TW201235451A - Polymerizable compound, polymerizable liquid crystal composition, polymer and alignment film - Google Patents

Abstract

To provide: a polymerizable compound represented by formula (1) or formula (2); a polymerizable liquid crystal composition which contains the polymerizable compound; a polymer, a coating film and an alignment film, each of which is obtained from the polymerizable liquid crystal composition; and an optical member which is provided with the alignment film. (In the formulae, n1 and n2 each independently represents an integer of 3-10, and m represents an integer of 3-10.)

Description

201235451 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a polymerizable compound having a benzophenone moiety, a polymerizable liquid crystal composition containing the same, and a polymer and alignment obtained by using the polymerizable liquid crystal composition. film. More specifically, it is a polymerizable compound containing a polymerizable compound which is used as a material for optical characteristics such as a display device and a recording material, in particular, a polarizing plate for a liquid crystal display device and a phase difference plate. A composition and a polymer obtained from the polymerizable liquid crystal composition and an alignment film. [Prior Art] When a liquid crystal display device is required to improve the display quality and light weight, it is required to improve the optical compensation film such as a polarizing plate and a phase difference plate, and to control a polymer film having an internal molecular alignment structure. Developed as required, a film having optical anisotropy of a polymerizable liquid crystal compound is used. The polymerizable liquid crystal compound to be used in this case is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (having a structure portion of a spacer portion and a crystal source portion). The polymer group is widely used as an acrylic group. Such a polymerizable liquid crystal compound is generally formed by polymerizing a film by irradiation with ultraviolet rays or the like to form a polymer (film). For example, a method in which a specific polymerizable liquid crystal compound having an acrylic group is carried between a known support, and a polymer is obtained by irradiating radiation in a liquid crystal state (Patent Document 1), JP-A-62-7 0407 And a method of irradiating ultraviolet rays to obtain a polymer by adding a photopolymerization initiator to a mixture of two polymerizable-5-201235451 liquid crystal compounds having an acrylic group or a mixture obtained by mixing the mixture with a chiral liquid crystal (Patent Document 2: Japanese Unexamined Patent Application Publication No. Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. 9-2008 The polymer (film) obtained by the above-mentioned methods is mounted on a display device such as a monitor or a television, and a display device used in a high-temperature environment, such as a monitor or a television, in the form of a film for a polarizing plate or a phase difference plate. Therefore, in the high-temperature environment, it is possible to maintain transparency with respect to materials for display devices. In recent years, in the field of display devices, the steps for actively reviewing such materials as In Cell retardation films have been simplified. The materials used in the In Cell technology are required to have higher thermal stability. When the optically anisotropic film obtained by another step (e.g., extension of a polyvinyl alcohol-based film) is compared, the wavelength dependence of the optical anisotropy of the film obtained from the polymerizable liquid crystal compound is low. In addition, an anisotropic polymer obtained from a monomer having a benzophenone skeleton is known (Patent Document 3: German Patent Application Laid-Open No. 4206994). PRIOR ART DOCUMENT Patent Document Patent Document 1: JP-A-62- Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In view of the above, the object of the present invention is to provide a specific polymerization property of a site having a ketone-γ-butyrolactone moiety and a benzophenone to impart a high optical anisotropy and a high resistance compound (film). The polymerizable product containing the above polymerizable compound, and the polymer obtained from the polymerizable liquid crystal composition, and a method for solving the problem, in order to solve the above problems, the inventors of the present invention have intensively reviewed the α-methyl-γ-butyl group. The specific polymer of the ester moiety and the benzophenone moiety can impart a stable polymerizable liquid crystal having excellent polymerizability, and the polymer and film obtained from the polymerizable liquid crystal composition are more The optical anisotropy and chemical resistance of the present invention have been completed, and the present invention has been provided, that is, the present invention provides a polymerizable compound which is characterized by the following formula [is represented by an α-extension compound, which can be characterized. The polycrystalline liquid crystals constitute a film. Now, having a combined composition, may have or [2] [Chemical 1]

(wherein, nl & n2 each independently represent an integer of 3 to 1 ,, [1] [2] m represents an integer of 3 201235451 to ι〇), 2 · a polymerizable liquid crystal composition characterized by containing At least a liquid crystal compound selected from the polymerizable compounds represented by 1] and [2] [Chemical 2]

(in the formula, nl and n2 each independently represent an integer of from 3 to 10, an integer of from m to 10). The polymerizable liquid crystal composition according to the above item 2, wherein the above liquid compound is a liquid crystalline compound having a polymerizable group. 4. The polymerizable liquid crystal composition according to the above item 3, wherein the liquid crystal compound having the above-mentioned group is a compound having the following formula [3] and/or [polymerizable group represented by the formula [Chemical 3]". (7) The formula [1 species, [1] [2] indicates that 3 crystallized and polymerized 4]

[4] 201235451 (wherein the dotted line is a bonding bond), the polymerizable liquid crystal composition according to the above item 3 or 4, wherein the liquid crystalline compound having a polymerizable group is represented by the following formula [5] and [ 6] at least one compound selected from the group of compounds represented by the compound [Chemical 4] MH〇H2)n-〇

[5] Μ2-(0Η2)η-〇

0—(CH2)〇—Μ3 [6] (wherein, Μ1, M2, and M3 are each independently of the following formula [3] or [4 [5]

[4] (wherein, the dotted line is a bond) a group represented by a radical; X is a fluorine atom, a cyano group or a monovalent hydrocarbon group having a carbon number of 4 to 8; Π and f2 each independently represent an integer of 2 to 9, and g represents 2 An integer of 9), a polymer obtained from the polymerizable liquid crystal composition of any one of the above items 2 to 5, -9-201235451 7. A film of the above-mentioned item 2 to 5 Any one of the liquid crystal compositions, which is obtained from any of the compliant liquid crystal compositions of the above items 2 to 5, and an optical member which is an alignment film of the polymer of the above item 6. Advantageous Effects of Invention The polymerizable liquid crystal group containing the polymerizable compound of the present invention has a high optical anisotropy and chemical resistance, and a polymerizable liquid crystal composition having the polymerizable compound of the present invention is polymerized, and does not appear. The alignment of the chaos, and the atomization is low. Further, by adding the polymerizable compound of the present invention, the polymerizability of the liquid crystal composition is determined by the addition of the liquid crystal composition of the polymerizable compound of the present invention, and no disorder is observed. Therefore, the polymer obtained from the polymerizable liquid crystal composition containing the compound of the present invention is suitably used as an optically anisotropic film such as a polarizing plate, and is particularly suitable for forming a pattern by a lithography method. Mode for Carrying Out the Invention The present invention will be described in more detail below. In the present specification, the term "polymerizable liquid crystal compound" means a compound having a polymerizable group 'crystalline phase such as an acryl group or an α-methyl lactone ring. The "liquid crystal composition" means a polymer having a polymerizability which is present or a component of the former term. From the film obtained, it is lifted by adding. Further, in the film-polymerized light-receiving plate or the phase gas, a composition of the liquid crystal phase of the liquid crystal phase is present. "Liquid crystallinity" means a liquid crystal phase. [Polymerizable compound] The polymerizable compound of the present invention is represented by the following formula [1] or [2] 〇 [Chemical Formula 6]

(wherein nl and n2 each independently represent an integer from 3 to 10 indicating an integer from 3 to 10). The polymerizable compound represented by the formula [1] or [2] is a compound having a ketone moiety and an α-methyl-γ-butyrolactone moiety. Α-methyl-γ-butyrolactone is such that it has a polymerizable group; alkyl-γ-butyrolactone can also reduce the influence of steric hindrance, and it is highly polymerizable. Excellent results. Therefore, the glass transition temperature (Tg) and heat resistance can be effectively imparted to the benzoic site of the photopolymerization of the polymerizable compound represented by the formula [1] or [2] obtained by using the compound, by light. A polymer which can be subjected to a dimerization reaction. Therefore, by using the polymerizable compound of the present invention, it is represented by [1] [2J, m has diphenyl L (X-sub-highly expandable glass polymer ketone moiety can be crosslinked to enhance -11 - 201235451 material) Sensitivity. In the formula [1] or [2], the overlapping portion of the methyl group is a so-called spacer portion, wherein nl, n2 and m represent the number of repeating methyl groups, each independently 3 to 10 The integer is preferably an integer of 4 to 6. The polymerizable compound is, for example, a compound represented by the following formulas (1) to (29), but is not limited thereto. -12- (1) 201235451 [ 7]

(2) (3) (4) (5) (6) (7) (8) -13- 201235451 [Chem. 8]

CH,)-ο

(9) ο 〇-(CHj).v

(10) (11) (12)

〇-(CH2)10 (13) (14) (15) ο,

CH2)10-〇

(16) -14- 201235451 [Chem. 9]

(17) (18) (19) (20) (21) (22) (23) -15- 201235451 [Chem. 10] Ο.

