JP2019095613A - Photosensitive monomer, optical alignment polymer, and film produced using the same - Google Patents

Abstract

To provide an optical alignment film which is highly sensitive to ultraviolet rays of long wavelengths, and a retardation film using the optical alignment film.SOLUTION: There is provided an optical alignment polymer having a constitutional unit represented by formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a polymer having a cinnamic acid moiety as a photosensitive group, an alignment film using the polymer, a retardation film using the polymer, and an optical film using the same. More particularly, it relates to a photoalignable polymer material having high exposure sensitivity to a light source having a wavelength of 365 nm. By using the polymer as a liquid crystal alignment film, an alignment film which gives high alignment to liquid crystals can be produced with a low exposure amount. Alternatively, by imparting liquid crystallinity to the polymer to form a photoalignable retardation material, a retardation film having desired optical properties can be produced with a low exposure amount without the need for a liquid crystal alignment film.

  Liquid crystal display devices are used in various liquid crystal display devices such as smartphones, notebook computers, and monitors of desktop computers, as well as viewfinders of video cameras, projection displays, and televisions. Furthermore, it is utilized also as optoelectronics related elements, such as an optical printer head, an optical Fourier-transform element, and a light valve. As a conventional liquid crystal display element, an element using nematic liquid crystal is the mainstream, and the alignment direction of the liquid crystal in the vicinity of one substrate and the alignment direction of the liquid crystal in the vicinity of the other substrate are twisted at an angle of 90 °. The TN (Twisted Nematic) mode has been put to practical use.

  However, in the TN mode, the viewing angle at which the image can be properly recognized is narrow, and when viewed from an oblique direction, the brightness and contrast may be lowered, and the brightness may be inverted in the middle tone. In recent years, the problem of this viewing angle is due to the MVA (Multi-domain Vertical Alignment) mode combining the vertical alignment and the technology of the protrusion structure, and further, the monomer mixed in the liquid crystal alignment state is polymerized to pretilt the liquid crystal. It is improved by the PSA (Polymer Stabilized Alignment) mode which applied C., or the IPS (In-Plane Switching) mode of a transverse electric field method.

  Advances in the technology of liquid crystal display elements are achieved not only by the improvement of these driving methods and element structures but also by the improvement of members used for display elements. Among the members used for the display element, the optical compensation film and the retardation film are one of the important elements related to the image display quality in order to realize the improvement of the contrast of the image display device and the expansion of the viewing angle range. As the quality of display devices has become higher, they have played an important role year after year. As such an optical compensation film or retardation film, a stretched film having refractive index anisotropy has been used. Recently, in order to improve the image quality, a film in which a polymerizable liquid crystal compound is aligned and polymerized has begun to be used.

  In order to align the polymerizable liquid crystal, an alignment film is mainly used. The alignment film exhibits liquid crystal alignment ability by being imparted with anisotropy, and as a means for imparting this anisotropy, a photoalignment method has been put into practical use in recent years. As the alignment mechanism of the photoalignment, many have been proposed such as a photolysis method, a photoisomerization method, a photodimerization method, a photocrosslinking method and the like (see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4). ).

  For example, in recent years, a passive glasses type 3D display has been put to practical use, and in this display, a 3D image is obtained by providing a patterned retardation film on the viewer side of the display. This retardation film is produced by applying a polymerizable liquid crystal composition on an alignment film subjected to alignment division processing by a photo alignment method, aligning the liquid crystal, and curing it. The orientation division processing is performed by irradiating the light alignment film with linearly polarized light having different polarization directions. Linearly polarized light is generally obtained by passing light from a light source through a polarizing plate, but at this time, the light intensity decreases to about 1/3 or less of the light source light. Therefore, in order to improve the productivity of the alignment film, an alignment film with high sensitivity is required. In particular, there is a demand for the above-mentioned alignment film to which the widely used i-ray exposure apparatus can be applied.

  As a photoalignment agent to which such an i-line exposure apparatus can be applied, a polyamic acid photoalignment agent as disclosed in Patent Document 5 has been proposed. However, in general, as a substrate for forming a retardation film, plastics such as triacetyl cellulose (TAC) and cyclic olefin polymers are often used. Since such plastic substrates have lower solvent resistance and heat resistance compared to glass, it is difficult to use the above-described polyamic acid-based photoalignment agent.

  Many photoalignment agents that can be used for such plastic substrates have recently been proposed, and examples thereof include Patent Document 6 and Document 1. However, materials that can be applied to widely used i-ray exposure apparatuses and have higher sensitivity are required.

  In addition, recently, retardation films have been proposed in which liquid crystal polymers are irradiated with light to control molecular orientation (see Patent Documents 7 to 11). The liquid crystalline polymer has a photosensitive group that responds to light irradiation, which makes it possible to control the alignment axis. Therefore, it is possible to produce a retardation film without using an alignment film. Also in such a so-called photo-alignable phase difference material, in order to improve the productivity, a more sensitive material is required.

International Publication No. 2011/115079 brochure JP, 2005-275364, A Patent No. 4011652 Unexamined-Japanese-Patent No. 12-212310 Patent No. 4620438 gazette JP, 2014-501813, A JP 2008-276149 A Japanese Patent Laid-Open No. 2002-202409 Unexamined-Japanese-Patent No. 2003-307619 JP, 2008-50440, A International Publication 2012 / 115017A1

Liquid Crystal, 27 (3), 349 (2000).

  An object of the present invention is to provide a photoalignable polymer with high exposure sensitivity. It is another object of the present invention to provide a non-colored photoalignable polymer which can be used at a plurality of exposure wavelengths, and is particularly orientable at a wavelength of 365 nm. Furthermore, it is to provide such a material inexpensively.

  As a result of intensive research and development, the present inventors have found that the above problem is solved by using a photosensitive group and a polymer having a specific structure. That is, the present invention is as follows.

式（１）中、Ｒ^１は独立して水素またはメチルであり；
Ｓｐはメチレンまたは炭素数２〜２０のアルキレンであり、このアルキレンにおける少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ａは独立して、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、インドール、またはカルバゾールから選ばれるいずれかの二価基であり、該二価基において、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
Ｗ^１およびＷ^２は独立して水素、フッ素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシであり；
Ｘ^１は単結合、−Ｏ−、または−ＮＨ−であり；
Ｒ^２は水素原子、メチル、炭素数２〜２０のアルキル、または上記の基Ａであり、該アルキルにおける少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 [1] A photoalignable polymer having a structural unit represented by the formula (1).

In formula (1), R ¹ is independently hydrogen or methyl;
Sp is methylene or alkylene having 2 to 20 carbon atoms, and at least one -CH _2- in this alkylene is replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C- May be
A is independently any divalent group selected from benzimidazole, benzoxazole, benzothiazole, indole, or carbazole, and in the divalent group, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
W ¹ and W ² are independently hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
X ¹ is a single bond, -O-, or -NH-;
R ² is a hydrogen atom, methyl, alkyl having 2 to 20 carbon atoms, or the above-mentioned group A, and at least one —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH = It may be replaced by CH- or -C≡C-.

[2] In the formula (1), Sp is-(CH ₂ ) _n O- and n is an integer of 1 to 10; W ¹ and W ² are hydrogen; and X ¹ is -O- A photoalignable polymer according to [1], wherein R ² is alkyl having 1 to 10 carbon atoms;

[3] In the formula (1), Sp is-(CH ₂ ) _n O- and n is an integer of 1 to 10; W ¹ and W ² are hydrogen; X ¹ is a single bond; The photoalignable polymer according to [1], wherein R ² is any divalent group selected from indole and carbazole.

[4] The photoalignable polymer according to [1] to [3], which has a structural unit formed from a monomer having a hydrogen bonding group in addition to the structural unit represented by the formula (1).

[5] The photoalignable polymer according to [4], wherein the hydrogen bonding group is a carboxyl group.

式（２）中、Ｒ^３は水素またはメチルであり；Ｑは単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおける少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｘ^２は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−であり；Ａ^２は独立して１，４−フェニレン、１，４−シクロへキシレン、ピリジン−２，５−ジイルまたはナフタレン−２，６−ジイルから選ばれるいずれかの二価基であり、該二価基において、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；Ｚ^２は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−であり；ｃは０〜２の整数であり；Ｙ^１は単結合、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。 [6] The photoalignable polymer according to [5], wherein the structural unit formed from the monomer having a hydrogen bonding group at the end is a structural unit represented by Formula (2).

