TW201202278A - Polymerizable liquid crystal composition and cholesteric reflective film and reflective polarizer using the same - Google Patents

Abstract

The present invention provides a polymerizable liquid crystal composition which can easily enlarge the wavelength range of reflective selection of a cholesteric reflective film and which has a good productivity. Additionally, provided is a cholesteric reflective film and a reflective polarizer, both comprising said polymerizable liquid crystal composition and having good appearance. The polymerizable liquid crystal composition and the cholesteric reflective film made by said polymerizable liquid crystal composition are characterized by: containing (a) one or more liquid crystal compounds represented by the general formula (I); containing (b) one or more liquid crystal compounds only having one polymerizable functional group; containing (c) one or more liquid crystal compounds having two or more polymerizable groups; containing (d) one or more chiral compounds having one or more polymerizable functional groups; and containing (e) one or more polymerization initiators. R1-Z1-B-A-B-Z2-R2…………………………(I).

Description

201202278 VI. Description of the Invention: The present invention relates to a polymerizable liquid crystal composition which is very useful as a liquid crystal element, a display, an optical component, a colorant, a security target, a laser light-emitting member, and the like. And a __polarizing film and a reflective polarizing plate are obtained from the polymerized liquid crystal composition. [Prior Art] The development of a polarizing plate using reversed-and-infrared characteristics of cholesteric liquid crystals has been popular since 199 。. In order to use the cholesteric liquid crystal as a polarizing plate, it is necessary to select a reverse wave in the visible light range, and to obtain a polarized light by setting the pitch of the cholesteric liquid crystal to a predetermined value. However, when a chiral compound is added to a nematic liquid crystal, the pitch thereof is generally maintained at a fixed pitch to selectively reflect a specific narrow wavelength range. Therefore, there are two Ϊ^9 biliary crystal compositions that expand the wavelength range of selective reflection. For one of the methods, it has been revealed that in a polymerizable cholesteric liquid crystal, a dye which is controlled by an absorption wavelength which overlaps the absorption wavelength of a photocatalyst of a non-irradiated surface of an irradiation surface of a light, a sterol liquid crystal composition In the absorption of the photoinitiator in the middle, and by the difference in the polymerization rate between the emitting surface and the non-irradiated surface, the problem of productivity is controlled by controlling the cholesterol in the spiro=flower wavelength range and the six-day person. Also, because the dye is not

StJ ί! With the increase in the amount of addition, there is a good coloring of the film, directed cholesterol deficiency. In addition, it is also known that the dye which is not in the polymerization wavelength overlaps with the absorption wavelength of the if initiator, and the composition of the unused liquid is formed (see Patent Document 2). ^5 201202278 Μ· 2 is another method' exemplified by optically converting the cholesteric liquid crystal composition. The material is changed to a non-polymerized type, and it is easy to pick up the pitch (in this method, by irradiating the weak light on the irradiation surface, the cholesteric liquid crystal composition is gradually photopolymerized from the irradiation surface to disperse the pitch. In the above-mentioned methods, there is a problem of productivity. However, it takes a long time to produce a cholesterol reflective film in the wavelength range in which the selective reflection is made. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent No. 3224467 [Patent Document 2] Japanese Patent No. 4271729 (29 pages, Example 8) [Non-Patent Document] [Non-Patent Document 1] Liquid Crystal, Vol. 34, Νο. 9, 1009. to 1018 (2007) [Summary of the Invention] [Problem to be Solved by the Invention] The present invention is to solve the problem of providing a wavelength range in which the growth wavelength of the coffee alcohol reflective film is increased, and a polymerizable liquid crystal domain which is excellent in productivity, and further, a method is provided. A cholesterol antireflection type polarizing plate excellent in appearance of the polymerizable liquid crystal composition is used. [Technical means for solving the problem] Since the dye disclosed in the prior art has an orientation deficiency due to an increase in the amount of addition, the present case hair The present invention provides a polymerizable liquid crystal composition, which is characterized in that it has an ability to approximate a dye, and increases the amount of a compound capable of becoming a liquid crystal, and is also difficult to cause orientation defects. The liquid crystal compound containing one or two or more liquid crystal compounds represented by the formula (1), and b) one or two or more liquid crystal compounds having only one functional group, and containing c) Two or more kinds of liquid crystal compounds having two or more kinds of functional groups, d), one or more optically active compounds having one or more functional groups, or two or more kinds of starting agents 2 or more types. 3

S 4 201202278 R1 —Zi—B—A—B—Z2—R2 (1) (wherein R! and R2 are independent of each other, and represent a fluorine atom, a gas atom, a cyano group, and a carbon number of 1 to 12, Or a dilute group having a carbon number of 2 to 12, and one or more of the hydrogen atoms contained in the group may be substituted by a fluorine atom; & represents a single bond, —〇—, __s

_, -COO-, -oco-, -OCH2-, -CH=CH-, -CH=CH-COO-, or an OCO-CH=CH-; Z2 represents a single bond, -〇___s_,

-COO---OCO-,-CH20---CH=CH---CH=CH-COO

—, or an OCO—CH=CH—; A represents a 〇C—, a C=N—, _N=N—, or a C=N~N=C—, or any of the following ring structures;

& represents a fluorine atom, a gas atom, an alkyl group having 1 to 6 carbon atoms, a oxy group having 1 to 6 carbon atoms, or a cyano group; and B represents the following structure;