CH2)5-〇

0—(ch2)4

〇-(ch2)6

〇

CH2)5-〇

[Synthesis of Polymerizable Compound] The polymerizable compound of the present invention can be synthesized by a combination of organic methods, and the synthesis method is not particularly limited. A method having a structure of α-extended methyl-γ-butyrolactone such as Talaga et al. (P. Talaga, M. Schaeffer, C. B enezr a Stampf, Synthesis, 530 (1990)) is as follows. As the synthesis scheme (Al), a method of reacting 2-(bromomethyl)propionic acid (2-bromomethyl) prope with an aldehyde or a ketone is used. Further, 2-(bromomethyl)propane Ramarajan et al. (K. Ramari amalingam, DJ OOonnell and KD Berlin ) (25) ) (26) ) (27) ) (28) ) (29) Cheng chemistry Can be synthesized by, and J. L. The SnCl2 makes η o i c acid enoic acid ij an, K. K , Organic -16- 201235451

Synthesis, vol. 61, pp. 56-69 ( 1983) ) ° [Chem. 11]

SiiCl>/Ainberlvst 15 THF/Hi〇

R (Al) COOEt Formaldehyde solution HO^ COOEt COOEt NaHC03, H. / COOEt

COOH

R-CHO (wherein R represents a monovalent organic group. THF represents tetrahydrofuran. Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Lomman Corporation) 0 and can also use 2-(bromomethyl) of SnCl2 In the reaction of acrylic acid, an α-methyl-γ-butyrolactone structure is obtained by reacting a substituted aldehyde or a ketone with an acetal or a ketal. The acetal or ketal has a compound such as a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxyl group or a 1,3-dioxoalkane. The synthesis method using an acetal or a ketal is as shown in the following scheme (Α2).

COOH R-PG +

(A2)

SaCWAnibeilyst 15 THF/H2Q_

(wherein R is the same as above. The broken line is a bonding key). -17- 201235451 An intermediate of the compound represented by the formula [1] or [2] can be synthesized by the method of the following synthesis scheme (B) by the method of the above-mentioned synthesis scheme (A1) or (A2). HO-H〇-(CH2)u+l-Br /==\ C〇〇CH^ '-'TOAcetone " H〇-(CH2U-OH^jKOOOCH^ H〇-(CH2X1+1- 〇COOCHi PCC CH2Ch 0HC-(CH2)Il+1-0 ^-cooch3 (B)

(CH2)n-〇 ~Qt c〇〇ch3 /—Br OHC-(CH2^1-〇 \j~ COOOi3

COOH

SaQi/Amberlyst 15 thf/h2o

l) NaOH (aq) EtOH

2) Ainbeilyst 15 THF

(CH2)n-0

COOH (wherein n is the same as above. PCC represents pyridyl chlorochromate). The polymerizable compound represented by the formula [1] can be synthesized by the following synthesis scheme (C). [Chem. 14]

-18- 201235451 (wherein η is the same as above. DCC represents dicyclohexylcarbodiimide, and DMAP represents N,N-dimethyl-4-aminopyridine). When n = m in the formula [2], the compound represented by the formula [2] can be synthesized by the following synthesis scheme (D).

2 °) y ^ DCC / DMAP CH2C12 ^ (where η is the same as above). In the case of n#m in the formula [2], the compound represented by the formula [2] can be synthesized by the following synthesis scheme (E). [Chemistry 16]

(wherein η and m are the same as described above). -19-201235451 [Polymerizable liquid crystal composition] The polymerizable liquid crystal composition of the present invention is obtained by mixing at least the selected one selected from the polymerizable compounds represented by the above formulas [1] and [2]. A compound of a liquid crystal structure (hereinafter referred to as a specific compound) is obtained. The specific compound to be mixed may be used singly or in combination of plural kinds. The above specific compound is required to be a liquid crystal compound (liquid crystal compound). The above specific compound may be a polymerizable group having an acryl or propyl ester ring or the like, or may not. When the polymerizable group is present, the above specific compound may be monofunctional or polyfunctional. The above specific compound may have a polymerizable group such as a group represented by the following formula [3] or [4]. [Chem. 17]

(In the formula, the dotted line indicates the bonding key). The specific compound having the above polymerizable group is particularly preferably a compound represented by the following formula [5] or [6]. -20- 201235451 [Chem. 18]

(wherein, Μ1, Μ2 and Μ3 are each independently a group represented by the above formula [3] or [4]. X is a fluorine atom, a cyano group or a monovalent hydrocarbon group having 4 to 8 carbon atoms. fl and f2 each independently represent 2 An integer of up to 9, g represents an integer from 2 to 9. The addition ratio of the specific compound is not particularly limited, but is preferably 900 to 200 parts by mass, more preferably 400 to 200 parts by mass, per 100 parts by mass of the polymerizable compound represented by the above formula [1] and/or [2]. . Specific examples of the specific compound include, for example, a compound represented by the following formulas (30) to (120), a nematic liquid crystal, a ferroelectric liquid crystal, a commercially available liquid crystal composition, and the like, but are not limited thereto. -21 - 201235451 [Chem. 19]

(30) (31) (32) (33) (34) (35) (36) (37) -22- (38) 201235451 [Chem. 20]

(39) (40) (41) (42) 23- (43)201235451 [Chem. 21]

Ο (44) Ο,

(cn^o Η〇-^ο*ΟΌ·〇Μβ (45)

(ch^-o :(3⁄4)疒 〇

Ο m (47) 〇;

(CH山一〇 ο (48) α

((:η2.)4-〇 〇, Χ>:r>

(CH2) 4-〇 〇 ‘

ο, ;ch>)4-〇 (CH山一〇 (CH Shanyi 〇(ΟΗ2)4-〇(CH2)4-〇

O'iCH^-O· .〇—(CHA-O_O-iCHA-o. .-^ch2w O-^CH^-O' 0~td (49) ο (50)

0 (51) (52) (53) (54) -24- (55) (56)201235451 [Chem. 22]

(CHyJ.-O Ο,

(CH2)5-〇

CN (57) Hey,

(CH) 5-〇 (58) °x>.

(CH2).,-〇

(CH,) 5-〇 0,

(CHj) Hirose

Q

(CH>),-〇

((3⁄4) Factory 〇 〇,

(CH2).,-〇 〇.

(CH山一(] (03⁄4)-0 (CHZ) Guang 〇

(59) (60) (61) (62) (63) (64) (65) (66) (67) -25- (63) (69) 201235451 [Chem. 23]

(ch^6-〇 °x>' a

(CH on) (CH2)e-〇

OMa (70) (71) (72)

(CHi)6

〇-(CH2)2-〇- (73) o (74)

iCHz) 6-0 0.

(CHx)6-〇 :x>

(CHJg-O

〇

(CH2)6-〇

(CHi)fi-O

--. CHA-cT 0 , Λ^ ο (75) (76) (77) (7S) (79) (SO)

ο -26 - (81) (82)201235451 [Chem. 24]

(CH2) 7-0

(CH2)7-〇

Ο—(ch山一σ ο

〇-(CH2)8-a ο,

(CHp7-0 ο.