In formula (2), R ³ is hydrogen or methyl; Q is a single bond or an alkylene having 1 to 20 carbon atoms, and at least one -CH _2- in this alkylene is -O-, -COO-,- OCO-, -CH = CH- or -C≡C- may be replaced; X ² is a single bond, -O-, -COO-, -OCO-, -OCOO-, -CH = CH- or- C≡C-; A ² is any divalent independently selected from 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl or naphthalene-2,6-diyl Group, in the divalent group, any hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms or May be replaced by alkoxy prime 1 to 5; ^{Z 2} is independently a single bond, -O -, - COO -, - OCO -, - CH = CH-COO -, - CH 2 CH 2 -COO- _{, -CH 2 O -, - OCH} 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CH = CH -Or -C≡C-; c is an integer of 0 to 2; Y ¹ is a single bond, -CH ₂ CH ₂ -or -CH = CH-.

[7] In the formula (2), Q is alkylene having 1 to 12 carbons, and at least one -CH _2- in this alkylene may be replaced by -O-, -COO- or -OCO-; X ² is —O—, —COO— or —OCO—; A ² is any divalent group independently selected from 1,4-phenylene or naphthalene-2,6-diyl; In the valence group, any hydrogen may be replaced by fluorine, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons; Z ² is independently a single bond, -COO-, -CH = CH- _{COO -, - CH 2 CH 2} -COO -, - CH 2 O -, - CONH- or _-CH 2 CH ₂ - and are; ^{Y 1} is a single bond, photoalignment polymer according to [6].

[8] The photoalignable polymer according to any one of claims 1 to 7, which has liquid crystallinity.

[9] The photoalignable polymer according to any one of claims 1 to 8, which has a weight average molecular weight of 1,000 to 500,000.

[10] An ink comprising a solvent and at least one of the photoalignable polymers according to any one of [1] to [9].

[11] The ink according to claim 10, further comprising a non-photo-orientable polymer.

[12] A film produced using the ink according to [10] or [11], wherein the film has a retardation of 5 nm or less.

[13] A film produced using the ink according to [10] or [11], wherein the film has a retardation of 5 nm or more.

The display element manufactured using the film as described in [14] [12] or [13].

式（１Ｍ）中、Ｒ^１は独立して水素またはメチルであり；
Ｓｐはメチレンまたは炭素数２〜２０のアルキレンであり、このアルキレンにおける少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ａは独立して、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、インドール、またはカルバゾールから選ばれるいずれかの二価基であり、該二価基において、少なくとも一つの水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；
Ｗ^１およびＷ^２は独立して水素、フッ素、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシであり；
Ｘ^１は単結合、−Ｏ−、または−ＮＨ−であり；
Ｒ^２は水素原子、メチル、炭素数２〜２０のアルキル、または上記の基Ａであり、該アルキルにおける少なくとも一つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 [15] A photosensitive compound represented by the formula (1M).

In formula (1M), R ¹ is independently hydrogen or methyl;
Sp is methylene or alkylene having 2 to 20 carbon atoms, and at least one -CH _2- in this alkylene is replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C- May be
A is independently any divalent group selected from benzimidazole, benzoxazole, benzothiazole, indole, or carbazole, and in the divalent group, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
W ¹ and W ² are independently hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
X ¹ is a single bond, -O-, or -NH-;
R ² is a hydrogen atom, methyl, alkyl having 2 to 20 carbon atoms, or the above-mentioned group A, and at least one —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH = It may be replaced by CH- or -C≡C-.

  The present invention makes it possible to obtain an optical film on which liquid crystal is immobilized in a short tact time. This can reduce the production cost of the film.

The present invention will be described in detail.
By incorporating a constituent unit having a structure represented by the formula (1) into a material, a highly sensitive photoalignable polymer, which is a feature of the present invention, can be obtained. At this time, A is a group selected from benzimidazole, benzoxazole or benzothiazole. At this time, in order to increase the sensitivity, it is preferable to select benzothiazole.

Sp is methylene or alkylene having 2 to 20 carbon atoms, and at least one -CH _2- in this alkylene is replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C- It may be done. At this time, in order to further enhance the sensitivity, as Sp, an alkylene having 2 to 10 carbon atoms, or one -CH _2-of this alkylene is replaced by -O-, -CH = CH- or -C≡C- It is preferred to use a substituted group.

W ¹ and W ² are independently hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons. At this time, in order to further enhance the sensitivity, it is preferable to select hydrogen as W ¹ and W ² .

X ¹ is a single bond, -O- or -NH-, and R ² is a hydrogen atom, methyl or alkyl having 2 to 20 carbon atoms, and at least one -CH _2- in this alkyl is -O- , -COO-, -OCO-, -CH = CH- or -C≡C-. For greater this time sensitivity, it is preferable to select as the ^{X 1} -O- or -NH-, it is more preferred to select -O-. The R ² represents a hydrogen atom, it is preferable to select an alkyl group methyl or 2 to 10 carbon atoms, a hydrogen atom, it is preferable to select methyl, or an alkyl group having 2 to 5 carbon atoms.

  The photoalignable polymer of the present invention may contain the constitutional unit represented by formula (1) alone or may contain two or more.

  When the photoalignable polymer of the present invention is used as a photoalignment film for liquid crystal, a structural unit derived from a known (meth) acrylic monomer is added to the structural unit described in Formula (1) for the purpose of improving sensitivity. It can be copolymerized. Moreover, it is also possible to adjust the refractive index and the wavelength dispersion characteristic of the polymer by this method, and it is possible to improve the defect associated with the matching of the refractive index and the wavelength dispersion characteristic with other members such as liquid crystal.

As the above (meth) acrylic monomer, (meth) acrylic acid; alkyl mono (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (Meth) acrylates, aryl mono (meth) acrylates such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Hydroxyalkyl mono (meth) acrylates such as propyl (meth) acrylate; ω-carboxypolycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, and 2-hydroxy- - phenoxypropyl (meth) carboxyl group-containing mono (methacrylate) and hydroxyalkyl mono (meth) hydroxyl group-containing mono- other than acrylates (meth) acrylates such as acrylate;
1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Crylates, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) Acrylate, ethoxylated bisphenol F di (meth) acrylate, ethoxylated bisphenol S di (meth) acrylate, hydroxypropyl di (meth) acrylate, diethylene glycol bishydroxypropyl (meth) acrylate, and monohydroxypentaerythritol tri (meth) acrylate Silicones, fluorine-substituted alkyl groups, and polyfunctional (meth) acrylates having no photoalignable group, acrylamide, methacrylamide and the like. .

Moreover, as said (meth) acrylic monomer, a commercially available monofunctional monomer or polyfunctional monomer can also be used as it is. Specifically, Aloniax M-5400 (phthalic acid monohydroxyethyl acrylate), M-5700 (2-hydroxy-3-phenoxypropyl acrylate), M-215 (isocyanuric acid) manufactured by Toagosei Chemical Industry Co., Ltd. Ethylene oxide modified diacrylate), M-220 (tripropylene glycol diacrylate), M-245 {polyethylene glycol (n ≒ 9) diacrylate}, M-305 (pentaerythritol triacrylate), M- 309 (trimethylolpropane triacrylate), M-315 (isocyanuric acid ethylene oxide modified triacrylate), M-400 {a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (main component)} The M-450 (pentaerythritol tetraacrylate), the M-8060, and the M-8560;
Osaka Organic Chemical Industry Co., Ltd. Biscoat # 295 (trimethylolpropane triacrylate), # 300 (pentaerythritol triacrylate), # 360 (trimethylolpropane ethylene oxide modified triacrylate), and # 400 (trimethylolpropane ethylene oxide modified triacrylate) Pentaerythritol tetraacrylate);
Nippon Kayaku Co., Ltd. KAYARAD TMPTA (trimethylolpropane triacrylate), PET-30 (pentaerythritol triacrylate), DPHA {mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (main component)} D-310 (dipentaerythritol pentaacrylate), D-330, and DPCA-60.

  Among the above-mentioned known (meth) acrylic monomers, the following may be mentioned in order to maintain the sensitivity of the photoalignment film and to improve the solvent solubility of the photoalignment polymer for the purpose of improving unevenness when the photoalignment film is applied. It is preferred to select a monomer.

  Alkyl mono (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl mono (meth) acrylates such as acrylates, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate, trimethylolpropane triacrylate.

  The above known monomers can be used alone or in combination of two or more.

  There is no limitation on the ratio of the structural unit represented by the formula (1) in the photoalignment film and the structural unit derived from the above-mentioned known (meth) acrylic monomer in the photoalignable polymer of the present invention. However, in order to improve the above problems while maintaining the sensitivity, the ratio (weight ratio) of the constitutional unit represented by the formula (1) to the constitutional unit derived from a known (meth) acrylic monomer is 10: It is preferable that it is 0-1: 9, and it is more preferable that it is 10: 0-5: 5.