R·4 represents a fluorine atom, a gas atom, a group having a carbon number of 1 to 6, an alkoxy group having a hindrance of 1 to 6, or a cyano group. And a cholesteric reflective film which is a cholesterol reflective film composed of a cured product of a planar oriented polymerizable liquid crystal composition, and the polymerizable liquid crystal composition is the polymerizable liquid crystal composition. Further, a reflective polarizing plate is provided which is a reflective polarizing plate in which a substrate, a cholesterol reflecting film and a retardation film are laminated in this order, wherein the retardation film is the phase difference film. 201202278 Further, a reflective polarizing plate is provided which is a reflective polarizing plate in which a substrate, a cholesterol reflecting film, a retardation film, and a linear polarizing film are sequentially laminated, and the phase difference film is the retardation film. [Effects of the Invention] The polymerizable liquid crystal composition of the present invention has a function similar to that of a dye, and it is difficult to cause orientation defects by containing a compound capable of becoming a liquid crystal, and has a wavelength range in which selective reflection can be easily expanded. Characteristics. Further, in the polymerizable liquid crystal composition of the present invention, a cholesterol reflection film can be produced by a simple method, and productivity is also good. Therefore, the polymerizable liquid crystal composition of the present invention, the cholesterol reflection film, and the reflective polarizing plate can be applied to a liquid crystal element, a display, an optical component, a coloring agent, a security mark, and a member for laser light emission. [Embodiment] Hereinafter, the present invention will be described in detail. a) (liquid crystal compound represented by the formula (1)) The polymerizable liquid crystal composition of the present invention is a liquid crystal compound represented by the formula (1), but is added by having a photoinitiator It is preferable that the absorption wavelength of the wavelength overlaps, the dye, and the absorption of the photoinitiator contained in the cholesteric liquid crystal composition are suppressed, and the compound having a large conjugate bond of the liquid crystal compound is preferable. According to the above-mentioned viewpoints, in the liquid crystal compound represented by the general formula, R] and I are each independently ' and are a fluorine atom, a cyano group, a carbon number, an alkyl group, or an alkyl group having 2 to 12 carbon atoms. It is preferably a fluorine atom, an alkyl group having 3 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms.

Zl is more ideally a single bond, a 0-, a S-, a C00-, a 0C0- or ~0CH2-, the most ideal form is a single bond, _〇---C00- or a 0C0- . 4 The ideal state is a single bond, -0---s---C00---0C0 - or a 0CIi2~, the most ideal form is a single bond, - ο---COO - or a 0C0 - 〇

S 201202278 • N=N—, a C= A ideal state is—CBC—, —c=N—N-N=C-,

W6 white atom, gas atom, carbon number Bu _ base, stone illusion to listen to Wei Xuan, Wei 1 ~ 6 silk ^ (1) two liquid crystal compounds ❹ ideal form: \ / \ /~^Ν _Μ

The most ideal form is:

R4 rut ideal sample, money fluorine atom, carbon number 1~6 thief base, carbon number 201202278 appearance oxygen ίίϊί, 'the most ideal sample g is fluorine atom or micro 1~6 refining base. limited. 5. The general formula (1) is a liquid crystal compound as listed below, but it is not

R R (a-1) (a,2) (a-4) H3C-pCHa

c^c'~〇h-°fcH2);cH3 (a-5) H3C-f*CH2

n cscO-f (a-6) CH2VCH3 (a-7)

/A

C three c ~ ^ D ~ 〇 fcH seven

(a_8)

CSC (a-9) CHs (a-10) s 201202278 h3c ten ch2- )rc -CHH—CH (a-11)

(a-15)

(a-16)

(a-17)

(a-19)

9 201202278 〇-f-CH2nCH3

(a-23) CH3 (a-24) (a-22) (a-25) H3CfCH2^_/O~« H3C+-CH2 (a-26) (a-27) (a-28) (a-29 ) 0 ten ch2 ten ch3 (a-30) h3c4-ch2

ο ten ch2 ten ch3 (a-31) H3C4-CH:

CH2-j-CH3 n (a-32)

Ach

(a-33) s 201202278 (a-34) Outside 10 2"

(a-35) (a-36) (a-38) Leaf CH2tCH3 (a-37)

(a-40) ) y^CH VII CH3

.0 R

(a-42) (a-41) CH VII CH3 (a.43)

(a-45) /tCH2t\ 〇-{-CH2j-CH3 11 201202278

(a-46)

And seven h3 R (a-47) (a-48) h3c

(a-49) ch2

(a-50) Production (wherein, the claws and 11 are independent of each other) represent an integer of 0 to 7, and R represents a hydrogen atom, a chaotic atom or a burning group having a carbon number of 1 to 6. ^ General formula (1) The content of the compound is preferably from 0.1 to 20% by mass, more preferably from 〇5 to 1% by mass. b) (Liquid crystal compound having only one polymerizable functional group) The polymerizable liquid crystal composition of the present invention has only one polymerizable functional liquid = chemical composition, which is used alone or in combination with other liquid crystal compounds. The liquid crystal compound having only one polymerizable functional group is not particularly limited, and a known one can be used.

】 〗 〖 〗 〖 contained in the Handbook of Liquid Crystals (D

Vm0^ TM - SP-, V. V, ^, W% (Japanese too pH year), quarterly chemistry general No. 22, liquid crystal chemistry special Kaiping ii-_ 2:, Kai Kaiping 8-29618, 曰Bent Kaiping 11 -1480797 Ba Hao" Bent Kaiping 11-116538, Japan's cyclohexyl and other structures have the connection of a plurality of I4 - phenyl, 1, 4 ~ 冉 液 液 mes (mesggen) Rigid part

S 12 201202278 base) propylene sulfhydryl, ethylene oxy-complex liquid crystal compound; or bar = poly-glycidyl polymerizable functional group bar-shaped poly-opening 2004-99446 No. 8 Japanese Patent No. 4-23373, Japanese Crystal Compound. 1 towel is particularly suitable for the heteropolymerization of the filament of the silk of the i(4) = base ring = (f% / or maleimine group, etc., and according to the viewpoint of productivity, the preferred form is acrylonitrile Or (meth)acrylonitrile group. The polymerizable liquid crystal composition of the present invention has only one polymerizable functional group, and specifically, a liquid crystal compound as shown below can be listed.