(CH2)7-〇

(ΟΗ^,-Ο

Ο—(CH^p-O" o-CCH^io-r/ ο (83) (84) (85) (10) (87) (88) (89) (90)(91) (92) (93) ( 94) -27 - 201235451 [Chem. 25]

(CHJg-O : 〇Ηλ) 8-ΰ

°xy^-〇^H<><y〇x^

(CH^s-O- o

(CH^s-O

Q

(CH2)3-〇 :ch2)8-o ;ch2)8-o [CH^g-O CCH2)3-〇 (CH2)8-〇

0-(03⁄4)^ O-iCH^- O-CCH^-O O-iCH,.),- 〇-tCHz)6-〇^ O-^CHJ 广〇_ O-tCH^g-O" o

0 0 (95)(96) m(98)(99) (100) (101) (102) (103) (104) (105) (106) (107) -28- (108)201235451 [Chem. 26]

(CH2)9-〇

Call) 9 call (CH,) 9-0

DMe

(CH^-0

(03⁄43⁄4-Ο

〇—(CH2.)2-

(CHi) 9-0

(13⁄43⁄4-o

(CH^o-0 0,

(CH2)9-〇

(CH^)9~〇

(CHp9-0

((73⁄43⁄4 - O

(CHA - O

o-iCH^-o- 0—(CH2.\,-(T 〇-(〇ήζ)6-〇·- ο—(ΟΗ^,-σ 〇-(CH,)s-〇- o-^chut 0-(03⁄4) 10-〇" o (]09)(Π0)(Π1) (112) (113) (114) (Π5) (116) (117) (1)8) 〇19) (120) -29- 201235451 In the polymerizable liquid crystal composition of the present invention, a photopolymerization initiator, a thermal polymerization initiator, a sensitizer, etc. may be added in order to enhance the polymerization reactivity. Photopolymerization initiators such as benzoin A a benzyl ketal such as a benzoin ether such as a hydroxy ether or a benzyl ketal such as a benzyl dimethyl ketal such as diethoxy acetophenone or the like. The photopolymerization initiator may be used alone or in combination. The amount of the photopolymerization initiator to be added in combination with the total amount of the polymerizable compound represented by the formula [1] and/or [2] and the specific compound having a polymerizable group is preferably 100 parts by mass, preferably 5 parts by mass or less, more preferably 〇. 5 to 2.0 parts by mass. A thermal polymerization initiator such as 2,2'-azobisisobutyronitrile, etc. The thermal polymerization initiator may be used alone or in combination of plural kinds. The amount added is relative to the polymerizable compound represented by the formula [1] and/or [2] and the polymerizable group. The total amount of the compound is 100 parts by mass, preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass. Further, the above photopolymerization initiator may be used in combination with at least one of the thermal polymerization initiators. In the polymerizable liquid crystal composition, a stabilizer may be added in order to improve the storage stability. A stabilizer such as hydroquinone monoalkyl ether such as hydroquinone or hydroquinone monomethyl ether, 4-t-butyl tea A phenol or the like. The stabilizer may be used singly or in combination of plural kinds, and the amount thereof is added to the total amount of the polymerizable compound represented by the formula [1] and/or [2] and the specific compound having a polymerizable group. In the polymerizable liquid crystal composition of the present invention, an adhesion promoter may be added to improve the adhesion to the substrate. The adhesion promoter may be, for example, two. a chlorodecane such as methyl chlorodecane, dimethylvinyl chlorodecane, methyl diphenyl chlorodecane or chloromethyl dimethyl chloro decane; trimethyl methoxy decane, dimethyl diethoxy矽, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, two An alkoxy decane such as phenyl dimethoxy decane or phenyl triethoxy decane; hexamethyldioxane, hydrazine, Ν'-bis(trimethyl decyl) urea, dimethyl three a decyl alkane such as methyl decylamine or trimethyl decyl imidazole, vinyl trichloro decane, γ-chloropropyl trimethoxy decane, γ-aminopropyl triethoxy decane, γ- a decane such as methacryloxypropyltrimethoxypropane, γ-glycidoxypropyltrimethoxydecane or γ-(indolyl-piperidinyl)propyltrimethoxydecane; Oxazole, benzimidazole, oxazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, urazole, thiouracil, mercapto imidazole, mercaptopyrimidine, etc. a heterocyclic compound; a urea compound such as 1,1-dimethylurea or 1,3-diurea; a sulfur urea compound; The adhesion promoter may be used singly or in combination of two or more kinds, in an amount of 100 parts by mass relative to the total of the polymerizable compound represented by the formula [1] and/or [2] and the specific compound having a polymerizable group. It is preferably 1 part by mass or less. Further, in the polymerizable liquid crystal composition of the present invention, an organic solvent may be added in order to adjust the viscosity or the like. In the state containing an organic solvent at this time, liquid crystallinity may not be obtained. Organic solvents such as ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene-31 - 201235451, xylene, etc.; N,N-dimethylformamide, N-methyl-2-pyrrolidone Polar solvents such as ethyl acetate, butyl acetate, ethyl lactate, etc.: methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl methoxypropionate , alkoxy esters such as ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate; ethylene glycol dimethyl ether, propylene glycol dimethyl ether Ethylene glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, etc. Alcohol dialkyl ethers; ethylene glycol monomethyl ethers, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ethylene glycol monoalkyl ethers; Diethylene glycol monoalkyl ethers such as methyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc.: propylene glycol monomethyl ether acetate, carbitol Acetate, ethyl cellosolve Ester, etc. glycol monoalkyl ether esters: cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, etc., etc. ketones. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate are preferred from the viewpoints of stability in the global environment and working environment. These organic solvents may be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably 60 to 95% by mass in the polymerizable liquid crystal composition. Further, in the polymerizable liquid crystal composition of the present invention, a surfactant may be added in order to improve the affinity with the substrate. The surfactant is not particularly limited, and may be a fluorine-based surfactant, a polyoxyxide-based surfactant, a nonionic surfactant, or the like, and is preferably a fluorine-based surfactant having a high affinity improving effect on a substrate. -32- 201235451 Specific examples of fluorine-based surfactants (hereinafter referred to as trade names) such as EF301, EF303, EF3 52 (made by Tekken Co., Ltd.), F171, F173, R-30 (Daily Ink Chemical Industry ( FC430' FC4 31 3M(J^) Μ ), Isaiah, Safran S-382, SC 1 0 1 'SC 1 02 ' SC103, SC 1 04, SC 106 (Asahi Glass Co., Ltd.) And the like, but not limited to, the surfactants may be used singly or in combination of plural kinds. A preferred example of the polymerizable liquid crystal composition of the present invention is, for example, at least one of the polymerizable compounds represented by the formulas [1] and [2], and 400 to 200 parts by mass of the specific compound and part. The liquid crystal composition or the like formed by the following photoinitiator. The polymerizable liquid crystal composition described above is suitably used as a composition for forming an alignment and a coating liquid. The preparation method of the polymerizable liquid crystal composition of the present invention is not particularly suitable for mixing the components constituting the polymerizable liquid crystal composition. The order of addition of the components in the sequential mixing may be arbitrary. Further, when a plurality of compounds are used in one component, the resulting mixture may be premixed with other components, or may be separately mixed therewith. The polymerizable liquid crystal composition of the present invention is preferably produced at room temperature (the same as 20 to 20) in order to avoid the uniform alignment state of the undesired heat-immobilizable molecules in order to avoid photopolymerization in a liquid crystal state. The liquid crystal phase of stability. Further, when the polymerizable liquid crystal contains an organic solvent, it is preferred to exhibit an ampoule at room temperature when removing the solvent, and a germination of AG7 1 0 and SC105. In addition, the quality of the film is limited to 100 masses, and it is polymerized in the order of mixing the components. . , Composition of the liquid -33- 201235451 Crystal phase. [Polymer and film] The polymer is obtained by light irradiation or heat treatment with respect to the above polymerizable liquid crystal composition. Further, in a state where the polymerizable liquid crystal composition is held between the two substrates, or when the polymerizable liquid crystal composition is applied to the substrate by spin coating or casting, the film is subjected to light irradiation treatment to obtain a film. As the substrate, a plastic film such as glass, quartz, a plastic sheet, a filter, or a triacetyl cellulose (TAC) can be used. Further, among the two substrates, a glass, a plastic sheet, a plastic film, and a metal strip or a cylinder for plating or vapor-depositing stainless steel, chromium, aluminum, or the like can be used as the substrate. In the substrate to be used, in order to enhance the alignment of the obtained film, it is preferred to carry out the alignment treatment. The method of the alignment treatment may be carried out by applying an alignment material containing a polyimide precursor, a polyimide, a polyvinyl cinnamate or the like, performing a treatment by arranging or irradiating a polarized ultraviolet ray, and forming a cerium oxide. A known method such as a method of evaporating a vapor deposition film, a method of forming an LB film, or the like is appropriately selected and used. In the method of holding a polymerizable liquid crystal composition between two substrates, a void formation unit is formed between two substrates by a space or the like, and then polymerization is performed by a capillary phenomenon or a method of decompressing a void of the cell. The liquid crystal composition is injected into the unit, and the light is further irradiated for polymerization. Further, a more convenient method is to deposit a polymerization liquid crystal composition on a substrate having a gap, and then superimpose another substrate forming unit on the substrate to re-illuminate the light to carry out polymerization. In this case, the polymerizable liquid crystal composition may be fluidized, or placed on a substrate, and then heated or the like to be fluidized. However, the polymerizable liquid crystal composition needs to be fluidized before the other substrate is superposed. In the method of applying the polymerizable liquid crystal composition, in addition to the step of applying the polymerizable liquid crystal composition, in the step of performing polymerization by light or heat, a step of heating with a hot plate or the like may be added as necessary. In particular, when a polymerizable liquid crystal composition (coating liquid) containing an organic solvent is used, this step is an effective method for removing the organic solvent from the composition. In any of the above methods, the polymerizable liquid crystal composition is polymerized in a state of exhibiting a liquid crystal phase, so that a film having an optical anisotropy of alignment can be obtained. In order to obtain a polymer in a multi-domain state having different alignments in the adjacent fields, a method of multi-domain formation by a polymerization step or a method of multi-domain formation of a substrate can be used. The method of multi-domain polymerization by a polymerization step is, for example, a method of forming a polymerization on a polymerizable liquid crystal composition in which a mask is exposed to ultraviolet light in a liquid crystal state, and a method of polymerizing in an isotropic liquid state. Further, a method of multi-layerizing a substrate is, for example, a method of brushing an alignment material formed on a substrate with a mask, or a method of irradiating ultraviolet rays with a mask. According to these methods, the field after the brushing and the field of irradiating ultraviolet rays are the portions of the alignment treatment, and the other is the multi-domain substrate of the untreated portion. The polymerizable liquid crystal composition formed on the multi-domain substrate is affected by the alignment material layer and is multi-domain. -35- 201235451 In addition to the above-described alignment processing method, a method using an electric field or a magnetic field can also be used. Since the film obtained from the polymerizable liquid crystal composition of the present invention has optical anisotropy, it is suitably used as a polarizing plate, a phase difference plate, or the like. [Embodiment] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Further, the measurement methods and measurement conditions of the respective physical properties in the examples are as follows.