式（２）中、Ｒ^３は水素またはメチルであり；Ｑは単結合または炭素数１〜２０のアルキレンであり、このアルキレンにおける少なくとも一つの−ＣＨ₂−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｘ^２は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−であり；Ａ^２は独立して１，４−フェニレン、１，４−シクロへキシレン、ピリジン−２，５−ジイルまたはナフタレン−２，６−ジイルから選ばれるいずれかの二価基であり、該二価基において、任意の水素はフッ素、塩素、シアノ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、トリフルオロメチル、炭素数１〜５のアルキルまたは炭素数１〜５のアルコキシで置き換えられてもよく；Ｚ^２は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−であり；ｃは０〜２の整数であり；Ｙ^１は単結合、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−である。 As a photoalignable polymer of the present invention using a structural unit having a structure represented by the formula (1), a material provided with liquid crystallinity is used, and after forming a thin film, exposure is performed, and the liquid crystal temperature of the polymer is used if necessary. By heating above, the photoalignable polymer itself of the present invention can be used as a retardation film. (Herein, in the present specification, the term "liquid crystalline" is not limited to the meaning of having a liquid crystal phase, and when it is mixed with another liquid crystal compound even if it has no liquid crystal phase itself) In addition, it is used as a term including the meaning of having the property that it can be used as a component of a liquid crystal composition.) Such a so-called photoalignable retardation material has the formula shown below in the photoalignable polymer of the present invention It can be realized by incorporating the constituent unit of (2).

In formula (2), R ³ is hydrogen or methyl; Q is a single bond or an alkylene having 1 to 20 carbon atoms, and at least one -CH _2- in this alkylene is -O-, -COO-,- OCO-, -CH = CH- or -C≡C- may be replaced; X ² is a single bond, -O-, -COO-, -OCO-, -OCOO-, -CH = CH- or- C≡C-; A ² is any divalent independently selected from 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl or naphthalene-2,6-diyl Group, in the divalent group, any hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms or carbon. May be replaced by the number 1-5 alkoxy; ^{Z 2} independently represents a single bond, -O -, - COO -, - OCO -, - CH = CH-COO -, - CH 2 CH 2 -COO- _{, -CH 2 O -, - OCH} 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CH = CH -Or -C≡C-; c is an integer of 0 to 2; Y ¹ is a single bond, -CH ₂ CH ₂ -or -CH = CH-.

In the so-called photo-alignable retardation material of the present invention, Q, X ² , A ² , Z ² , Y ¹ , and Q 2 in the formula (2) are used to suppress defects such as haze generation and obtain desired retardation. Regarding c, it is preferable to make the following selection. That is, Q is alkylene having 1 to 12 carbons, and at least one -CH _2- in this alkylene may be replaced by -O-, -COO-, or -OCO-; and X ² is -O -, - COO-, or a -OCO-; ^{a 2} is either a divalent radical selected from independently 1,4-phenylene or naphthalene-2,6-diyl; ^{Z 2} is independently single _{bond, -COO -, - CH = CH} -COO -, - CH 2 CH 2 -COO -, - CH 2 O-, or _-CH 2 CH ₂ - a and; c is an integer of 0 or 1; Y ¹ is a single bond.

  For the same reason as described above, the following may be mentioned as the most preferable specific examples of the structural unit represented by the formula (2).

  The present invention is not limited by these specific examples.

When the photoalignable polymer of the present invention is used in a photoalignable retardation material application, the ratio of the structural unit represented by the above formula (1) in the polymer to the structural unit represented by the above formula (2) There is no limit.
However, in order to obtain a uniform + A plate while maintaining the exposure sensitivity, the ratio (weight ratio) of the constitutional unit represented by the formula (1) to the constitutional unit represented by the formula (2) is 9: 1 It is preferably 1 to 9 and more preferably 5: 5 to 1: 9.

  The structural unit represented by Formula (2) may be contained independently, or two or more may be contained.

  When the photoalignable polymer of the present invention is used in a photoalignable retardation material application, it is derived from still another known (meth) acrylic monomer for the purpose of adjusting the liquid crystal transition temperature of the photoalignable polymer of the present invention, etc. Can be copolymerized. As such purpose, alkyl mono (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, Particular preference is given to using hydroxyalkyl mono (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, trimethylolpropane triacrylate.

  When the photoalignable polymer is used in a photoalignable retardation material application, the weight average molecular weight of the polymer is preferably 1000 to 500,000 in order to develop the target sensitivity. Further, even in the case of laminating a material such as a polymerizable liquid crystal on the photoalignable retardation material, a polymer having a weight average molecular weight in this range is preferable because it has a certain solvent resistance.

  A polymer that exhibits liquid crystallinity but does not have a photoreactive group is called a liquid crystalline polymer.

In the description of the present specification, the term "arbitrary" used in describing the symbols of chemical formulas means that "the number of elements (or functional groups) can be freely selected as well as the positions". And, for example, the expression "any A may be replaced by B, C or D" means that one A may be replaced by any one of B, C and D, and any two of A One may be replaced by two of B, C or D, and may be replaced by B and C, B and D, or C and D. That is, when a functional group has one or more of A and there is an expression that "optional A may be replaced by B, C or D" for the functional group, the presence on the functional group It means that any one selected from B, C and D (where the selected species is X) may be disposed instead of at least one of A. Here, when a plurality of A's are substituted, a plurality of X's disposed in place of the A's may be the same or may be different from each other. However, the number of X placed instead of A is one for one A. Therefore, when it is assumed that any —CH ₂ — may be replaced by —O—, such a replacement that does not result in a linking group —O—O— is not included.

  In addition, having one polymerizable group may be referred to as monofunctional. In addition, having two or more polymerizable groups may be referred to as polyfunctional or as a designation according to the number of the polymerizable groups (for example, bifunctional having two polymerizable groups).

In addition, a compound obtained by introducing an arbitrary functional group into a certain compound A, or a compound obtained by replacing an arbitrary atom or the like may be referred to as a derivative or an A derivative.
The photoalignable polymer may be simply referred to as the polymer. Moreover, a liquid crystal display element may be abbreviated as a display element, and a liquid crystal alignment film may be abbreviated as an alignment film.

  The polymer composition of the present invention to which another polymer is further added as a second component in addition to the photoalignable polymer having the structure of the formula (1) is also useful for application to photoalignment film applications and the like. By this method, for example, it is possible to improve the exposure sensitivity described above and adjust the refractive index of the polymer and the wavelength dispersion characteristics. When the polymer composition is formed into a film by controlling the surface tension of each of these polymers to further improve the properties, the component ratio of the photoalignable polymer to the second polymer is inclined in the film thickness direction of the film. Method is more effective. According to this method, for example, the photoalignable polymer having the structure of the formula (1) of the present invention can be concentrated at the air interface and the second polymer can be concentrated on the substrate surface. Thereby, when the present material is used for a photo alignment film, it can be made a material having higher exposure sensitivity and less occurrence of defects.

  In order to produce a film in which component ratios of a plurality of polymers as described above exist with an inclination, with good reproducibility, the photoalignable polymer of the present invention having a constitutional unit represented by the formula (1) is a siloxane It is preferable to introduce a structural unit having a fluoroalkyl group or the like. By the introduction of the structural unit, the surface tension at the time of film formation of the photoalignable polymer of the present invention is lowered, and the photoalignable polymer is easily segregated at the air interface in the film.

  As a monomer which has a silicone group, the monomer etc. which are represented by following formula (3M-1)-(3M-3) are mentioned, for example.

（式中、Ｒ^１１は炭素数１〜２０のアルキル基を示し、ｒ１は２又は３、ｎ１は１〜１００の整数を示す。）

(Wherein, R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, r 1 represents 2 or 3, and n 1 represents an integer of 1 to 100).

Among these monomers, n1 is 1 to 1000, and R ¹¹ is a monomer represented by the above formula (3M-1) in order to maintain the solvent solubility of the polymer while improving the layer separation property in the film. It is preferred to use a compound in which is an alkyl group of 1 to 5 carbon atoms. Furthermore, it is preferable to use a compound in which n1 is 1 to 100 and R ¹¹ is an alkyl group having 1 to 5 carbon atoms.

  The content of the monomer having a silicone group is preferably 0.01 to 50% by weight with respect to all the monomers, in order to maintain the solvent solubility of the polymer while improving the layer separation when forming a film. More preferably, it is 0.1 to 10% by weight.