,〇-(ch2)-〇 0

P—(ch2)w〇 Ο

-(C H)0 -· 0

O

-(CHj)一O

P (ch2)—o m

, 0, <y O—(CH2)-~_CH3 (b-l)

cscO^~ (b-2) (b-3) (CH2)—ch3

(b-4) P

(b-5)

(CH2 Bu CH3 (b-6) 13 201202278

〇 P—(Ch2)—ο =7 (CH2)—0

(CH2)—ch3 0—(CH2)—ch3 (b-7) (b-8)

〇-(CH2)-CH3 O—(CH))_CH3 (b-11)

H3c (b-9) (b-10)

(b-18) 14

S ,0201202278 0—(CH2)^ Ο〇—(ch2)X Ο

Ο—(CH2)—ch3 (b-19) 〇 0-(0^)-0 〇 (CH2)^i

c 〇 〇

H3c

(b-20)

O—(CH2)—ch3 (b-21)

(b-22) (CH2)—ch3 (b-23)

(ch2)——ch3 (b-24)

(CH2)~ch3 (b-25)

(ch2)—ch3 (b-27)

yN—(CH2)—O

(b-29) 15 201202278

(b-30)

〇 (b-31)

(b-32) n represents 0 to 1 〇 These liquid crystal compounds ' may be used singly or in combination of two or more types. Further, when the liquid crystal compound having only one polymerizable functional group is a compound represented by the formula (2), the phase of the selective reflection can be further expanded.

- (wherein, L represents a hydrogen atom or a sulfhydryl group; Sp represents a single bond or a carbon number of 丨~(7), X represents a single bond, a 0-, an S-, a coo-, a ~~〇c〇- ,—〇2—, —CH=CH—, —CH=CH—COO—or —oco—CH=CH—; G! represents a single bond, 1,4—phenylene, naphthalene-2,6—diyl Or L4 - a cyclohexyl group, but one or more hydrogen atoms present in the 4 group may be a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Substituted or substituted by cyano; Μ represents a single bond, -0-, -S-, -COO-, -OCO-, -〇CH2-, -CH=CH---CH=CH-COO- or a 〇c〇 —ai=CH~~, but (^ means a single bond, M means a single bond 'G! means 1,4—stretching phenyl, naphthalene-2,6-diyl or 1,4—extension of cyclohexyl, Μ Represents a Ο—, a s—, a C00—, a 0C0—, a

16 S 201202278

OCH2_, -CH=CH-, -CH=CH-COO- or -〇c〇-CH=CH-; G2 represents a hydrogen atom, a phenyl group, a cyclohexyl group, a naphthyl group, an alkyl group having a hindrance of 丨~(1), carbon a 1 to 1 烷 alkoxy group, a carboxyl group, an amine sulfhydryl group, a cyano group, a nitro group or a halogen atom, but the hydrogen atom in the phenyl group, the hexyl group or the naphthyl group may not be substituted, or may be 1 or 2 More than one halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cyano group substituted. The hydrogen atom in the thiol or amine ketone group may be unsubstituted or may be carbon number. 1 to 10 alkyl groups; 1 and 丫2 each independently' represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The preferred aspect of the liquid crystal compound represented by the formula (2) is a hydrogen atom. The Sp of the liquid crystal compound represented by the formula (2) is preferably a single bond or an alkyl group having 3 to 6 carbon atoms, and the most preferable form is an alkyl group having 3 to 6 carbon atoms. The X of the liquid crystal compound represented by the general formula (2) is preferably a single bond, -0-, a COO-, a 〇c〇- or a 〇c〇-CH=CH-, and most preferably The pattern is a single bond, a 0- or an OCO-. When G represents 1,4 to phenyl, naphthalene-2,6-diyl or ι,4-cyclohexylene, the μ of the liquid crystal compound represented by the general formula (2) is preferably _ 〇—, —C00-, —OCO-, —CH=CH-, —CH=CH—COO—or an OCO—CH=CH—, and the most ideal form is—〇---c〇〇__ _〇c〇-〇 is a g2 of a liquid crystal compound represented by the formula (2), and preferably a hydrogen atom, a phenyl group, a cyclohexyl group, a naphthyl group, an alkyl group having a carbon number of 川~chuan, and a carbon number 丨An alkoxy group, a carboxyl group, an amine sulfhydryl group, a cyano group, a fluorine atom or a chlorine atom, and the most preferable one is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 6 carbon atoms, and a cyano group. Or a fluorine atom. Preferably, the liquid crystal compound represented by the formula (2) is a hydrogen atom, a fluorine atom, a chlorine atom f, a cyano group, an alkyl group having a carbon number of i to 6 or an alkoxy group having a carbon number of 丨6. The most preferable form is a hydrogen atom, a fluorine atom, an alkyl group having a carbon number of 〜3 or an alkoxy group having a carbon number of 1 to 3. ^ Y2 of the liquid crystal compound represented by the general formula, which is preferably a ruthenium atom, a ruthenium atom, a gas atom, a cyano group, an alkyl group having a carbon number of 66 or an alkoxy group having a carbon number of 6, 6 201202278 The most desirable form is an alkoxy group of a hydrogen atom. A chaotic atom, a slave number of 1 to 3 alkyl groups or a carbon number of 1 to 3 〇Λ 、, 旦 () - 卞 卞 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶 液晶The most desirable form is 1〇~7〇% by mass. Further, the liquid crystal compound represented by the second embodiment may be used singly or in combination of two or more types. The liquid crystal compound represented by the formula (2) may specifically be a liquid crystal compound as shown, but is not limited thereto. juice