[1] NMR The compound was dissolved in deuterated chloroform (CDC13) or deuterated dimethyl hydrazine (DMSO-d6), and 1H-NMR^ was measured using a nuclear magnetic resonance apparatus (30 〇mHz, manufactured by Gyor Corporation). 2) The liquid crystal phase was observed by the liquid crystal phase. The sample was heated on a hot stage (MATS-2002S, manufactured by Tokai Seitech Co., Ltd.), and then observed using a polarizing microscope (manufactured by Nikon Corporation). The phase transition temperature was measured using a differential scanning calorimeter (DSC3100SR) manufactured by Purka Co., at a scanning rate of 10 °C/min. [3] Atomization 値 -36- 201235451

The atomization enthalpy of the film was measured using a Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku Co., Ltd. [4] Phase difference of film 相位 The phase difference 波长 at a wavelength of 5 90 nm was measured using a phase difference 値 measuring device (RETS-100, manufactured by Otsuka Electronics Co., Ltd.). [Synthesis Example 1] Synthesis of a polymerizable liquid crystal compound (E 1 ) [1] Synthesis of an intermediate compound (A 1 ) [Chem. 27]

Br-(CH2)3-OH K>C〇3 Acetone

4-cyano-4'-hydroxybiphenyl 9.8g (50.0mmol), 3-bromo-1-propanol 7.0g (5 0 _ Ommo 1 ), potassium carbonate 1 3.8 g (100 m mo 1 ) 150 mL of acetone was placed in a 500 mL eggplant type flask equipped with a cooling tube, and the mixture was obtained, and the mixture was stirred at a temperature of 64 ° C for 48 hours to carry out a reaction. After completion of the reaction, the solvent was evaporated under reduced pressure to give a yellow solid. Thereafter, the solid and water were mixed with 1 40 mL, and then diethyl ether 100 mL was added for extraction. After three extractions, magnesium sulfate was added to the organic layer after separation, dried, filtered, and the solvent was evaporated under reduced pressure to give a yellow solid. The solid was recrystallized using a mixed solvent of hexane / ethyl acetate = 2 / 1 to give 8.7 g of a white solid. The solid was measured by NMR, and the results are shown below. From the results, it was confirmed that the white solid was the intermediate compound (A 1 ) (yield 70%). -37- 201235451

1H-NMR ( CDC13 ) δ : 2.09 ( m - 2H ) ' 3.90 ( t ' 2H ), 4.20 ( t, 2H) , 6.99 ( d, 2H) , 7.52 ( d, 2H), 7.66 (m, 4H) » [2] Synthesis of a polymerizable liquid crystal compound (E i ) [Chem. 28]

NC -〇-(ΟΉ2)3-〇Η

Et3N Aqyloyl Cliloride THF(Diy)

O a (CH2)r〇 (El)

(Al) 1 2.0 g of the intermediate compound (A 1 ) obtained above and 7.7 mL of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were dissolved in tetrahydrofuran (THF). After stirring at room temperature in 40 mL, the solution obtained by dissolving 4.6 mL of acrylonitrile chloride in 40 mL of THF was added dropwise over 15 minutes by cooling in a water bath. After the dropwise addition, the mixture was stirred for 30 minutes, and the mixture was stirred overnight while removing the water bath, and the precipitated triethylamine hydrochloride was filtered. Distilling about 3/4 of THF from the obtained filtrate, adding 50 mL of dichloromethane, and sequentially washing the organic layer with 50 mL of saturated sodium carbonate aqueous solution, 50 mL of 0.5N hydrochloric acid, and 50 mL of saturated brine, and magnesium sulfate. After drying, the solvent was distilled off to give a product. The results of measurement of the polymerizable liquid crystal compound (E1) 6 · 0 g 〇 1 H-NMR after recrystallization from ethanol are shown below.

'H-NMR ( CDC13 ) δ : 2.20 ( m, 2H ) , 4.10 ( t » 2H ), 4.40 (t, 2H) , 5.81 (d'lH) > 6.15 ( m > 1 H ), -38- 201235451 6.41 (d,lH) > 6.99 ( d > 2H ) > 7.55 ( d > 2H ) , 7.66 ( m, 4 H ). [Synthesis Example 2] Synthesis of a polymerizable liquid crystal compound (E2) [1] Synthesis of an intermediate compound (A2) [Chem. 29]

Br-(CH,V〇H K2CO3 / Acetone

0—(CH,)6-〇H (A2) 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25 -6 mmol) of 6-bromo-1-hexanol, potassium carbonate 7.0 g (50 mm ο I ), and 50 mL of acetone were placed in a 1 mL front flask equipped with a cooling tube, and the mixture was stirred at 64 ° C for 24 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to give a yellow wet solid. Thereafter, the solid and water were mixed at 7 mL, and then 50 mL of diethyl ether was added thereto for extraction. Three extractions were performed. Magnesium sulphate was added to the organic layer after liquid separation, dried, and then passed through a furnace, and the solvent was evaporated under reduced pressure to give a yellow solid. Dissolve the solid in 3 mL of ethyl acetate' by sand column chromatography (column: chopping 6 〇, Ο.·〇.2〇〇_'Merku company, eluate: hexane/acetic acid Ethyl vinegar = ι / i) refined. The solvent was distilled off from the obtained solution, and 6 g of a white solid. The solid was measured by NMR, and as a result, it was confirmed that the white solid was the intermediate compound (A2) (yield: 91%) of 1.69 (m, 06 (d, 2H) 'H-NMR ( DMSO-d6 ) § · 1 , '1 ·26 ( m , 6H ) , 2H ) 2H ) , 3.37 ( t,2H ) , 4.〇3 r 39 201235451 , 7.69 ( d,2H ) , 7.85 ( m, 4H ). [2] Synthesis of intermediate compound [B2] [Chemical 30] NC~0 PCC, CH, CK —\)~〇(CH2)6~〇h NC{ ^~(^)-0 -(CH2)5-CHO (A2) (B2) Next, 2.2 g (10.0 mmol) of pyridyl chlorochromate (PCC) and 0.0 mL of CH2C12 3 were placed in a 200 mL three-necked flask equipped with a cooling tube, and the intermediate compound obtained above was added dropwise with stirring. (A 2 ) 2.9 5 g (10.Ommol) was dissolved in CH 2 CI 2 (50.0 mL), and then stirred at 40 ° C for 5 hours. Thereafter, 90 mL of diethyl ether was added to a solution obtained by removing the oil attached to the wall of the flask, and after filtration under reduced pressure, the solvent was evaporated under reduced pressure to give a concentrated green solid. The solid was dissolved in 3 mL of ethyl acetate by silica gel column chromatography (column: 矽60' 0.063-0.200 mm' manufactured by Merco, eluent: hexane/ethyl acetate = 丨/1) refined. The solvent of the obtained solution was evaporated to give 2.8 g of a colorless solid. The solid was measured by NMR, and the results are shown below. From this result, it was confirmed that the colorless solid was the intermediate compound (B2) (yield 93%).

