mmol) was dissolved in 10 mL of THF with 1.5 mL of triethylamine and a small amount of BHT, stirred at room temperature, 0.9 mL of chloride dissolved in 10 mL of THF under cooling by a water bath Acryloyl was added dropwise over 15 minutes. After the dropwise addition, the reaction solution was stirred for 30 minutes, stirred overnight while removing the water bath and returning to room temperature, and the precipitated triethylamine hydrochloride was filtered. About 3/4 of THF is distilled off from the obtained filtrate, 50 mL of dichloromethane is added, and the organic layer is washed successively with 50 mL of saturated aqueous sodium hydrogen carbonate solution, 50 mL of 0.5 mol / L hydrochloric acid and 50 mL of saturated brine. After drying over magnesium sulfate, the solvent was distilled off to obtain the product. After recrystallization from methanol, 1.7 g of the target 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, 1 H), 6.41 (d, 1 H), 6.99 (d, 2 H), 7.55 (d, 2 H), 7. 66 (m, 4 H).

Synthesis Example 3 Synthesis of Polymerizable Compound (M3)

Under stirring at room temperature, 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. The solution was suspended in 10 mL of dichloromethane, and a solution of 0.5 g (2.5 mmol) of DCC dissolved in 5 mL of dichloromethane was added thereto and stirred overnight. The precipitated DCC urea is filtered off, and the filtrate is washed successively twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogencarbonate solution and 50 mL of saturated brine, dried over magnesium sulfate, and the solvent is distilled off. It was removed and purified by recrystallization with ethanol to obtain 0.6 g of the objective polymerizable compound (M3) (yield 62%). The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4 H), 1.75 (m, 2 H), 1. 85 (m, 2 H), 2.61 (m, 1 H), 3.07 (m, 1 H), 4.06 (t, 2 H) ), 4.54 (m, 1 H), 5.63 (d, 1 H), 6. 24 (d, 1 H), 6. 97 (d, 2 H), 7. 29 (d, 2 H), 7. 35 (m, 1 H), 7. 45 (m, 2 H) , 7.62 (m, 4H), 8.17 (d, 2H).

Synthesis Example 4 Synthesis of Polymerizable Compound (M4)

29.2 g (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 at room temperature Under stirring, the solution was suspended in 200 mL of dichloromethane, and a solution of 24.0 g (116 mmol) of DCC dissolved in 100 mL of dichloromethane was added thereto and stirred overnight. The precipitated DCC urea is filtered off, and the filtrate is washed successively twice with 150 mL of 0.5 mol / L hydrochloric acid, 150 mL of saturated aqueous sodium hydrogen carbonate solution and 150 mL of saturated brine, dried over magnesium sulfate, and the solvent is distilled off. It was removed and purified by recrystallization with ethanol to obtain 39.6 g of the target polymerizable compound (M4) (yield 89%). 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), 4.00 (m, 2H), 4.19 (m, 2H), 5.82 (m, 1H) ), 6.12 (m, 1 H), 6. 39 (m, 1 H), 6. 97 (d, 2 H), 7. 29 (m, 2 H), 7. 36 (m, 1 H), 7. 47 (m, 2 H), 7.62 (m, 4 H) , 8.18 (m, 2H)

Synthesis Example 5 Synthesis of Polymerizable Compound (M5)

2.9 g (10 mmol) of 4- (6-acryloyloxy-1-hexyl) benzoic acid (manufactured by SYNTHON Chemicals), 1.8 g (10 mmol) of methyl 4-hydroxycinamate, 0.06 g of DMAP, and a small amount of BHT at room temperature Under stirring, the reaction solution was suspended in 30 mL of dichloromethane, and a solution of 2.4 g (12 mmol) of DCC dissolved in 10 mL of dichloromethane was added thereto and stirred overnight. The precipitated DCC urea was filtered off, and the filtrate was washed successively twice with 0.5 mol / L hydrochloric acid 20 mL, 20 mL saturated aqueous sodium hydrogen carbonate solution and 30 mL saturated brine, dried over magnesium sulfate and then reduced pressure The solvent was distilled off with to give a yellow solid. The solid was purified by recrystallization from ethanol. 3.4 g of the target polymerizable compounds (M5) were obtained (yield 72%). The measurement results of ¹ H-NMR are shown below.
¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4 H), 1. 76 (m, 2 H), 1. 86 (m, 2 H), 3.81 (s, 3 H), 4.04 (m, 2 H), 4.19 (m, 2 H) ), 5.84 (d, 1 H), 6.14 (m, 1 H), 6. 40 (m, 1 H), 6. 97 (d, 2 H), 7.22 (m, 3 H), 7.57 (d, 2 H), 7. 70 (d, 1 H) , 8.17 (d, 2H).