,0-(f〇-(四)-(2]) 0

0—(CH2)- 0

0—(CH2)—〇 ο 〇_<p^tec-〇-R h3c (2-2)

(2-3) O——(CH2)—〇

o (2-4)

P-(CH2)-〇

0 (2-5)

0—(CH2) ~〇-O~csc o

P—(ch2)—〇 ^D~csc

O H3c—0 18 201202278

o

P—((3)七〇Ο Ο—(CH2)-〇ο ,〇—卿ο p—(CH2)-o 〇-(ch2)-o I—(CH2)^〇- O—(CH2)—0 〇 —(CH2) — rmo

(2-12) (2-13) (2-14) (2-15) (2-16) (2-17) (where m represents an integer of i~6, and R represents a nitrogen atom and a carbon number 1 〇 基, a carbon number of 1 to 10 alkoxy, carboxyl, benzoic acid, nitro, but when the group is a carboxyl group or an amine formazan group, too, or a carbon number of 1 to 10 The ruthenium atom of the group may not be taken. Further, when only one liquid crystal compound represented by At Α is represented by a polymer, it is also desirable because the compound has a general formula: Wavelength 19 201202278

(wherein, L represents a hydrogen atom or a fluorenyl group; Spi represents a single bond or an alkyl group having a carbon number of 1 to 〇; X! & X2 are each independently, and represent a single bond, a 0---s___COO-, - OCO-, -OCH2-, -CH=CH-, -CH=CH-COO_ or - OCO_CH=CH-; Y3, Y4, Y5 and Y6 are independent of each other, indicating a hydrogen atom and a carbon number of 1 to 6 a methoxy group having a carbon number of 1 to 6, a carboxyl group, an aminomethyl group, a cyano group, a nitro group or a halogen atom, but the hydrogen atom in the alkyl group or alkoxy group may be one or more halogens. The atom may be substituted, and the hydrogen atom in the carboxyl group or the amine carbenyl group may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.) The liquid crystal compound represented by the general formula (3) is preferably in a preferred form. It is a hydrogen atom. The Sp] of the liquid crystal compound represented by the formula (3) is preferably an alkyl group having 1 to 10 carbon atoms, and most preferably an alkyl group having 2 to 6 carbon atoms. The X丨' of the liquid crystal compound represented by the general formula (3) is preferably _〇_, -COO-, one OCO-, one CH=CH-, ~~qi==CH-COO- or one OCO. -CH=CH-, and the most ideal state is one 〇-, _c〇〇- or one 〇CO-- X2 of the liquid crystal compound represented by the general formula (3), and the ideal state is -〇_ , -COO-, -oco-, -CH=CH-, ~~CH=CH_C00- or - OCO-CH=CH-, and the most ideal form is ~c〇〇-, one 0C0-, one CH= CH—or a 0—. Γ3, γ4, 丫5, and γ6 of the liquid crystal compound represented by the general formula (3) are preferably independent of each other and are a halogen atom, a carbon number of 1 to 6 carbon atoms, and a carbon number of 1 to 6. The alkoxy group, the carboxyl group, the amine sulfhydryl group, the cyano group or the fluorine atom, and the most preferable one is a hydrogen atom, a carbon group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms to form a cyano group. These liquid crystal compounds may be used singly or in combination of two or more kinds. The liquid crystal compound represented by the formula (3), specifically, the liquid crystal compound shown below is listed, but is not limited thereto.

S 20 201202278 ρ—(CH2)—ο

(3-1)

(3-3) (3-2)

0-(CH2) 0-(CH2)——o

(3-4) (3-5)

(3-6)

O—(CH2)— (3-7)

P—(ch々〇

P-(CH 七 0 P-(CH 七 0

(3-8) (3-9) (3-10)

,〇—(ch2)^〇

(3-11) 21 i(:' 201202278

O—(CH2)-0

P—(CH2)—o

0—(CH2)-0 0

,〇—(ch2)-o o

P—(ch2)-o o H3C—o

(3-12) (3-13)

(3-14) (3-15) (3-16) (wherein m represents an integer of 丨~(1), and R represents a hydrogen atom, a carbon number 丨~6 fluorenyl group, a carbon number of 1 to 6 alkoxy group, An aryl group, an amine aryl group, an aryl group, a nitro group, but the group is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having a carbon number of 丨6, which may be unsubstituted or 1 on 2 _Atom substituted. When the group is an indenyl group or an amine group, the terminal hydrogen atom may be unsubstituted or substituted by a carbon number alkyl group.) tu Μ represents a hydrogen atom, a carbon number of 1 to 3, a carbon number of 1~ The oxy group or cyano group of 3 is preferred. This can be used alone or in combination of two or more. Two or more liquid crystal compounds are used, and the polymerizable functional groups used in the above rc? crystal composition are limited to two liquids, and a known one can be used. For example, there are no more than 22 liquid crystal compounds. 201202278 For example, it can be mentioned as follows: ^ D_, JW Go〇dby, G. w 〇〇 ^f Liquid Crystals (I). - VCH company issued, W8 years), W·钿 ,, edited by V. Vill, Wi% (Edited by the Chemical Society of Japan, the Year of the Brain), 匕 总 总 No No. 22, Liquid Crystal Chemistry, Japan Kaikaiping ^8· No. ^ or 曰日 2 Kaiping 4-22 Bulletin, ^ 11-148079 ' 曰本特开2G02-3 咖啡1号, R 开178233 5虎公告, :ttf842号=(ΐί =:ί) is called the rigid part of the liquid crystal base, and is called acryl 醯a rod having a polymerizable functional group of a glycidyl group, or a rod having a maleic amine group as disclosed in Japanese Laid-Open Patent Publication No. 2004-2373 It is easy to produce a low temperature containing room temperature as a liquid. _. and < η has a water-based 5-type rod-like polymerizable liquid crystal compound. 'Either ethylidene, vinyloxy, propylene, (methacrylic, glycidyl, glycidol, propylene, or yttrium) can be cited, depending on the production point The preferred embodiment is an acrylonitrile group or a (meth) acrylonitrile group. Two or more liquid crystal compounds having a polymerizable functional group used in the polymerizable liquid crystal composition of the present invention may be specifically listed. The liquid crystal compound shown below is not limited thereto.