'H-NMR (CDC13) δ : 1.84 ( m - 6H) , 2.50 ( m, 2H ) > 4.02 ( m > 2H ) > 6.99 ( d > 2H ) , 7.53 (d, 2H), 7.91 ( m, 4H ) > 9.80 ( s * 1 H ). -40- 201235451 [3] Synthesis of a polymerizable liquid crystal compound (E2) [Chem. 31]

(B2) SnCl2 Ambeilyst 15 THF/H20 --NC

(E2) Finally, the intermediate compound (B2) obtained above was 3.0 g (10. Ommol) and 2. (bromomethyl)acrylic acid 1.65 g (l〇.〇mmol),

Amberlyst (registered trademark) 15 1.6g, THF 16.0mL, tin (II) chloride 1.9g (10.Ommol) and pure water 4.0mL were added to a 50mL eggplant flask with a cooling tube, and the mixture was stirred at 70 °C. The reaction was carried out for 7 hours. After the completion of the reaction, the reaction solution was filtered under reduced pressure and then a mixture of 3 mL of purified water and 50 mL of diethyl ether. Three extractions were performed. Magnesium sulphate was added to the organic layer after extraction, and after drying, the solvent was evaporated under reduced pressure to give a yellow solid. The solid was dissolved in 2 mL of ethyl acetate and chromatographed on silica gel column (column: silica gel 60, 0.06 3 -0.200 mm, manufactured by Mercury, eluent: hexane/ethyl acetate = 2/1) refined. The solvent of the obtained solution was evaporated to give 1.5 g of white solid. As a result of NMR measurement, it was confirmed that the white solid was the objective liquid crystal compound (E2) (yield: 41%). The measurement results of 1H-NMR are shown below.

'H-NMR (CDC13) δ : 1.57 ( m » 6H ) , 1.85 ( m, 2H -41 - 201235451 )> 2.60 ( m > 1Η ) , 3.50 (m'lH) > 4.〇ι ( t , 2h ), 4.54 (m, lH) > 5.63 (m1 1H) > 6.23 ( m > ih ) , 700 (d, 2H) > 7.52 ( d * 2H) , 7.68 (m, 4H). Further, the liquid crystallinity of the polymerizable liquid crystal compound (E2) was observed, and as a result, it was in an isotropic liquid state at 84 ° C, and the phase was transferred to a liquid crystal phase (nematic phase) at 61 ° C at the time of temperature drop. [Synthesis Example 3] Synthesis of a polymerizable liquid crystal compound (E3) [1] Synthesis of an intermediate compound (A3) [Chem. 32] H〇-^^C〇〇CH^ Η〇-(ΟΗ2)β-〇^^-〇 〇〇αίΛ (A3) 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9. 丨g (50.0 mmol) of 6-bromo-1-hexanol, 1 3 · 8 g (100 mmol) of potassium carbonate, and 70 mL of acetone was placed in a 200 mL eggplant type flask equipped with a cooling tube, and the mixture was stirred at a temperature of 64 ° C for 24 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated. This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Melco, eluent: hexane/ethyl acetate = 1/1). After distilling off the solvent from the obtained solution, 11.3 g of white solid was obtained. From the results, it was confirmed that the white solid was an intermediate compound (A3) (yield: 90%). 'H-NMR (CDC13) δ : 1.3-1.7 ( m - 8H) , 3.67 ( m ' -42- 201235451 2H ) > 3.88 ( s > 3H ) > 4.03 ( t > 2H ) , 6.91 (d , 2H), 7.99 (d, 2H). [2] Synthesis of Intermediate Compound (B3) [Chem. 33] Η〇-(ΟΗ2)6-〇-^~^-〇〇〇αΗ3 PCC, CH2C12 · 〇HC-(CH2)5-〇~^~^- 〇〇〇CHj (A3) (B3) Next, PCC 2.2g (10.Ommol) and CH2C12 15_0mL were placed in a 100 mL three-necked flask of a cathode cooling tube, and the intermediate compound (A3) obtained by the above dropping was stirred and mixed. 2.5 g (10.Ommol) of the solution obtained by dissolving in CH2C12 (15,0 mL) was stirred for 6 hours at room temperature. Thereafter, 90 mL of diethyl ether was added to a solution obtained by removing the oil adhering to the inner wall of the flask, and the mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a thick green solid. The solvent of the obtained solution was purified by silica gel column chromatography (column: 矽60, 0.06 3 -0.2 00 mm, manufactured by Merkaku, eluent: hexane/ethyl acetate = 2/1). Colorless solid 1. 3 g. The solid was measured by N M R and the results are shown below. From the results, it was confirmed that the colorless solid was an intermediate compound (?3) (yield: 50%). 'H-NMR (CDCh) δ : 1.3-1.8 ( m > 6H) , 2.49 ( t, 2H ) , 3.88 (s, 3H) , 3.99 (t, 2H) , 6.87 (d, 2H) , 7.99 (d , 2H ) > 9.78 ( s · 1H ). -43- 201235451 [3] Synthesis of Intermediate Compound (C3) [Chem. 34]

/—Βι. COOH ohc-(ch2)广0 〇 COOCHi (B3)

SnCli/Anibeilyst 15 THFy^O____

(CH2)j-0'

OOOCH» (C3) 1.25 g (5.0 mmol) of the intermediate compound (B3) obtained above, 0.83 g (5.0 mmol) of 2-(bromomethyl)acrylic acid, 15 0.8 g of Amberlyst (registered trademark), 8.0 mL of THF, Tin (II) chloride 〇.95 g (5.0 mmol) and 2.0 mL of pure water were placed in a 50 mL eggplant type flask equipped with a cooling tube, and the mixture was stirred at a temperature of 70 ° C for 5 hours to carry out a reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, and then 40 mL of pure water was mixed, and then 50 mL of diethyl ether was added thereto for extraction. Three extractions were performed. Magnesium sulphate was added to the organic layer after extraction, dried, filtered under reduced pressure, and the solvent was evaporated to give a white solid. From the results, it was confirmed that the colorless solid was the intermediate compound (C 3 ) (yield 94%). H-NMR ( DMSO-d6) δ : 1.3-I.8 ( m,8H) > 2.62 ( m

, 1H) > 3.04 ( s > 1H ) , 3.81 (s, 3H) , 4.05 (t, 2H ) > 4.54 ( m > 1H ) , 5.70 (s, lH) , 6.01 (s, lH), 7.03 ( d > 2H ) , 7.89 ( d, 2H ). -44- 201235451 [4] Synthesis of Intermediate Compound (D3) [Chem. 35]

A 巧)5 一 〇

OCEi> (C3)

1) NaOH (aq) / EtOH 2) Aniberivst 15 THF

°x> (CH,)5-0 Ot COOH (D3) 35 m of ethanol, the intermediate compound (C3) obtained above, 1.5 g (4 · 7 mm ο 1 ), and 10% aqueous sodium hydroxide solution 5 m L The mixture was placed in a 10 OmL eggplant type flask equipped with a cooling tube, and the mixture was stirred at a temperature of 85 ° C for 3 hours to carry out a reaction. After the reaction was completed, water (300 ml) and the reaction liquid were placed in a 500 ml beaker, stirred at room temperature for 30 minutes, and then 10 mL of 10% hydrochloric acid was added dropwise thereto to obtain a white solid (1.3 g). Next, the obtained white solids 1.lg, Amberlyst (registered trademark) 15 l.Og, and 20.0 mL of tetrahydrofuran were placed in a 50 mL eggplant type flask equipped with a cooling tube, and the mixture was stirred at a temperature of 70 ° C for 5 hours to carry out a reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, and then the solvent was evaporated to give a yellow solid. The yellow solid was recrystallized (hexane / ethyl acetate = 1 / 1). The solid was measured by NMR, and the results are shown below. From the results, it was confirmed that the white solid was the intermediate compound (D3) (yield 71%). 'H-NMR ( DMSO-d6) δ : 1.2-1.8 ( m > 8H) - 2.60 ( m , 1H) > 3.0 9 ( m 1 1H ) , 4.04 ( m, 2H) > 4.55 ( m > 1H ), 5.69 ( s, 1H ) ' 6.02 ( s, 1H ) , 6.99 ( d, 2H ), 7.88 ( d > 2H) , 12.5 (s, broad, 1H). -45- 201235451 [5] Synthesis of Compound (p3) [Chem. 36] HO—(GH2)j—Br +

EtjN THF

Bi—(CH,)3—O (P3)