  Examples of the methacrylic acid ester having a fluorine-substituted alkyl group include methacrylic acid 1H, 1H, 2H, 2H-nonafluoroheptyl, methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, methacrylic acid 1H, 1H, 7H-dodeca Fluoroheptyl, methacrylic acid 1H, 1H, 2H, 2H-tridecafluorooctyl, methacrylic acid 1H, 1H-perfluorononyl, methacrylic acid 1H, 1H, 2H, 2H-perfluorododecyl etc. may be mentioned. As itaconic acid derivatives having a fluorine-substituted alkyl group, itaconic acid 1H, 1H, 2H, 2H-nonafluoroheptyl, itaconic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, itaconic acid 1H, 1H, 7H-dodeca Fluoroheptyl, itaconic acid 1H, 1H, 2H, 2H-tridecafluorooctyl, itaconic acid 1H, 1H-perfluorononyl itaconic acid 1H, 1H, 2H, 2H, 2H-perfluorododecyl, methyl itaconic acid 1H, 1H, 2H , 2H-nonafluoroheptyl, methylitaconic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, methylitaconic acid 1H, 1H, 7H-dodecafluoroheptyl, methylitaconic acid 1H, 1H, 2H, 2H- tridecafluoro Octyl, methyl itaconic acid 1 H, 1 H-Perf Orononiru, methyl itaconic acid IH, IH, 2H, etc. 2H- perfluoro dodecyl and the like. Among the methacrylic acid ester having a fluorine-substituted alkyl group and the itaconic acid derivative having a fluorine-substituted alkyl group, methacrylic acid 1H, in order to maintain the solvent solubility of the polymer while improving the layer separation in the film. 1H, 2H, 2H-nonafluoroheptyl, methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, methacrylic acid 1H, 1H, 7H-dodecafluoroheptyl, methacrylic acid 1H, 1H, 2H, 2H-tridecafluoro Octyl, 1H, 1H-perfluorononyl methacrylate, and 1H, 1H, 2H, 2H-perfluorododecyl methacrylate are preferred.

  The content of the monomer having a fluorine-substituted alkyl group in the total monomer mixture to be used is preferably 0 with respect to all the monomers in order to maintain the solvent solubility of the polymer while improving the layer separation in the film. .01 to 50% by weight, more preferably 1 to 10% by weight.

  Furthermore, for the same reason as described above, alkyl monomers having a short alkyl chain such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate as raw material monomers for the second polymer Mono (meth) acrylates; hydroxyalkyl mono (meth) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate It is preferred to use an acrylate. It is because the surface tension at the time of film-forming raises the polymer which uses this monomer as a raw material, and this polymer becomes easy to segregate at the board | substrate interface in a film. Among the above monomers, it is most preferable to use a hydroxyalkyl mono (meth) acrylate, in particular, in order to maintain good solvent solubility and improve such segregation effect.

  The method for producing the photoalignable polymer of the present invention is not particularly limited, and a general method which is industrially treated can be used. Specifically, vinyl as a constituent monomer, that is, a monomer capable of forming a constituent unit represented by Formula (1), a monomer capable of forming a constituent unit represented by Formula (2), and other constituent units Can be produced by a cationic polymerization method, a radical polymerization method or an anionic polymerization method utilizing an ethylenically unsaturated double bond contained in each of the monomers capable of forming H. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

  When the photoalignable polymer of the present invention has one or more monomers as a structural unit, a random copolymer, a block copolymer, or a graft copolymer can be formed from the arrangement order of the structural units. The arrangement order of the constituent units is not particularly limited, but a random copolymer is particularly preferable in view of the easiness of the polymerization method.

  In the present invention, the photoalignable polymer is a monomer capable of forming the constitutional unit represented by the formula (1), and a monomer capable of forming the constitutional unit represented by the formula (2) optionally used and the like. The monomer capable of forming a structural unit of can be suitably obtained by radical polymerization in the presence of a suitable polymerization initiator.

As a polymerization initiator for radical polymerization, known compounds such as a radical thermal polymerization initiator and a radical photopolymerization initiator can be used.
A radical thermal polymerization initiator is a compound which generates a radical by heating above the decomposition temperature. Such radical thermal polymerization initiators include, for example, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; diacyl peroxides such as acetyl peroxide and benzoyl peroxide; hydrogen peroxide, tert-butyl hydroperoxide Hydroperoxides such as oxides and cumene hydroperoxides; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; peroxyketals such as dibutylperoxycyclohexane, peroxy Neodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy-2-ethylcyclohexanoic acid-tert-amyl ester Alkyl per esters of potassium persulfate, sodium persulfate, ammonium persulfate and the like; and azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile And azo compounds such as Such radical thermal polymerization initiators can be used alone or in combination of two or more.

  The radical photopolymerization initiator is not particularly limited as long as it is a compound which initiates radical polymerization by light irradiation. Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Ndidyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminoethylbenzoate, 4-dimethylaminobenzoate isoamyl, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-biimidazole (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' -Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2 -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2,4-cyclopentadi) -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2 -(3-Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1 3- benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

  The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used. The same applies to other polymerization methods, and the details thereof are described in “Polymer synthesis (upper)” (by Takeshi Endo, Kodansha 2010 issue). The outline of the solution polymerization method which is a general radical polymerization method will be described below.

  Solution polymerization is a reaction in which polymerization is carried out in a solvent using an oil-soluble polymerization catalyst. These organic solvents can be arbitrarily selected in the range suitable for the object and effect of the invention. These organic solvents are usually organic compounds having a boiling point of 50 to 200 ° C. at atmospheric pressure, and organic compounds capable of uniformly dissolving monomers, polymerization process components and the like are preferable.

  The organic solvent used here is not to have an inhibitory effect on radical polymerization, preferably aromatic compounds such as benzene, toluene, xylene and ethylbenzene; such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane Aliphatic compounds; alcohols such as methanol, ethanol, 1-propanol, 2-propanol and ethylene glycol; dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethers such as tetrahydrofuran and dioxane; acetone, methyl ethyl ketone, methyl isobutyl Ketones and ketones such as cyclohexanone; esters such as ethyl acetate, butyl acetate, amyl acetate and γ-butyrolactone; It is. In addition, it is possible to use these organic solvents individually or in combination of 2 or more.

  The solution polymerization conditions are also not particularly limited, but for example, heating for 10 minutes to 20 hours in a temperature range of 50 to 200 ° C. is preferable. Furthermore, it is preferable to perform an inert gas purge such as nitrogen, not only during solution polymerization but also before solution polymerization is initiated, so that the generated radicals are not inactivated.

  A radical polymerization method using a chain transfer agent is particularly effective in order to control the molecular weight of the photosensitive polymer, to homogenize the molecular weight distribution, or to promote polymerization. This makes it possible to obtain a polymer having a more uniform molecular weight distribution in a preferred molecular weight range.

  As a chain transfer agent, β-mercaptopropionic acid, β-mercaptopropionic acid methyl ester, isopropyl mercaptan, octyl mercaptan, decyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol and p-nonyl thiophenol, thiosalicyl Acid, mercaptoacetic acid, and mercaptans such as mercapto; carbon tetrachloride, chloroform, butyl chloride, polyhalogenated alkyls such as 1,1,1-trichloroethane and 1,1,1-tribromooctane; α-methylstyrene, Low activity monomers such as α-methylstyrene dimer can be used. The amount of the chain transfer agent used is determined by the activity of the chain transfer agent, the combination of monomers, the solvent, the temperature, other polymerization conditions, and the like. Usually, it is about 0.01 mol% to 50 mol% with respect to the total number of moles of monomers used.

[Additive]
The film using the photoalignable polymer of the present invention is mainly formed on a substrate and used. The film is required to have properties required for an optical film or an optical display element, such as good orientation, adhesion to a substrate, coating uniformity, chemical resistance, heat resistance, permeability, gas barrier properties, and the like. Additives can be used to impart such properties.

The addition amount of various additives is determined according to the required properties, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the photosensitive polymer of the present invention.
Additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, coatability improvers such as silicone resins, and silane cups Adhesion improvers such as ring agents, ultraviolet absorbers such as alkoxybenzophenones, aggregation inhibitors such as sodium polyacrylate, thermal crosslinkers such as oxirane compounds, melamine compounds or bisazide compounds, alkali solubility such as organic carboxylic acids There is an accelerator etc.

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methyl coumarin, 7-hydroxy 4-methyl coumarin, ketocoumarin, carbonyl bis coumarin), aromatic 2-hydroxy ketones, and amino-substituted ones Aromatic 2-hydroxy ketone (2-hydroxy benzophenone, mono- or di-p- (dimethylamino) 2-hydroxy benzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoyl methylene-3) -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-Methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-Methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) )) 3-Methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Futoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p) -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, furocumarin and the like.
Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl bis coumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone ketal.