(C-1) (C-2) (C-3) 23 201202278

(C-5) (C-7)

R

(C-10) (C-ll)

(C-12) s 201202278

(C-13)

(C-19)

O—(CH2)—Ο / m

0—(CH2)7〇

(C-20) rr°, 0

(C-21) (wherein m and n are each independently and represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or an amine. a mercapto group, a cyano group, a nitro group or a li atom, but when the group is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having a carbon number of 1 to 6 25 201202278, all of them may not be substituted. For the county, the amine (four), one or two or more _ sub-takes are taken from the alkyl group having a carbon number of 1 to 10. The hydrogen atom at the end of the earth may not be substituted, or the R is preferably a hydrogen atom or a carbon ^ Alkoxy or cyano. The liquid crystal compounds of the alkyl group and the inverse electrode number 1 to 3 of the formula 3 may be used alone (d) (at least having a polymerizable official material of the fu surface or more), and may be used as long as it is taken from the base. The optically active compound) is at least one polymerizable month used for its 1 gamma I polycrystalline liquid crystal composition. The optically active compound of the above-mentioned clay is not particularly limited, and a known conventional one can be used, for example, as described in Japanese Patent Laid-Open No. 11 _ 193287 #八*3 . ^.1 2001-158788 ^^ ί Special Open 20G7- 269639, Japanese made = scaly, containing isoamyl alcohol, isoflavone, and having a rigid portion such as M-extended phenylcyclohexylene, 私 为 曱 曱 曱 、 、 、 A polymerizable optically active compound having a glycidyl group-polymerizable functional group; a polymerizable optically active compound comprising a terpenoid derivative described in JP-A-8-23%66; in NATURE VOL35 467 ~ 469 pages (issued on November 30, 1995), NATUREVOL 392 476~479 (issued on April 2, 1998), etc. Polymeric optically active compounds composed of a liquid crystal group and a spacer having an optically active portion Or a polymerized optically active compound containing a binaphthyl group as described in JP-A-2004-504285 and JP-A-2007-248945. In particular, it is preferable to produce a helical twisting force (HTP or a large optically active compound) of the polymerizable liquid crystal composition of the present invention. The polymerizable liquid crystal composition of the present invention has at least one polymerizable functional group. The optically active compound, specifically, the liquid crystal composition shown below is listed, but is not limited thereto.

S 26 201202278 〇_(CH七Ο Ο-(ch2)t〇

Ο—(CH2)—ο η ν (d-2) 0-(CH2)—ο

p Ο-(CHj)—ο

Ο—(CH2)——ο η ' (d-4) 0-(CH2)—ο

Ο—(ch2 卜 ο (d.5) ο

〇-(CH2)-ο-* m ο

Ο—(ch2)—d

(d-6) Ο 〇 'o-(ch2)—6

0-(CH2)-0

(d-7) (d-8)

(d-9) • II 27 201202278

ο

s 201202278

(d-24) (wherein m and n are each independently and represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or an amine. a mercapto group, a cyano group, a nitro group or a halogen atom, but when the group is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all of them may be unsubstituted or 1 or 2 More than one halogen atom is substituted. When the group is a carboxyl group or an amine fluorenyl group, the terminal hydrogen atom may not be substituted, or 201202278 may be substituted by an alkyl group having 1 to 10 carbon atoms.) The optically active compound may be used alone. It can also be used by mixing two or more types. 〇 (Polymerization Initiator) The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used for polymerizing the polymerizable liquid crystal composition of the present invention. A known photopolymerization initiator which can be used for polymerization by light irradiation can be used. For example, 2-hydroxy-2-methyl-1'-phenylpropanone ("DAROCUR1Π3" manufactured by Merck & Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty)

"IRGACURE 184" manufactured by Chemicals Corporation), 1-(4-isopropylphenyl)-2-hydroxyl-2-mercaptopropan-1-one (rDAR〇CUR 1116, manufactured by Merck), 2-methyl 1-[(Methylthio)phenyl]-2-indolylpropanone ("IRGACURE 907", manufactured by Ciba Specialty Chemicals Corporation); phenylhydrazinyl ketal ("IRGACURE651", manufactured by Ciba Specialty Chemicals Corporation" , 2-benzoyl- 2 -didecylamino-l-(4-pipelinyl)butanone ("IRGACURE369", manufactured by Ciba Specia丨ty Chemicals Corporation), 2-didecylamino-2 - (4-mercaptophenyl fluorenyl) - 1 - (4 - stimuli - 4 - phenyl) butyl ketone ("IRGACURE 379", manufactured by Ciba Specialty Chemicals Corporation), 2,2-dimethoxy 1,2~diphenylethyl-1-ketone, bis(2,4,6-trimercaptobenzoyl)-phenylphosphine oxide (DAR0CURTP0), 2,4,6-trimercaptobenzoquinone Bis-diphenylphosphine oxide ("IRGACURE 819" manufactured by Ciba Specialty Chemicals Corporation), 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-phenylhydrazine)肟)] ("IRGACUREOXEOl" by Ciba Specialty Chemicals Corporation), B@同,1 - [9_Ethyl-6-(2_mercaptobenzoyl)- 9H-b 〇 — -3 -基] -, 1 — ( 0 — B hearing loss (IRGACUREOXEO2) by Ciba Specialty Chemicals Corporation); 2,4-diethyl oxysulfonium ("KAYACUREDETX" manufactured by Nippon Kayaku Co., Ltd.) and p-diamine phenylhydrazine Mixture of acid ethyl ester ("KAYACUREEPA" manufactured by Nippon Kayaku Co., Ltd.), isopropyl sulfoxide