Synthesis Example 6 Synthesis of Polymer (1)

In a flask equipped with a condenser, 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 were charged, and the inside of the flask was purged with nitrogen, and then reacted by stirring at 60 ° C. for 20 hours. The resulting reaction solution was poured into 300 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum dried at room temperature to obtain 2.6 g of a polymer (1) (yield: 96%).
Mn of the obtained polymer (1) was 20,643 and Mw was 64,612 (Mw / Mn = 3.13).

Synthesis Example 7 Synthesis of Polymer (2)

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

Synthesis Example 8 Synthesis of Polymer (3)

In a flask equipped with a condenser, 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 AIBN 12 mg were charged, and the inside of the flask was purged with nitrogen and then reacted by stirring at 60 ° C. for 20 hours. The resulting reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum dried at room temperature to obtain 0.5 g of a polymer (3) (yield: 78%).
Mn of the obtained polymer (1) was 15,877, and Mw was 51,759 (Mw / Mn = 3.26).

Synthesis Example 9 Synthesis of Polymer (4)

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

[Preparation of film-forming composition and film preparation / evaluation]
The composition for film formation was prepared using the polymer obtained by the said synthesis example, the film was produced according to the following conditions, and the characteristic was examined.
Film preparation conditions:
Spin coating: 300rpm / 5sec, 500-1000rpm / 20sec
Prebaking: 50 ° C / 30 sec (hot plate)
Exposure: linear polarized ultraviolet light, vertical irradiation, irradiation dose 1,000 mJ / cm ² (wavelength 313 nm)
Post bake: 100 ° C or 120 ° C / 20 minutes (hot plate)

Example 1
A solution of polymer (1) was obtained by dissolving 150 mg of polymer (1) and 0.3 mg of R-30 (surfactant manufactured by DIC Corporation, hereinafter the same) in 850 mg of cyclohexanone.
This solution was applied to a glass substrate by spin coating, prebaked, and 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. The obtained film had a thickness of 1.4 μm, and when observed with a polarization microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And, the Δnd was 43 nm and the haze value was 0.3%. FIG. 1 shows the angular dependence of Δnd of the above-mentioned film.

Example 2
150 mg of polymer (2) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (2).
This solution was applied to a glass substrate by spin coating, prebaked, and allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.
Next, the coated film formed on the glass substrate was exposed and then post-baked. The obtained film had a thickness of 1.6 μm, and when observed with a polarization microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And, the Δnd was 53 nm, and the haze value was 0.0%. FIG. 2 shows the angular dependence of Δnd of the above-mentioned film.

[Example 3]
150 mg of polymer (3) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (3).
This solution was applied to a glass substrate by spin coating, prebaked, and allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.
Next, the coated film formed on the glass substrate was exposed and then post-baked. The obtained film had a thickness of 1.8 μm, and when observed with a polarization microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And, the Δnd was 79 nm, and the haze value was 0.4%. FIG. 3 shows the angular dependence of Δnd of the above-mentioned film.

Comparative Example 1
150 mg of polymer (4) and 0.3 mg of R-30 were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (4).
This solution was applied to a glass substrate by spin coating, prebaked, and allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.
Next, the coating film formed on the glass substrate was exposed and then post-baked on a hot plate at 100 ° C. for 20 minutes. The obtained film had a thickness of 1.5 μm, and when observed with a polarizing microscope, a horizontally oriented film was not obtained, its Δnd was 25 nm, and its haze value was 4.0%. FIG. 4 shows the angular dependency of .DELTA.nd of the above-mentioned film.

  The above results are summarized in Table 1 below.

Claims (6)

What is claimed is: 1. A composition for forming a film, which comprises at least one polymer containing repeating units represented by the formulas [1a] and [1b] and an organic solvent.

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

(In the formula, R ¹ is a hydrogen atom or a methyl group. The 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, 1 to 10 carbon atoms Or an alkoxy group having 1 to 10 carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms, and the broken line indicates a bond.
m and n are numbers satisfying 0 <m <100, 0 <n <100, and m + n ≦ 100, respectively
q and r are each independently an integer of 2-9. ]   The film forming composition according to claim 1, wherein the weight average molecular weight of the polymer is 3,000 to 200,000.   The composition for film formation according to claim 1 or 2, wherein m and n are numbers satisfying 20 ≦ m ≦ 90, 10 ≦ n ≦ 80, and m + n ≦ 100.   The composition for film formation according to any one of claims 1 to 3, wherein the organic solvent is contained in an amount of 60 to 95% by mass in the composition. The single layer coating type horizontal alignment film obtained from the composition for film formation of any one of Claims 1-4. 5. Symbol mounting of the single layer coating type horizontal alignment film optical element comprising a.

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