19.2 g (138.0 mmol) of 3-bromo-1-propanol and 18.9 mL of triethylamine and a small amount of BHT were dissolved in 100 mL of THF, stirred at room temperature, cooled by a water bath, and then added with propylene chloride in 15 minutes. 12.2 mL (150 mmol) of the solution obtained by dissolving 50 mL of THF was stirred for 30 minutes, then the water bath was removed, and the mixture was returned to room temperature while stirring overnight. After filtering the precipitated TEA hydrochloride, the THF was distilled off from the filtrate, and diethyl ether (10 mL) was added thereto, and the organic layer was washed successively with 80 mL of saturated aqueous sodium hydrogencarbonate solution, 0.5 N hydrochloric acid and saturated brine. Drying with magnesium sulfate and distilling off the solvent ' ί # compound (Ρ 3 ) 1 8 · 2 g. The solid was measured by NMR, and the result was as follows: 'H-NMR (CDC13) δ: 2.20 (m > 2H) > 3.45 ( ), 4.33 (t, 2H) - 5.84 ( d > 1 H ) , 6.13 ( M'l 6.44 ( d,1 H ). [6] Synthesis of intermediate compound (G3) -46 - 201235451 [Chem. 37]

4-hydroxy-4'-bi-diphenol 1 7.6 g (94.3 mmol), compound (P3) 1 8.2 g (94.3 mmol), potassium carbonate 24.0 g (190 mmol), acetone 25 0 mL were added to a cooling tube of 500 mL of eggplant In the flask, the mixture was stirred at a temperature of 54 t for 20 hours to carry out a reaction. After the completion of the reaction, the reaction mixture was filtered under reduced pressure, and the solvent was evaporated under reduced pressure to give a yellow solid. This solid was purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merku, eluent: hexane/ethyl acetate = 2/1). The solvent was evaporated to give a white solid (6.1 g). The solid was measured by NMR, and the results are shown below. From the results, it was confirmed that the white solid was an intermediate compound (G 3 ) (yield 22%). 'H-NMR ( CDC13 ) δ : 2.21 ( m > 2H ) , 4.13 ( t, 2H ), 4.40 ( t, 2H ) , 4.99 ( s > 1H ) , 5.87 ( d,1H ), 6.1 5 ( m * 1H ) ' 6.40 ( d * 1H ) , 6.87 (d, 2H) > 6.99 (d, 2H) 1 7.46 (m > 4H). [7] Synthesis of a polymerizable liquid crystal compound (E3) -47 - 201235451 [Chem. 38]

Intermediate compound (D3) 6.1 g (20.0 mmol), intermediate compound (G3) 6.0 g (20.0 mmol), N,N-dimethyl-4-aminopyridine (DMAP) 0.08 g and a small amount of BHT were stirred at room temperature. It was suspended in 10 mL of dichloromethane, followed by the addition of 4.7 g (23.0 mmol) of dicyclohexylcarbodiimide (DCC) to a solution of 20 mL of dichloromethane. After stirring overnight, the precipitated DCC urea was filtered off. Then, the filtrate was washed twice with 60 mL of 0.5 N hydrochloric acid, a saturated aqueous sodium hydrogencarbonate solution and saturated brine. After drying with magnesium sulfate, the solvent was distilled off, and recrystallization was carried out by ethanol to obtain 8.8 g (yield: 75%) of the polymerizable liquid crystal compound (E3). The measurement results of 1 H-NMR are shown below.

'H-NMR (CDC13) δ : 1.53 ( m * 6H) , 1.81 ( m, 2H ), 2.20 (m, 2H) , 2.60 (m, lH) 5 3.07 ( m - 1H ), 4.06 ( t, 2H ) , 4.12 ( t, 2H ) , 4.40 ( t, 2H ) , 4.54 ( m, lH) , 5.63 (d, lH) 5.85 ( d > 1 H ) - 6. 1 0 ( m - 1H ) > 6.24 ( d > 1H ) . 6.42 ( d > 1H ) > 6.97 ( d > 4H ) > 7.25 ( m - 2H ) , 7.54 ( m, 2H) , 7.59 ( m, 2H), 8. 1 7 ( d, 2H). The liquid crystal phase of the polymerizable liquid crystal compound (E3) was observed, and as a result, the temperature was changed to -48-201235451, the phase was transferred to a disc phase at a temperature of 109 ° C, and the phase was transferred to a nematic phase at a temperature of 168 ° C for each phase. Isotropic liquid state. [Example 1] Synthesis of a polymerizable compound (Z i ) [Chem. 39]

DCODMAP CH>C1>

The intermediate compound (D3) 6.1 g (20.0 mmol), 4-dibenzophenone 4.0 g (20.0 mmol), DMAP O.lg and a small amount of BHT were stirred at room temperature, and suspended in 80 mL of dichloromethane. Add DCC 5.2g (25.0mmol) and stir overnight. After filtering off the precipitated DCC urea, the filtrate was washed twice with 50 mL of 0.5 N hydrochloric acid, 50 mL of a saturated aqueous sodium hydrogen carbonate solution and 10 mL of saturated brine, and dried over magnesium sulfate. The solid was recrystallized (ethanol), and purified to give 7.2 g (yield: 74%) of the desired polymer compound (Z1). The measurement results of iH-NMR are shown below. *H-NMR (CDC13) δ : 1.40- 1.9 5 ( m > 8H) ’ 2.58 ( m

,1H) , 3.07(m,lH) ,4.07(t,2H) * 4.55 ( m > 1H ),5_64(s,lH) > 6.25 ( s > 1H ) '6.99(d'2H) ' - 49- 201235451 7.35 (d'2H), 7.48 (m, 2H), 7.61 (m, lH) - 7.82 (d, 2H), 7.92 (d, 2H), 8_17 (d, 2H). [Example 2] Synthesis of a polymerizable compound (Z2) [Chem. 40]

DCC/DMAP CHjCIj (Z2) The intermediate compound (D3) 6.1 g (20.0 mmol), 4,4'-dihydroxybenzophenone 2.1 g (10.Ommol), DMAP O.lg and a small amount of BHT were stirred at room temperature. It was suspended in 80 mL of dichloromethane, and then DCC 5.2 g (24.Ommol) was added and stirred overnight. After filtering off the precipitated DCC urea, the filtrate was washed twice with 50 mL of 0.5 N hydrochloric acid, 50 mL of a saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated brine, and dried over magnesium sulfate. Yellow solid. The solid was recrystallized from ethanol to give 6.2 g of a white solid. The solid was measured by NMR, and the results are shown below. It was confirmed by NMR measurement that the white solid was a polymerizable compound (z2) (yield: 79%). The measurement results of 1 Η-NMR are as follows. 'H-NMR (CDC13) δ : 1.45- 1.95 ( m . 16H) - 2.58 ( m,2H) , 3.07 ( m,2H) > 4.05 ( t > 4H ) , 4.54 ( m, -50- 201235451 2H ), 5.64 (s, 7.32 (d, 4H) 2H), 6.24 (s, 7.91 (d, 4H) 2H), 6.98 (d, 8.18 (d, 4H) [Examples 3 to 6, Comparative Examples 1] Modulation of polymerizable liquid crystal composition estimator (film) The compounds used in the following examples and comparative examples are as follows. The compositions of the compositions prepared in Examples 3 to 6 and Comparative Example 1 are as shown below. 4H) And evaluation. Also, Table 1 [Chem. 41]