30 S 201202278 jWordprekinsop rCANTACmE—Ιτχ”) is a mixture of a diammonium group and a ruthenium phthalate, and a ruthenium based oxygen (BASF 3 system “Lu— τρ〇”). The photopolymerization initiator is preferably 1% by mass, and the most ideal sample L:, '2~7 shellfish/0. 5 hai, etc. can be used alone or in combination of 2 or more types. . Further, as the thermal polymerization initiator used in the thermal polymerization, it is possible to use a known conventional ΐ田1, such as I, acetonitrile acetate® 1, cumene argon peroxide, peroxygen peroxide, and bis (4). -Secondary butylcyclohexyl)peroxydicarbonate, benzoyl peroxide, methyl ethyl ketone peroxide, U-double (tri-hexyl peroxide) 3,3,5-^, thief = bad, burned, on five Hydrogen peroxide (p-pentahydr〇Peroxide), tertiary butyl pervaporated IL, dicumyl peroxide, isobutyl peroxide, bis(3-methyl-3-methoxybutyl) peroxidation Di-carbonitrile compound such as @|, 丨i-double (^, such as organic peroxide; 2, 2, - azobisisobutyronitrile #^ double Tf2> - fluorenyl valeronitrile); 2, 2, _Azobis(2_mercapto_n propylene trace) azo lung compound such as dihydrogenated hydrogen, 2,2,-even (10){2 - Y-based-N__ f ) 2 -ylidylethyl]-propyl The content of the azo-nitride compound such as azo-amine compound, 2^', and nitrogen=(2,4,4-trimethylpentane) is 丨~1() f. Quantities of % ^ ϋ 〜6质量^ These can be used alone or in combination with two types of sorrows The thermal polymerization initiator may be used according to the respective use or 0 (solvent) composition, including the composition and solvent of the polymerizable liquid, and the % solvent, as long as it is coated on the substrate, The solvent of the base material 3 /if oriented film is incomplete and the solvent of the present invention is not particularly limited, but a solvent which exhibits good solubility is preferable. The /sa sputum is a solvent as described above, and examples thereof include aromatic hydrocarbons such as toluene and xylene; methyl acetate vinegar, ethyl acetate, and propyl acetate; 31 201202278 糸, agent; methyl ethyl ketone, methyl methacrylate Butadiene, cyclohexyl __solvent; dimethoxy group calcined, benzene __solvent; n, n-dimethyl hydrazine, 2rrf ° f equivalent _ solvent; propylene glycol monomethyl or mixed T Hey: Ding @θ, "etc. These can be made separately =.=, the composition of the body, body composition "^

Sa ether acetate '80 : 20 ', and in view of coatability, it is more desirable to be g) (promoting planar orientation of surfactant or polymer) since the polymerizable liquid crystal composition of the present invention is oriented in a plane If you want to make a bribe into the plane-oriented boundary secret _^分^" ' Sex agent Ben: Do not use the plane-oriented interface to promote a / now in the poly / night crystal composition, and in the polymer liquid When the cloth is dry, the material segregated at the air interface on the opposite side of the substrate can be specially limited to the autumn _ interface, but it is ideal. . . . a heart 々 H horse season and polymerizable 1: 99~60: 40 functional group liquid crystal compound surface tension small surfactant = solid film, called surface miscellaneous · can be recorded. ^Higher, uniform, high-component T for promoting planar orientation used in a liquid crystal composition to be *soluble in a polymerized liquid crystal composition, and at the air interface on the opposite side of the wire during polymer coating drying The segregated material is ^, , · main = Γϋΐ ί =:, the ideal form is more than the polymerizable ΐ energy base a polymer having a small surface tension of a liquid crystal compound, as described above; c: polyethylene, alkene, olefin, money, fossil or gasified liquid stone butterfly, polyvinylidene fluoride, etc. II a mass average of the polymer The ideal molecular weight is 2〇〇1000000 32 201202278. The ideal form is the full ~ dirty 〇. Promote the boundary of the thousand face © © live _ or polymer is 0.01 ~ 3 mass. The most ideal form is the mailing heart... h) (stabilizer)., Li Wei. The polymerizable liquid crystal composition of the rabbit, in order to uniformly coat the sterol, or for various purposes If necessary, it can be added in such a range that the liquid crystal 24 can be remarkably lowered, and the agent, the contact agent, the surfactant, the ultraviolet absorber, the infrared absorber, the antioxidant, the surface treatment agent, the polymerization inhibitor, etc. (Cholesterol Reflecting Film) The present invention is a cholesterol reflecting film comprising a cured product of a planar oriented polymerizable liquid crystal composition, wherein the polymerizable liquid crystal composition contains a) One or two liquid crystal compounds represented by formula (1) One or more liquid crystal compounds containing b) only one polymerizable functional group, and c) one or more liquid crystal compounds having two or more polymerizable functional groups, and d) having polymerization One or more kinds of optically active compounds, one or more kinds of optically active compounds, or two types or more of 'containing e) polymerization initiators. R1—Z “B—A—B—Z2-R2 (1) Wherein ':^ and 尺2 are each independently, and represent a fluorine atom, a gas atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, and a hydrogen atom contained in the group. One or more may be substituted by a fluorine atom; Z! represents a single bond, -〇---s -' -C00- > -0C0- > -〇CH2- ' -CH=CH- > -CH =CH-COO-, or -OCO-CH=CH-; z2 represents a single bond, -ο-, -s-,