  In addition, the photoalignable polymer of the present invention has a polymerizable group as a monomer capable of forming another structural unit when obtaining the photoalignable polymer instead of blending the photosensitizer as an additive. The photosensitizing ability can also be imparted by using a sensitizer. In this embodiment, as the photosensitive polymer, a structural unit derived from a photosensitizer having a polymerizable group, that is, an ethylenically unsaturated double bond or the like included in the photosensitizer having a polymerizable group A polymer further comprising a structural unit formed by opening of a π bond constituting the polymerization reactive multiple bond will be used. In the present invention, as the "photosensitizer having a polymerizable group", one having a polymerizable group introduced into a prototype photosensitizer is used to constitute a "photosensitizer having a polymerizable group". Examples of the polymerizable group include acryloyl, methacryloyl, vinyl, maleimide, itaconyl and derivatives thereof.

  Below, the specific example of the structural unit derived from the photosensitizer which has a polymeric group is shown. However, the present invention is not limited by these specific examples.

これらの化合物において、Ｒ^３は独立して水素またはメチルであり；ｑは独立して１〜１２の整数である。

In these compounds, R ³ is independently hydrogen or methyl; q is independently an integer of 1-12.

  In the present invention, the structural unit derived from the “photosensitizer having a polymerizable group” in the photosensitive polymer is represented by the structural unit represented by the formula (1) and the formula (2) It can be contained in a ratio of 30 to 1 mole, preferably 5 to 1 mole, where the total number of moles with the structural unit is 100.

  As an additive, a coupling agent can be used to improve the adhesion to the substrate. As the coupling agent, silane based, aluminum based and titanate based compounds are used. Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and aluminums such as acetoalkoxyaluminum diisopropylate And titanate compounds such as tetraisopropyl bis (dioctyl phosphite) titanate.

  As an additive, a surfactant can be used to improve the wettability to the underlying substrate, the leveling property, and the coating property. As the surfactant, silicone surfactants, acrylic surfactants, fluoro surfactants and the like are used. Specifically, silicone-based surfactants such as Byk (registered trademark) -300, 306, 335, 310, 341, 344, and 370 manufactured by Big Chemie Co., Ltd., Big Chemie Acrylic surfactants such as Byk (registered trademark) -354, 358, 361 manufactured by KK Co., Ltd., SC-101 manufactured by Asahi Glass Co., Ltd., EF-351 manufactured by Tochem Products Co., Ltd., etc. And fluorine-containing surfactants.

When the photoalignable polymer of the present invention is used for retardation film applications and the like, a liquid crystalline low molecular weight compound may be contained for the purpose of adjusting the liquid crystal temperature range and the optical anisotropy. Among the liquid crystalline low molecular weight compounds, compounds having a polymerizable group are preferable.
[Ink composition for photo alignment]

The photoalignment ink composition (photoalignment agent) of the present invention is typically used as a coating solution in which the photoalignment polymer of the present invention is dissolved in an organic solvent.
As the organic solvent used at this time, the solvent used at the time of polymerization of the photosensitive polymer may be used as it is, or the solvent at the time of polymerization may be once removed and a new solvent may be used again. At this time, as organic solvents to be newly used, aromatic compounds such as benzene, toluene, xylene and ethylbenzene; aliphatic compounds such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane; methanol, ethanol, 1- Alcohols such as propanol, 2-propanol and ethylene glycol; Ethers such as dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ethyl acetate , Esters such as butyl acetate, amyl acetate and γ-butyrolactone; and the like. From the viewpoint of toxicity and environmental impact, 1-propanol, 2-propanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, 2-butoxyethanol, 3-methoxy-3-methylbutanol, ethylene glycol monomethyl ether, ethylene glycol Preferred are dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, butyl acetate and the like. Further, from the viewpoint of solvent resistance to a plastic substrate, 1-methoxy-2-propanol, methyl isobutyl ketone, cyclohexanone, cyclopentanone and the like are preferable. These organic solvents can be used singly or in combination of two or more.
[Photo-alignment film]

  The film produced from the photoalignable polymer of the present invention can be produced by the method described above (for example, spin coating, gravure coater, reverse gravure, Mayer bar coater, die coater, reverse roll coater, fountain reverse roll coater) Applied to the substrate by a kiss roll coater, a bar coater, a knife coater, a lip coater, a resist coater, an ink jet method), and after removing the organic solvent, the coated film obtained is irradiated with polarized light, and heat treatment is performed if necessary. It can be oriented and obtained.

  At this time, polarized light irradiation to the coating film is performed to orient the photoalignable polymer of the present invention, and is performed by irradiating the film with light from a single direction. The light irradiation forms an orientation axis on the photoalignable film. At this time, X-rays, electron beams, ultraviolet rays, visible light or infrared rays (heat rays) are used as the irradiation light, and ultraviolet rays are particularly preferably used.

Since the photoalignable film of the present invention has high sensitivity in the long wavelength region of ultraviolet light, particularly at 365 nm, it is suitably used for an exposure machine having a light source of this wavelength. However, since the photoalignable film of the present invention is sensitive to a wide range of ultraviolet rays other than 365 nm, an exposure machine which emits a wavelength of 254 to 360 nm can also be used.
As a light source, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a high pressure discharge lamp, a short arc discharge lamp (metal halide lamp), or an LED lamp is used, preferably a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp Alternatively, an LED lamp is used.

The type of light used for alignment can be used regardless of polarization and non-polarization, but in order to more reliably impart an alignment function, it is particularly preferable to use linear polarization. Irradiation dose is preferably ^{10mJ / cm 2 ~20000mJ / cm 2} , and most preferably ^{20mJ / cm 2 ~5000mJ / cm 2} .

The photoalignable film of the present invention can also be suitably used as a retardation film. In the present invention, a retardation film is obtained by irradiating a light film containing linearly polarized light to a coating film formed of the above-described photoalignable polymer of the present invention, and further heating the film if necessary. The heat treatment is performed to further increase the anisotropy of the photoalignable film imparted by the polarized light irradiation, whereby a retardation film is obtained. At this time, the heating temperature T is such that the lower limit and the upper limit of the temperature at which the polymer has a liquid crystal phase are Tm and Ti, respectively
Tm-80 ° C. ≦ T ≦ Ti
Is preferred. In general, the temperature is about 60 ° C. to 250 ° C., and preferably about 80 ° C. to 150 ° C. Tm is the crystal phase-liquid crystal phase transition temperature or glass transition temperature of the polymer, and Ti corresponds to the liquid crystal phase-isotropic phase transition temperature.

  After the heat treatment, light may be irradiated again to fix the induced orientation. The light for fixing the orientation is preferably ultraviolet light, and may be linearly polarized light or non-polarized light.

  Furthermore, a dichroic dye may be added to the photoalignable ink composition of the present invention. A film prepared from the photoalignable ink composition can be used as an information recording device, a polarizing plate, an anti-counterfeit medium, and the like.

[Laminate]
The photoalignable film of the present invention has the ability to align liquid crystal materials. Therefore, a film having optical anisotropy and a laminate thereof can be easily formed by applying a polymerizable liquid crystal, a liquid crystalline polymer or the like on the retardation film. Examples of the polymerizable liquid crystal material include polymerizable liquid crystal compositions containing a liquid crystalline (meth) acrylic compound having at least one polymerizable group in the molecule, a liquid crystalline oxirane compound, a liquid crystalline oxetane compound, and the like. Among these, it is more preferable to use a polymerizable liquid crystal composition using a liquid crystalline (meth) acrylic compound because the alignment property is good.

  Below, the specific example of a polymeric liquid crystal compound is shown. However, the present invention is not limited by these specific examples.

これら（ＬＣ−１）〜（ＬＣ−１０）の化合物において、ｒは独立して１〜１２の整数である。

In the compounds (LC-1) to (LC-10), r is independently an integer of 1 to 12.

  The optical film of the present invention is useful as various optical members, display elements such as liquid crystal display elements, and other optical elements.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum. The unit of phase transition temperature is ° C, C represents a crystal, G represents a glass state, S represents a smectic phase, N represents a nematic phase, and I represents an isotropic liquid phase. Below, the measuring method of physical-property value is shown.

<Structural confirmation of compound>
The structure of the compound synthesized was confirmed by measurement of 500 MHz proton NMR (Bruker: DRX-500). The stated values represent ppm, s is a singlet, d is a doublet, t is a triplet, and m is a multiplet.