(E3) (Z2) -51 - 201235451 [Table 1] i Dimer (mg) El E2 E3 Z1 Z2 Example 3 120 90 60 30 Example 4 90 90 .60 60 Example 5 90 60 60 90 Example 6 90 90 60 60 Comparative Example 1 150 90 60 [Example 3] 20 mg of the polymerizable liquid crystal compound (E 1 ), 90 mg of the polymerizable liquid crystal compound (E2 ), 60 mg of the polymerizable liquid crystal compound (E3 ), and a polymerizable compound ( Z1) 30g g, photopolymerization initiator, Ikekai 369 (trade name) 4mg, and surfactant R-30 (made by Dainippon Ink Chemical Industry Co., Ltd.) 〇.6mg dissolved in the ring In the 0.70 g of the ketone, a polymerizable liquid crystal composition was obtained. The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1, 〇〇〇 rpm, 20 seconds) on a hot plate at a temperature of 1 ° C. After preheating for 60 seconds, let it cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with the liquid crystal alignment film used at this time was a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) coated on the ITO surface of the ITO-attached glass substrate by a spin coater at a temperature of 230 ° C. After baking, a film having a thickness of 10 nm is formed, and the material obtained by the brushing treatment is applied. Secondly, a metal halide lamp is used in the air, and a strong light of 2,000 mJ/cm 2 is irradiated onto the coating film formed on the substrate with the liquid crystal alignment film. The film obtained by polymerizing the polymerizable liquid crystal composition was a film thickness of 1.9 μm, and was observed by a polarizing microscope. As a result, it was confirmed that the film was horizontally (tilted) to the substrate surface at -52 to 201235451. Further, the phase difference 値 is 288 nm (Andl), and the atomization 値 is 〇_16. The film was heated on a hot plate at 160 ° C for 30 minutes, and the phase difference 値 was 240 nm (And 2 ), and the atomization enthalpy was 0.08. Thereafter, the film was heated at 160 ° C for 30 minutes and placed on a hot plate at 200 ° C for further 1 hour, and the phase difference 値 was 207 nm (And3 ), and the atomization enthalpy was 0. 〇 9. [Example 4] 90 mg of the polymerizable liquid crystal compound (E 1 ), 90 mg of the polymerizable liquid crystal compound (E2), 60 mg of the polymerizable liquid crystal compound (E3), 60 mg of the polymerizable compound (Z1), and a photopolymerization initiator 4K of Irkai 3 69 (trade name) manufactured by Bakai Co., Ltd. and R-30 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) of surfactants. 6 mg dissolved in 0.70 g of cyclohexanone to obtain a polymerizable liquid crystal. Things. The polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film by a spin coater (1, 〇〇〇 rpm, 20 seconds) on a hot plate at a temperature of 10 ° C. After preheating for 60 seconds, let cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. The substrate with the liquid crystal alignment film used at this time was a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) coated on the ITO surface of the ITO-attached glass substrate by a spin coater at a temperature of 230 ° C. After baking to form a film having a thickness of 100 nm, the brushing treatment was carried out, and then a metal halide lamp was used in the air, and 2,000 mJ/cm 2 of strong 201235451 light was irradiated onto the substrate i-type liquid crystal composition formed on the liquid crystal alignment film. The obtained film had a film thickness of 1.9 μm, and it was confirmed by partial eccentricity that the film was oriented at a level (tilt) to the substrate surface. Δ ndl) was 267 nm and the atomization enthalpy was 0.08. The film was heated to a temperature of 30 females (Δnd2) to 233 nm and an atomized enthalpy of 0.16 on a 160 °C hot plate. Thereafter, the thin moon was heated at 160 ° C for 30 minutes for 1 hour, and the phase difference And (And3 ) was 0.09. [Example 5] 90 mg of a polymerizable liquid crystal compound (El), 60 mg of (E2), a polymerizable liquid crystal compound (90 mg of E3 compound (Z1), and 4 mg of a photopolymerization initiator, JI 3 69 (trade name), and 6 mg of a surfactant was dissolved in a cyclohexanone liquid crystal composition. The object was coated on a liquid crystal substrate with a liquid crystal alignment film by a spin coater (1, 〇〇〇 rpm, 20 seconds), and preheated for 60 seconds on a hot plate equipped with a liquid crystal alignment film, and then allowed to cool to room polymerization. The sexual composition is in a liquid crystal state. In this case, the substrate used was a liquid crystal alignment agent (曰SE-1410) coated on a coating film of an ITO-attached glass substrate by a spin coater, and observed by a polymerization microscope. As a result, the phase difference 値 (clock) As a result, the phase difference is placed at 203 nm on a hot plate at 200 ° C, the atomized ruthenium is a polymerizable liquid crystal compound) 60 mg, and the polymerized Bakai company Irkai R-30 (Greater Japan Ink 〇.7〇g The polymerizable liquid crystal composition is polymerized onto the film surface at a temperature of temperature. At this time, the liquid crystal alignment film on the substrate is formed on the ITO surface of the chemical industry company, and calcined at a temperature of -54 - 201235451 2 30 °C. After the film of 10 0 nm thick, the material obtained by the brushing treatment is applied. Next, a strong metal light of 2,000 mJ/cm 2 is applied to the coating film formed on the substrate with the liquid crystal alignment film by using a metal halide lamp in the air. The polymerizable liquid crystal composition was polymerized. The obtained film was a film thickness of 1.9 μm, and observed by a polarizing microscope, and it was confirmed that the film was horizontally (inclined) aligned to the substrate surface. Further, the phase difference And (And 1 ) was 255 nm, and the atomization enthalpy was 0.08. 16 (heated on the hot plate of TC) The film was subjected to a film for 30 minutes, and the phase difference 値(Δ nd2) was 22 8 nm, and the atomization enthalpy was 0.08. Thereafter, the film was heated at 160 ° C for 30 minutes, and the film was placed on a hot plate at 200 ° C for 1 hour, resulting in a phase difference.値(And3) is 204 nm, and the atomization enthalpy is 0.08. [Example 6] 90 mg of the polymerizable liquid crystal compound (E 1 ), 90 mg of the polymerizable liquid crystal compound (E2 ), and 60 mg of the polymerizable liquid crystal compound (E3), polymerizability Compound (Z2) 60 mg, photopolymerization initiator, Irkai 3 69 (trade name) 4 mg, and surfactant R-30 (manufactured by Dainippon Ink Chemicals Co., Ltd.) 6.6 mg dissolved A polymerizable liquid crystal composition was obtained in cyclohexanone oxime. 7 〇 g. The polymerizable liquid crystal composition was applied onto a substrate with a liquid crystal alignment film by a spin coater (1, 〇〇〇 rpm, 20 seconds). The liquid crystal alignment film was preheated on a hot plate at a temperature of 10 ° C for 60 seconds, and then allowed to cool to room temperature. At this time, the polymerizable composition of -55 - 201235451 on the substrate was in a liquid crystal state. The substrate to which the liquid crystal alignment film is attached is a liquid crystal alignment agent by a spin coater (manufactured by Nissan Chemical Industries, Inc.) E-1410) coated on the ITO surface of the ITO-attached glass substrate, baked at a temperature of 230 ° C to form a film having a thickness of 100 μm, and then subjected to a brushing treatment. Secondly, a metal halide lamp is used in the air, and 2,000 mJ is used. The strong light of /cm2 was irradiated onto the coating film formed on the substrate with the liquid crystal alignment film to polymerize the polymerizable liquid crystal composition. The obtained film was a film thickness of 1.8 μm, and observed by a polarizing microscope, and the film level (tilt) was confirmed. Oriented to the substrate surface. Further, the phase difference 値 (Δ ndl) was 267 nm, and the atomization enthalpy was 0.08. The film was heated on a hot plate at 160 ° C for 30 minutes, and the phase difference 値(Δnd2) was 245 nm, and the atomization enthalpy was 0.08». Thereafter, the film was heated at 160 ° C for 30 minutes and then placed in a heat of 200 ° C. When the plate was heated for 1 hour, the phase difference 値 (Δη(13) was 218 nm, and the atomization enthalpy was 0.08. [Comparative Example 1] The polymerizable liquid crystal compound (E 1 ) 1 50 mg, the polymerizable liquid crystal compound (E2 ) 90 mg 60 mg of a polymerizable liquid crystal compound (E3), 4 mg of Ikekai 3 69 (trade name) manufactured by Gibakai Co., Ltd., and R-30 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) .6 mg was dissolved in 0.70 g of cyclohexanone to obtain a polymerizable liquid crystal composition. The polymerizable liquid crystal composition -56-201235451 was coated on the liquid crystal by a spin coater (1, 〇〇〇 rpm, 20 seconds) After preheating for 60 seconds on the liquid crystal of the substrate of the alignment film, the substrate is cooled to a liquid crystal state. The substrate used at this time is a liquid crystal alignment agent by a spin coater (曰SE- 1410) After coating at 230 ° C on a glass substrate with ITO, a film having a thickness of 100 nm is formed, and then the object is removed. In the case where a metal halide lamp is used, a film obtained by irradiating light onto a substrate-formed liquid crystal composition formed on a liquid crystal alignment film has a film thickness of 1.9 μm, and it is confirmed by polarized light that the film is horizontally (tilted) to the substrate surface. 299 nm ( ΔηίΠ The atomization enthalpy is 0.09. The film is heated to 30 234 nm (And2) on a 160 t hot plate, and the atomization enthalpy is 0.08. Thereafter, the film is heated at 160 ° C for 30 minutes and then heated for 1 hour. As a result, the phase difference 値(AncH ) was 0.08. Figs. 1 to 5 show the phase difference of the above film, Angle indicates the incident angle, No Bake indicates that the firing was only performed at 160 ° C for 30 minutes, and Bake was baked at 200 ° C for 60 minutes. Comparative Examples 1 to 4 (Figs. 1 to 4) and t Results No Bake and Ageing on the film surface of Figs. 1 to 4, at a temperature temperature. At this time, the liquid crystal alignment film on the substrate was manufactured by Chemical Industry Co., Ltd. On the ITO surface, a 2,000 mJ/cm2 strong coating film was subjected to a brushing treatment at a temperature, and a polymerization microscope was observed. As a result, the phase difference 値 was a clock, and as a result, the phase difference 値I was placed at 200 ° C. 2 0 5 nm, atomization 値 angle dependence. After treatment, Ageing shows Ageing and then: 匕Comparative Example 1 (Fig. 5), the line is close, and it is known that -57-201235451 can improve the polymerizability. Also, Figure 6 shows the addition of the polymerizable compound (zi). A graph of the thermal stability represented by the amount of film Δηίΐ. In Fig. 6, Stability indicates stability, BPGBL Addition indicates the addition amount of the polymerizable compound (Z1), Ageing indicates baking at 160 ° C for 30 minutes, and Bake indicates Ageing and then baked at 200 ° C for 60 minutes. △ nd Stability (%) in Ageing is determined by And Stability (%) = ( And2/Andl) x 1 00 in Bake by △ nd Stability ( % ) = ( And3/And2 ) x 1 00 . .