-COO---OCO---CH20---CH=CH---CH=CH - COO

—, or an OCO —CH=CH— ; A denotes an OC—, a C=N—, an N=N—., or a C=N—N=C—, or any of the following ring structures; 33 201202278

The reverse 3 represents a fluorine atom, a chlorine atom, a carbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group; and B represents the following ring structure;

R·4 represents a fluorine atom, a chlorine atom, an alkyl group having a hindrance of i to 6, and an alkoxy group having a carbon number of 1 to 6 or a cyano group. The cholesterol reflective film of the present invention is preferably a cholesterol reflective film having a polarized reflection band of 300 nm or more. (Method for Producing Cholesterol Reflective Film) (Substrate) The substrate used for the cholesterol reflective film of the present invention is generally used for a liquid crystal cell, and exhibits an n-tree or an optical display substrate, as long as it is in the present invention = 1 When the liquid crystal composition is dried after application, or when the liquid crystal element is scaled, it is resistant to heat-resistant materials, and there is no particular limitation. For example, the substrate, the ceramic fiber, the naphthalene substrate, etc. When the base material is an organic material, the cellulose I derivative, the polyanthracene hydrocarbon, the polycarbonate, the polyacrylic acid vinegar, the polyaromatic = sturdy, the polyphenylene sulfide, the polystyrene , nylon, or polyphenylene wind, polyimine, especially in the poly I, polystyrene, poly-smoke, ester, polycarbonate and other plastic substrates are ideal. One substance, I square incense In order to improve the polymerization of this turn, the group of secrets, adhesion, also 34 201202278 the surface treatment of the material. The surface treatment may, for example, be an ozone treatment, a plasma rate, or a treatment of a Weiwei coupling agent. Further, in order to adjust the penetration of light, oxide:::, etc.: 有机 an organic thin film or an inorganic substrate may be provided on the surface of the f-material, in order to impart an optically-valued ii filter or the like. In particular, it is preferable to have a higher added value of the read head, a phase difference film first expansion boat, and a shirt color filter. The polymerizable liquid crystal composition film of the present invention is applied and dried. The second day of the second day, and the object of the object, can be applied to the general orientation treatment, or set the orientation of the injection i: it I ΐ stretching treatment, friction treatment, polarized ultraviolet visible light if 3 sub ί treatment. When an oriented film is used, the oriented film is made of an oriented film of the well-known conventional r', which may be 11 (tetra) imine, oxyxan, heteroamine, polyethyl ruthenium polystyrene, polystyrene, polyphenyl hydrazine, polyarylate, Poly-p-dicarboxylic acid, poly@«, epoxy resin, epoxy acrylate sl resin, acrylic resin, material, chalcean compound, cinnamic acid vinegar compound, cinnamic acid compound, azo compound, arylene compound And other compounds. Preferably, the compound treated by the rubbing is such that the crystallization of the material can be promoted by the orientation treatment or the second heating step. It is preferred to use a photo-alignment material in the ruthenium-treated compound. (Coating) A coating method for obtaining the cholesterol reflective film of the present invention can be carried out by a known method such as a smear printing method, a flexographic printing method, an inkjet printing method, a cloth method, a dipping method, and the like. Methods. Usually, = a polymerizable liquid crystal composition diluted with a solvent is applied, and thus the coating is hanged. u (polymerization step) The polymerization age of the polymerizable n-radical of the present invention, after removing the solvent in the liquid composition by ruthenium or the like, in the plane orientation state, generally by the ultraviolet light or It is carried out by heating. When polymerizing by silk, 1 body, 35 201202278 ideal form is _. =; composition decomposition etc. ", = ideal situation. The light is more ideal than the ideal state, especially when using t agent, use its cracking temperature in the above temperature range in addition to the above temperature range _ Outside the limit, the polymerization speed of the light 1; ^°' layer is not much different, and the two options of the liquid film are selected. Heating temperature, polymerization 4 =;; === ==??: heat-induced inhomogeneity Polymerization temperature ί=ΐί Lt ιΐί Li Glass exceeding the substrate made of organic material; t=./outer: For example, the polymerizable group is (meth) propyl _= It is preferably carried out at a low temperature of the vehicle 90 C. The solvent resistance and heat resistance of the cholesterol-reflecting film of 2 to 2 are stabilized, and it is preferable that the heating is performed at the above-mentioned polymerizable liquid crystal: ΐ, usually not more than In the case of the material J, the glass-forming temperature of the substrate is ideal. In addition, the light irradiation treatment is performed. At this time, the liquid crystal δ substance in the cholesterol reflection film is such that it does not decompose by light irradiation. It is preferable. (Reflective polarizing plate) The reflective polarizing plate of the present invention is a laminated substrate and a lining in sequence. a reflection type polarizing plate of a reflection film or a retardation film, or a laminated base material, a cholesterol reflection film, a retardation film, and a line-backed anti-containment polarizing plate, and the cholesteric reflection film of the present invention Membrane. Also 'reflective type bias t has 2 poor film on her hunger X, and the phase difference