<Phase transition temperature>
The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 10 ° C./min. The temperature at which one phase transferred to another was measured. C is a crystal, G is a glass state, N is a nematic phase, and I is an isotropic liquid. The NI point is the upper limit temperature of the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. “C 50 N 63 I” indicates that the crystal transitioned from the crystalline phase to the nematic phase at 50 ° C., and the transition from the nematic phase to the isotropic liquid at 63 ° C. The parentheses show a monotropic liquid crystal phase.

<Weight average molecular weight (Mw) and polydispersity (Mw / Mn)>
Shimadzu LC-9A gel permeation chromatograph (GPC) manufactured by Shimadzu Corporation and column Shodex (registered trademark) GF-7M HQ (trade name: THF, standard substance: polystyrene of known molecular weight) were used.

<Copolymerization ratio>
The reprecipitated polymer sample was subjected to 1 H NMR measurement, and the actual copolymerization ratio in the polymer was calculated from the proton ratio of each monomer component.

<Film thickness measurement>
The film thickness of the alignment film was measured using an optical film thickness measurement system (DF-1030R, Techno Synergy, a limited company). The film thickness of the retardation film was obtained by scraping the retardation layer portion from the glass substrate, and measuring the film thickness of the step at that portion with Alpha Step IQ manufactured by KLA TENCOR Co., Ltd. which is a fine shape measuring device.

<Exposure>
Ushio Electric Co., Ltd.'s 250 W ultra-high pressure mercury lamp (Multilight-250) was used. Alternatively, a UV-LED irradiation unit (365 nm) manufactured by Toshiba Litec was used. Linearly polarized light was obtained by using a wire grid polarizing plate for ultraviolet region (manufactured by Polatechno Co., Ltd.).

<Orientation of retardation film>
It confirmed by the method shown below.
(1) Visual Observation Method A substrate on which a retardation film was formed was sandwiched between two polarizing plates arranged in cross nicol, and observed, and the substrate was rotated in a horizontal plane to confirm the light and dark state. The substrate on which the retardation film was formed was observed with a polarizing microscope to confirm the presence or absence of alignment defects and light leakage. When the alignment control force with respect to the liquid crystal is weak, many broken light leakage is observed.

(2) Measurement by Polarization Analyzer A substrate on which a retardation film was formed was irradiated with light having a wavelength of 550 nm using OPTIPRO (registered trademark) polarization analyzer manufactured by Syntech Co., Ltd. The retardation was measured while decreasing the incident angle of this light from 90 ° to the film surface. The retardation (phase delay) is represented by Δn × d. The symbol Δn is the optical anisotropy value, and the symbol d is the thickness of the polymer film.

<Contrast measurement>
The contrast of the retardation film was calculated from the following equation.
Contrast = brightness in parallel nicol state / brightness in cross nicol state At this time, the brightness in the cross nicol state and the brightness in the parallel nicol state are obtained by using the substrate on which the retardation film is formed as two polarizations of polarization microscope. It pinched between boards and measured using a luminance meter. The luminance meter used YOKOGAWA 3298F. The base material was rotated horizontally, and the minimum luminance was taken as "luminance in cross nicol state". The base material was rotated in a horizontal plane, and the maximum luminance was taken as "luminance in the parallel nicol state".

Compound (2M-1) was synthesized according to the method described in JP-A-2009-191117.

Example 1 Synthesis of Compound (1M-1) Compound (1M-1) was synthesized according to the following scheme.

以下、化合物（１Ｍ−１）の合成について、より具体的に説明する。

Hereinafter, the synthesis of compound (1M-1) will be described more specifically.

(Step 1: Synthesis of Compound (ex-1))
A mixture of 25.0 g (144 mmol) 4-Chloro-3-nitrophenol, 25.6 g (187 mmol) 6-chlorohexanol, 2.4 g (14.5 mmol) KI, and 30.0 g (217 mmol) K2CO3 in DMF (125 ml) The mixture was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After cooling, the reaction solution was poured into pure water (200 ml) and extracted with toluene (200 ml). The organic layer was washed twice with pure water (100 ml) and then dried over anhydrous MgSO4. After filtration, the solvent was evaporated under reduced pressure to obtain the desired product (ex-1). This compound was used in the next reaction without further purification. 29.1 g (82%).

(Step 2: Synthesis of Compound (ex-2))
A mixture of 20.0 g (81.1 mmol) of compound (ex-1) and 48.0 g (200 mmol) of Na2S 9H2O was refluxed in pure water (140 ml) and EtOH (60 ml) under a nitrogen atmosphere for 8 hours. After cooling, acetic acid (12 ml) was slowly added with stirring. AcOEt (200 ml) was added to the reaction solution for extraction. The extract was washed twice with pure water (100 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 1: 1 → 1: 5) to obtain the desired product (ex-2). 8.4 g (43%).

(Third step: synthesis of compound (ex-3))
A mixture of 8.0 g (33.1 mmol) of the compound (ex-2), 6.0 g (31.5 mmol) of Methyl 4-formylcinnamate, and 3.50 g (33.6 mmol) of NaHSO3 was subjected to N, N-Dimethylacetamide (30 ml). The mixture was stirred at 80 ° C. for 2 hours under nitrogen atmosphere. After cooling, AcOEt (200 ml) was added to the reaction solution, and the extract was washed twice with pure water (100 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 5: 1) to obtain the desired product (ex-3). 9.6 g (74%).

(Step 4: Synthesis of Compound (1M-1))
A mixture of 9.0 g (21.9 mmol) of compound (ex-3), 4.0 ml (28.7 mmol) of Et3N, and 60 ml of CH2 Cl2 (60 ml) under a nitrogen atmosphere was 2.5 ml (26.5 mmol) of Chloro methacrylate. Add slowly below 10 ° C. After stirring overnight at room temperature, the reaction solution was washed twice with pure water (50 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 10: 1) to obtain the desired product (1M-1). 8.5 g (81%).

The NMR analysis value of the obtained compound (1M-1) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.10 (d, 2 H, J = 8.35 Hz), 7.75 (d, 1 H, J = 7.30 Hz), 7.73 (d, 1 H, J = 14.40 Hz), 7.64 (d, 2 H, J = 8. 30 Hz), 7.55 (d, 1 H, J = 2. 35 Hz), 7.05 (dd, 1 H, J = 8.80, 2.45 Hz), 6.53 (d, 1 H, J = 16.15 Hz), 6.10 (s, 1 H), 5.55 (s, 1 H), 4.17 (t, 2 H, J = 6. 55 Hz), 4.07 (t, 2 H, J = 6.40 Hz), 3.83 (s, 3 H), 1.95 to 1.48 (m, 11 H).

Example 2 Synthesis of Compound (1M-2)

(Step 1: Synthesis of Compound (ex-4))
It synthesize | combined similarly to the method of Example 1, and obtained the target object. 54% yield.

(Step 2: Synthesis of Compound (ex-5))
A mixture of 12.0 g (48.8 mmol) of compound (ex-4) and 11.0 g (103 mmol) of benzylamine was stirred at 130 ° C. for 2 hours under a nitrogen atmosphere. After cooling, the reaction solution was poured into pure water (100 ml) and extracted by adding ethyl acetate (100 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 5: 1) to obtain the desired product (ex-5). 8.0 g (52%).

Step 3: Synthesis of Compound (ex-6)
A mixture of 7.5 g (23.7 mmol) of compound (ex-5) and 750 mg of 10% Pd / C (NX type, NE Chemcat) in a mixed solvent of toluene / EtOH (100 ml / 100 ml) at room temperature overnight And hydrogen addition reaction (hydrogen pressure; 980 kPa). After filtering the catalyst, the reaction mixture was concentrated to obtain the desired product (ex-6). 4.7 g (95%). This compound was used as it was in the next reaction without further purification.

(Step 4: Synthesis of Compound (ex-7))
A mixture of 4.5 g (23 mmol) of compound (ex-6), 4.5 g (22 mmol) of Ethyl 4-formylcinnamate, and 2.5 g (24 mmol) of NaHSO 3 in N, N-Dimethylacetamide (20 ml) under a nitrogen atmosphere Stir at 80 ° C. for 2 hours. Here, Ethyl 4-formylcinnamate was synthesized according to Journal of Medicinal Chemistry, 59 (19), 8967-9004 (2016). After cooling, AcOEt (150 ml) was added to the reaction solution, and the extract was washed twice with pure water (100 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 5: 1) to obtain the desired product (ex-7). 5.4 g (65%).

(Step 4: Compound (Synthesis of 1M-2))
In a mixture of 5.0 g (13 mmol) of the compound (ex-7), 2.2 ml (16 mmol) of Et 3 N, and 50 ml of CH 2 Cl 2, 1.2 ml (13 mmol) of Chloro methacrylate slowly under nitrogen added. After stirring overnight at room temperature, the reaction solution was washed twice with pure water (50 ml). The organic layer was dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene: AcOEt = 10: 1) to obtain the desired product (1M-2). 2.2 g (38%).