Andl, And2, and Δη (13 uses Comparative Example 1 (Compound Z1, 〇% added amount), Example 3 (Compound Z1 '10% added amount), Example 4 (Compound Z1, 20% added amount), and Example 5 (Compound Z1 '30% addition amount) obtained. It can be seen from Fig. 6 that when the compound (Z1) is added in a large amount, only Ageing can obtain the same phase difference as Bake, thereby improving the polymerization property. The above results are shown in Table 2. -58- 201235451 [Table 2] 160t:/30 minutes after film exposure 160t: /30 minutes -2001/60 minutes after baking 厶ndl (nm) atomization 値厶nd2 ( Nm) atomization 値And2/ AndlW Δηά3 (nm) atomization 値Δηά3/ And2(%) Example 3 288 0.16 240 0.08 83.3 207 0.09 86.3 Example 4 267 0.08 233 0.16 87.3 203 0.09 87.1 Example 5 255 0.08 228 0.08 89.4 204 0.08 89.5 Example 6 267 0.08 245 0.08 91.8 218 0.08 89.0 Comparative Example 1 299 0.09 234 0.08 78.3 205 0.08 87.6 [Example 7, Comparative Example 2] Evaluation of film reduction [Example 7] by spin coater (l , 〇〇〇 rpm, 20 seconds) coating the polymerizable liquid crystal composition prepared in Example 4 The liquid crystal alignment film surface of the substrate with the liquid crystal alignment film was preheated on a hot plate at a temperature of 100 ° C for 60 seconds, and then allowed to cool to room temperature. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The substrate to which the liquid crystal alignment film is attached is a liquid crystal alignment agent (SE-1410 manufactured by Seiko Chemical Industry Co., Ltd.) coated on an ITO surface of an ITO-attached glass substrate by a spin coater, and baked at a temperature of 230 ° C. After the film of thickness l〇〇nm, the material obtained by the brushing treatment is applied. Next, in the half-substrate cover and the half-divided air, a strong light of 2,000 mJ/cm 2 is irradiated onto the substrate formed on the liquid crystal alignment film by using a metal halide lamp. After polymerizing the polymerizable liquid crystal composition on the coating film, propylene glycol monomethyl ether acetate (PGMEA) ' was used for development for 20 seconds at room temperature, and then washed with PGMEA at room temperature for 1 sec. After that, the film thickness of the exposed portion after development was the film thickness of the film of Comparative Example 4, and it was confirmed that the film thickness did not decrease. That is, the film of the example has high chemical resistance. -59- 201235451 Observing the film after imaging with a polarizing microscope It was confirmed that the film was horizontally aligned to the substrate surface, and the phase difference 値 was 25 Onm, and the atomization enthalpy was 0.16» [Comparative Example 2] Comparative Example 1 was obtained by a spin coater (1, 〇〇〇 rpm, 20 seconds) The prepared polymerizable liquid crystal composition was applied onto the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film, preheated on a hot plate at a temperature of 10 ° C for 60 seconds, and then allowed to cool to room temperature. At this time, the polymerizable composition on the substrate is in a liquid crystal state. In the substrate with the liquid crystal alignment film used in this case, a liquid crystal alignment agent (SE-1410 manufactured by Nissan Chemical Industries, Ltd.) was applied onto the ITO surface of the ITO-attached glass substrate by a spin coater at a temperature of 23 (TC). After baking to form a film having a thickness of l〇〇nm, the object obtained by the brushing treatment is further applied. Next, a half-division mask is used, and half of the air is used, and a strong light of 2,00 0 mJ/cm 2 is irradiated with a metal halide lamp to form a liquid crystal. The polymerizable liquid crystal composition was polymerized on the coating film on the substrate of the alignment film, and developed with PGMEA at room temperature for 20 seconds, and then washed with PGMEA at room temperature for 10 seconds. Thereafter, no unexposed portion was observed. The film thickness of the exposed portion after development was 1.5 μm, and when the film thickness of the film of Comparative Example 1 was compared, the film thickness was reduced to 79%. That is, the film of the comparative example was inferior in chemical resistance to the film of the example. The film after the development was observed by a polarizing microscope, and it was confirmed that the film was horizontally aligned to the substrate surface. Further, the phase difference 値 was 22 1 urn, and the atomization enthalpy was -60-201235451. The evaluation result of the pattern film reduction is shown in Table 3. [Table 3] Film thickness (ym) Δ nd (nm) Atomization 値Example 4 (development) 1.9 (100%) 267 (100%) 0.08 _ Example 7 (after development) 1.9 (100%) 250 (94%) 0.16 Comparative Example 1 (before imaging) 1.9 ( 100%) 299 (100%) 0.09 Comparative Example 2 (after development) 1.5 (79%) 221 (74%) 3.60 Industrial use possibility Polymerization obtained from the polymerizable liquid crystal composition containing the polymerizable compound of the present invention The object is applicable to an optically anisotropic film such as a polarizing plate and a phase difference plate. In particular, it is suitable for forming a pattern by using a light lithography method in air. [Simplified Schematic] FIG. 1 is a film showing the embodiment 3. Fig. 2 is a graph showing the angular dependence of the phase difference 薄膜 of the film of Example 4. Fig. 3 is a view showing the phase difference 薄膜 of the film of Example 5. Fig. 4 is a graph showing the angular dependence of the phase difference 薄膜 of the film of Example 6. Fig. 5 is a graph showing the angular dependence of the phase difference 薄膜 of the film of Comparative Example 1. Fig. 6 is a thermal stability represented by And of a film which is caused by the addition amount of the polymerizable compound (Z1) Line FIG -61--

Claims (1)

201235451 VII. Patent application scope: 1. A polymerizable compound characterized by the following formula [1] or [2]; (wherein nl and 112 each independently represent an integer from 3 to 10, and m represents an integer from 3 to 〇). 2. A polymerizable liquid crystal composition containing at least one selected from the group consisting of the polymerizable compounds represented by the following formulas [1] and [2], and a liquid crystal compound [Chemical 2] (wherein nl and n2 each independently represent an integer of 3 to 10, and m represents an integer of 3 to 10). The polymerizable liquid crystal composition according to claim 2, wherein the liquid crystal compound is a liquid crystal compound having a polymerizable group. 4. The polymerizable liquid crystal composition according to the third aspect of the invention, wherein the liquid crystalline compound having a polymerizable group is a compound having a polymerizable group represented by the following formula [3] and/or [4], [3] [3] [4] °X>..... (In the formula, the dotted line is the bond key). 5. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystalline compound having a polymerizable group is a group of compounds represented by the following formulas [5] and [6]. Select at least one compound [Chemical 4] (wherein, Μ1, M2 and M3 are each independently of the following formula [3] or [4 -63- 201235451 [化5] °X>··.[3] ^r0··- [4] (wherein The dotted line is a group represented by a bonding bond; X is a fluorine atom, a cyano group or a monovalent hydrocarbon group having a carbon number of 4 to 8, and Π and f2 each independently represent an integer of 2 to 9, and g represents an integer of 2 to 9. A polymer obtained by the polymerizable liquid crystal composition according to any one of claims 2 to 5. A film obtained by a polymerizable liquid crystal composition according to any one of claims 2 to 5. 8. An alignment film obtained by the polymerizable liquid crystal composition according to any one of claims 2 to 5. An optical member which is a polymer having a polymer as claimed in claim 6 or an alignment film according to item 8 of the patent application. -64-