The NMR analysis value of the obtained compound (1M-2) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 11.85 (s, 1 H), 8. 10 (d, 2 H), 7.73 (d, 1 H), 7.62 (d, 2 H), 7.38 (D, 1 H), 7. 29 (d, 1 H), 7.0 3 (dd, 1 H), 6. 50 (d, 1 H), 6. 10 (s, 1 H), 5.5 5 (s, 1 H) , 4.16 (t, 2H), 4.05 (t, 2H), 1.95 to 1.20 (m, 7H).

Example 3 Synthesis of Compound (1M-3) Compound (1M-3) was synthesized according to the following scheme.

インドール ３．３４ｇ （２８．５ ｍｍｏｌ）およびトリエチルアミン ４．８ ｍｌ （３４．４ ｍｍｏｌ） の塩化メチレン（６０ｍｌ）溶液に、化合物（ｅｘ−８） １０．０ｇ （２８．５ ｍｍｏｌ）の塩化メチレン（４０ｍｌ）溶液を、窒素雰囲気下、１０℃以下で加えた。この時化合物（ｅｘ−８）はＰｏｌｙｍｅｒ， ５２巻（２５号）， ５７８８（２０１１）に記載の方法に従って得た。反応液を室温で一晩撹拌後、純水（１００ｍｌ）にあけ、有機層を分離した。有機層は、さらに純水（８０ｍｌ）で洗浄後、無水ＭｇＳＯ４で乾燥し、ろ過後、溶媒を減圧留去した。残渣をカラムクロマトグラフィー（シリカゲル／トルエン→トルエン：ＡｃＯＥｔ＝１０：１）で精製する事により、目的物の（１Ｍ−３）を得た。３．２ｇ （２６％）。

Into a solution of 3.34 g (28.5 mmol) of indole and 4.8 ml (34.4 mmol) of triethylamine in 60 ml of methylene chloride, 10.0 g (28.5 mmol) of methylene chloride (28.5 mmol) of the compound (ex-8) 40 ml) solution was added below 10 ° C. under nitrogen atmosphere. At this time, the compound (ex-8) was obtained according to the method described in Polymer, 52 (25), 5788 (2011). The reaction solution was stirred at room temperature overnight, poured into pure water (100 ml), and the organic layer was separated. The organic layer was further washed with pure water (80 ml), dried over anhydrous MgSO4, filtered, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (silica gel / toluene → toluene: AcOEt = 10: 1) to obtain the desired product (1M-3). 3.2 g (26%).

The NMR analysis value of the obtained compound (1M-3) is as follows.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.54 (d, 1 H), 7.98 (d, 1 H), 7.68 (d, 1 H), 7.59 (d, 2 H), 7.12 (D, 1H), 6.95 (d, 2H), 6.69 (d, 1H), 6.10 (s, 1H), 5.55 (s, 1H), 4.17 (t, 2H) , 4.05 (t, 2H), 1.95 to 1.40 (m, 8H).

Example 4 Production of Polymer (1-1) for Photo-alignment Film The above monomer (1M-1) 4.5000 g, 2-hydroxyethyl methacrylate 0.5000 g, and azobisisobutyronitrile (AIBN) 0. The mixture of 1500 g was reacted in cyclopentanone (11.7 g) under nitrogen atmosphere at 85 ° C. for 2 hours and then at 90 ° C. for 1 hour. After cooling, the reaction solution was added to toluene (100 ml), and the resulting precipitate was filtered. After washing the precipitate with toluene (50 ml), the polymer was dried under vacuum to obtain about 4.3 g of polymer (1-1). Mw of the obtained polymer (1-1) was 32000, and Mw / Mn was 2.7. Moreover, the copolymerization ratio was 1M-1 = 0.72 and 2-hydroxyethyl methacrylate = 0.28 in molar fraction.

上記表中、カッコ内は全モノマーに対する該当モノマーの重量％を示す。 In the same manner as described above, as shown in Table 1, the following polymers for photoalignment film were produced.

In the above table, the parentheses indicate the weight% of the corresponding monomer with respect to all the monomers.

Example 13 Production of Polymer (1-10) for Photo-alignable Retardation Material Polymer (1-10) was polymerized from compound (1M-1) and compound (2M-1) according to the following procedure. A solution of 3.0000 g of compound (1M-1), 7.0000 g of compound (2M-1), and 0.3800 g of AIBN in THF (40 ml) was stirred under heating under reflux for 10 hours under a nitrogen atmosphere. The solution after reaction was poured into toluene to reprecipitate. The crystals were filtered and dried to obtain 7.3 g of polymer (1-10). The copolymerization ratio was 1M-1 = 0.21 and 2M-1 = 0. 79 in molar fraction. The obtained polymer (1-10) had an Mw of 18,000, an Mw / Mn of 2.8, and a liquid crystal phase in the range of 71 ° C to 145 ° C.

In the same manner as described above, as shown in Table 2, the following polymers for photoalignable retardation materials were produced.

Example 17 Preparation of Photoalignment Film and Retardation Film in which Polymerizable Liquid Crystal is Laminated (First Step: Preparation of Photoalignment Film)
The polymer (1-1) was dissolved in cyclopentanone to form a solution with a solid concentration of 3% by weight. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a photo-alignment agent (AM-1). The AM-1 was applied by spin coating on a glass substrate (rotational speed: 1200 rpm). At this time, the coatability was good. The substrate was heated at 80 ° C. for 2 minutes to remove the solvent to form a coating. Next, using a super high pressure mercury lamp as a light source, a filter for cutting a wavelength of 320 nm or less was passed, and this coated film was irradiated with linearly polarized light from the vertical direction with respect to the coated surface (exposure amount 200 mJ / cm ² , 365 nm). Thus, an alignment film (AF-1) subjected to the photoalignment treatment was obtained. As a result of measuring the film thickness of AF-1, it was about 120 nm.
(Second stage: lamination of retardation film)
The polymerizable liquid crystal composition (A-1) described in the example of JP-A-2015-127793 was prepared (solid content concentration was 17 wt%). This A-1 was apply | coated to the glass substrate in which said AF-1 was formed into a film by spin coating (rotation speed 1000rpm). The substrate was heated at 80 ° C. for 3 minutes, cooled at room temperature for 3 minutes and then exposed in air (exposure dose: 500 mJ at 365 nm) to obtain a cured liquid crystal film (retardation film). Observation of this retardation film revealed no orientation defect, and the contrast was 5600.

Example 18 Preparation of Photoalignment Film and Retardation Film in which Polymerizable Liquid Crystal is Laminated 2
A photoalignment film (AF-1-1) was obtained in the same manner as in Example 13, except that the photoalignment treatment was performed without using a cut filter and the exposure dose was 100 mJ / cm ² (365 nm). Furthermore, a polymerizable liquid crystal composition (A-1) was formed into a film on AF-1-1 in the same manner as in Example 17. When this retardation film was observed, no orientation defect was observed, and the contrast was 5,000.

Example 19 Photoalignment Process Using LED Light Source A photoalignment film (AF-1-2) was obtained in the same manner as in Example 17 except that an LED light source was used as a light source for the photoalignment process. Furthermore, a polymerizable liquid crystal composition (A-1) was formed into a film on AF-1-2 in the same manner as in Example 17. Observation of this retardation film revealed no orientation defect, and the contrast was 5800.

Photoalignment films AF-2 to AF-9 were formed in the same manner as in Example 17 using the polymers of the examples. Furthermore, A-1 was formed into a film on these photo-alignment films, and retardation film was obtained. The visual observation and the contrast measurement results are shown in Table 3 below.

[Example 24] Preparation of a polymer-blended photoalignment film and a retardation film in which a polymerizable liquid crystal is laminated thereon (the first step: polymerization of non-photoalignment polymer)
A non-photo-alignable polymer solution was obtained by the same method as described in Polymer Preparation Example 5 of JP-A-2013-177561. The non-photo-alignable polymer solution was subjected to re-precipitation in the same manner as in Example 4 except that heptane was used as a solvent for re-precipitation to obtain a non-photo-alignable polymer (NP-1). Mw of this NP-1 was 58000, and Mw / Mn was 2.3.

(Step 2: Preparation of polymer-blended photoalignment agent)
A mixture of 0.3000 g of the polymer (1-4) obtained in Example 7 and 0.7000 g of the non-photo-alignable polymer (NP-1) was dissolved in cyclopentanone (32 ml) to give a solid concentration of about 3% by weight Solution was obtained. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a photoalignment agent (BAM-4).

(Third step: Preparation of photo alignment film and retardation film)
A photoalignment film (BAF-4) was produced in the same manner as in Example 17. As a result of measuring the film thickness of BAF-4, it was about 100 nm. A retardation film was formed on this BAF-6 in the same manner as in Example 17 using the polymerizable liquid crystal composition (A-1). When this retardation film was observed, no orientation defect was observed, and the contrast was 6,100.

[Example 25]
A photoalignment film (BAF) prepared from a polymer alignment photoalignment agent in the same manner as in Example 24 except that the polymer (1-4) is used and the polymer (1-5) obtained in Example 8 is used. -5) was obtained. As a result of measuring the film thickness of BAF-5, it was about 100 nm. A retardation film was formed on this BAF-5 in the same manner as in Example 19 using the polymerizable liquid crystal composition (A-1). Observation of this retardation film revealed no orientation defect, and the contrast was 4800.

Example 26 Preparation of Retardation Film Using Photo-Alignment Retardation Material The polymer (1-10) obtained in Example 13 was dissolved in cyclopentanone to prepare a solution having a solid content concentration of 20% by weight. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a photoalignable phase difference agent (AM-10). The AM-10 was applied onto a glass substrate by spin coating (rotational speed 1500 rpm). At this time, the coatability was good. The substrate was heated at 80 ° C. for 2 minutes to remove the solvent to form a coating. Next, using a super high pressure mercury lamp as a light source, a filter for cutting a wavelength of 320 nm or less was passed, and this coated film was irradiated with linearly polarized light from a perpendicular direction to the coated surface (exposure amount 400 mJ / cm ² , 365 nm). The substrate was heated at 135 ° C. for 5 minutes to obtain a retardation film (AF-10). As a result of measuring the film thickness of AF-10, it was about 2.0 μm. When the retardation film (AF-10) was sandwiched between two crossed polarizers and rotated in a horizontal plane, it became bright and dark, and was confirmed to be in a horizontal orientation (homogeneous orientation). As a result of visual observation, there were no orientation defects. The retardation of the retardation film was 128 nm.

[Example 27] Preparation of retardation film using photoalignable retardation material 2
Retardation film (AF-11) was obtained in the same manner as in Example 21 except that the polymer (1-11) obtained in Example 14 was used and the annealing temperature was 130 ° C. As a result of measuring the film thickness of AF-11, it was about 2.0 μm. When the retardation film (AF-11) was sandwiched between two crossed polarizers and rotated in a horizontal plane, it became bright and dark, and was confirmed to be in a horizontal orientation (homogeneous orientation). As a result of visual observation, there were no orientation defects. The retardation of the retardation film was 119 nm.

このポリマーを用い、実施例１７と同様な方法に従い、位相差フィルムを作成した。この位相差フィルムを観察したところ配向欠陥は見られなかったが光抜けが多く、コントラストは３０００であった。 Comparative Example 1
The polymer which consists of a structural unit of following formula (10) of Unexamined-Japanese-Patent No. 2014-501813 was superposed | polymerized. This polymer had Mw of 35,000 and Mw / Mn of 2.8.

Using this polymer, a retardation film was produced in the same manner as in Example 17. As a result of observation of this retardation film, no orientation defect was observed but light leakage was frequent, and the contrast was 3,000.

  According to the comparison of Examples 17 and 20 to 23 and Comparative Example 1, when a photoalignment polymer having a constitutional unit represented by the formula (1) of the present invention is used, a photoalignment film which is sensitive to UV at a long wavelength can be obtained. I know that I can get it.

  The photoalignable polymer of the present invention has high sensitivity to long wavelength ultraviolet light represented by 365 nm. Therefore, by using the present material, it is possible to form a photoalignment film using a widely used i-line exposure apparatus or an exposure apparatus using a recently commercialized LED lamp. Furthermore, since the photoalignable polymer of the present invention has high sensitivity, it is possible to produce a photoalignment film with a high yield.

Claims (15)

Photoalignment polymer which has a structural unit represented by Formula (1).

In formula (1), R ¹ is independently hydrogen or methyl;
Sp is methylene or alkylene having 2 to 20 carbon atoms, and at least one -CH _2- in this alkylene is replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C- May be
A is independently any divalent group selected from benzimidazole, benzoxazole, benzothiazole, indole, or carbazole, and in the divalent group, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
W ¹ and W ² are independently hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
X ¹ is a single bond, -O-, or -NH-;
R ² is a hydrogen atom, methyl, alkyl having 2 to 20 carbon atoms, or the above-mentioned group A, and at least one —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH = It may be replaced by CH- or -C≡C-. Wherein (1), Sp is - _{(CH 2)} n is O-, n is located at integer from 1 to 10; ^{W 1} and ^{W 2} are hydrogen; ^{X 1} is -O-; ^{R 2} The photoalignable polymer according to claim 1, wherein is an alkyl having 1 to 10 carbon atoms. In the formula (1), Sp is-(CH ₂ ) _n O- and n is an integer of 1 to 10; W ¹ and W ² are hydrogen; X ¹ is a single bond; R ² is The photoalignable polymer according to claim 1, which is any divalent group selected from indole and carbazole.   The photoalignable polymer according to any one of claims 1 to 3, which has a structural unit formed from a monomer having a hydrogen bonding group in addition to the structural unit represented by the formula (1).   The photoalignable polymer according to claim 4, wherein the hydrogen bonding group is a carboxyl group. The photoalignable polymer according to claim 5, wherein the constituent unit formed from the monomer having a hydrogen bondable group at the end is a constituent unit represented by the formula (2).

In formula (2), R ³ is hydrogen or methyl; Q is a single bond or an alkylene having 1 to 20 carbon atoms, and at least one -CH _2- in this alkylene is -O-, -COO-,- OCO-, -CH = CH- or -C≡C- may be replaced; X ² is a single bond, -O-, -COO-, -OCO-, -OCOO-, -CH = CH- or- C≡C-; A ² is any divalent independently selected from 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl or naphthalene-2,6-diyl Group, in the divalent group, any hydrogen is fluorine, chlorine, cyano, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms or carbon. May be replaced by the number 1-5 alkoxy; ^{Z 2} independently represents a single bond, -O -, - COO -, - OCO -, - CH = CH-COO -, - CH 2 CH 2 -COO- _{, -CH 2 O -, - OCH} 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CH = CH -Or -C≡C-; c is an integer of 0 to 2; Y ¹ is a single bond, -CH ₂ CH ₂ -or -CH = CH-. In the formula (2), Q is an alkylene having 1 to 12 carbon atoms, and at least one -CH _2- in this alkylene may be replaced by -O-, -COO- or -OCO-; and X ² is -O-, -COO- or -OCO-; and A ² is any divalent group independently selected from 1,4-phenylene or naphthalene- ^{2, 6} -diyl, in the divalent group And any hydrogen may be replaced by fluorine, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons; Z ² is independently a single bond, -COO-, -CH = CH-COO-, _{-CH 2 CH 2 -COO -, -} CH 2 O -, - CONH- or _-CH 2 CH ₂ - and are; ^{Y 1} is a single bond, photoalignment polymer of claim 6.   The photoalignable polymer according to any one of claims 1 to 7, which has liquid crystallinity.   The photoalignable polymer according to any one of claims 1 to 8, which has a weight average molecular weight of 1,000 to 500,000.   An ink comprising at least one photoalignment polymer according to any one of claims 1 to 9 and a solvent.   11. The ink of claim 10, further comprising a non-photo-orientable polymer.   It is a film created using the ink of Claim 10 or 11, The retardation film of this film is 5 nm or less.   It is a film created using the ink of Claim 10 or Claim 11, The retardation film of this film is 5 nm or more.   The display element manufactured using the film of Claim 12 or Claim 13. The photosensitive compound represented by Formula (1M).

In formula (1M), R ¹ is independently hydrogen or methyl;
Sp is methylene or alkylene having 2 to 20 carbon atoms, and at least one -CH _2- in this alkylene is replaced by -O-, -COO-, -OCO-, -CH = CH- or -C≡C- May be
A is independently any divalent group selected from benzimidazole, benzoxazole, benzothiazole, indole, or carbazole, and in the divalent group, at least one hydrogen is fluorine, chlorine, cyano, hydroxy, Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
W ¹ and W ² are independently hydrogen, fluorine, trifluoromethyl, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
X ¹ is a single bond, -O-, or -NH-;
R ² is a hydrogen atom, methyl, alkyl having 2 to 20 carbon atoms, or the above-mentioned group A, and at least one —CH ₂ — in the alkyl is —O—, —COO—, —OCO—, —CH = It may be replaced by CH- or -C≡C-.