S 36 201202278 The film is also excellent in the form of a phase difference film having a different phase difference. The lamination of the substrate and the cholesterol reflective film is as described above. The lamination of the retardation film is exemplified by the following method (in the case of directly laminating on the cholesterol reflective film). An oriented film is formed on the cholesterol reflective film of the present invention, and is placed on the pot. The solution of the liquid crystal compound is dried and obtained by polymerization in a uniaxial state. That is, when the alignment film is not formed, and the liquid crystal compound is also described, the cholesteric ruthenium of the present invention is as described above. As described in the above, it is possible to use a two-pass method to coat the _' alignment film (in the case of bonding on a cholesterol reflection film) on the above-mentioned substrate by the above-described coating method. After the film is bonded, the known anti-two-position agent and the adhesive film of the present invention can be used by a known conventional use of an optical film. Further, the retardation film may be provided with two different phases (four) b green. Parallel (hQn¥_S i cit i , row (f-type A plate), parallel (positive type A plate) and vertical "tC plate", millennium (positive type a plate) and mixing (seesaw). In the case of a laminated film, when a linear polarizing film is provided on the retardation film, it is usually obtained by laminating a bonding agent or an adhesive film. Using a binder or a viscous film, the same method is used to laminate the phase difference with the above-mentioned biliary-reverse surface. The line is irradiated with Si or the electron shot is less. The polymer of the polymerizable liquid crystal composition of the present invention. The X-ray system has a wavelength of 01 to 100 in (Angstrom; the left and right Rays are emitted, and the f-rays are used to make the X-rays of the f. X-rays, Li's as long as in the hair _ _ _ _ 峨 峨 目 (10) line Zhao set 37 201202278 It is reasonable to solve the problem, specifically, the ideal thunder 'gray' 〇 another aspect, the electron ray (EB) is borrowed j ^ lOOkGy (go, the accelerated electron flow, usually used The electric power of the city f is given to the output of the power, as long as the cholesterol reflection film of the present invention is not | because of the electricity, the green electronic riding can be, with the spicy county, the _ is 1G ~ ^ i. Ming and = Ϊ ί Ϊ Ϊ Ϊ In the present invention, the present invention is not limited thereto, and the "parts" and "%" are qualitative (modulation of the polymerizable liquid crystal composition (1)) unless otherwise specified. a liquid crystal compound represented by the formula (1), a liquid crystal compound represented by the formula (Β-1), a liquid crystal compound represented by the formula (C-1), a crystalline compound represented by the formula (c-2), and a formula (D- 1) an optically active compound represented by the formula (e-g, a polymerization initiator, a polymerization initiator represented by the formula (Ε-2), liquid paraffin (G-1) The polymerizable liquid crystal composition of the present invention is obtained by mixing 0.5 parts of the mixture (d. 7 parts of 4-methoxyl-i-naphthol (H_i) 、, cyclohexanone (F) is added to the obtained polymerizable liquid crystal composition. - 1) After 60 parts, it was dissolved at 60 ° C to obtain the polymerizable liquid crystal composition (2) of the present invention.

(C-1) (C-2)

38 S 201202278

P—(CH 2 )——〇 (Dl) (T-combination liquid crystal composition (3) to (25), modulating the composition of the polymerizable liquid crystal composition (2) of the present invention to obtain the “sexuality” of the present invention The liquid crystal compositions (3) to (21) and the polymerizable liquid crystals of the comparative examples (22) to (25). Tables 1 to 6 show the polymerizable liquid crystal compositions () to (21) of the present invention and comparisons thereof. Specific composition of the polymerizable liquid crystal compositions (22) to (25). [Table 1] Polymerizable liquid crystal composition Compound (1) (2) (3) (4) U) Formula (1) A-1 10.0 10:0 A-2 10.0 10.0 A-3 A-4 (b) Liquid crystal compound B-1 having only one polymerizable functional group 11.9 11.9 11.9 11.9 B-2 (b) Formula (2) ^~Β -3 Β-4 (b) Formula (3) Β - 5 11.9 11.9 11.9 11.9 Β -6 (c) Two or more liquid crystal compounds having a polymerizable functional group C - 1 23.8 23.8 23.8 23.8 C - 2 31.8 31.8 31.8 31.8 C—3 C—4 (d) Optically active compound + D-1 7.0 7.0 7.0 7.0 D — 2 a 39 201202278 D-3 D-4 (e) Polymerization initiator E-1 2.8 2.8 2.8 2.8 E-2 0.2 0.2 0.2 0.2 E-3 E-4 (0 dissolution F-1 60.0 60.0 F-2 F-3 (g) surfactant or polymer G-1 0.5 0.5 G-2 (8) chelating agent II-1 0.07 'H-2 [Table 2] Polymerizable liquid crystal composition compound (5) (6) (7) (8) U) Formula (1) A-1 A-2 A-3 10.0 10.0 A to 4 10.0 10.0 (b) Liquid crystal compound B-1 having only one polymerizable functional group 11.9 11.9 11.9 11.9 B — 2 (8) Formula (2) B-3 B-4 (b) Formula (3) B-5 11.9 11.9 11.9 11.9 B-6 (c) Two or more liquid crystals having a polymerizable functional group Compound C-1 23.8 23.8 23.8 23.8 C-2 31.8 31.8 31.8 31.8 C —3 C-4 (d) Optically active compound D-1 7.0 7.0 7.0 7.0 D-2 D-3 D-4 (e) Polymerization initiator E-1 2.8 2.8 2.8 2.8 E-2 0.2 0.2 0.2 0.2 E-3 E-4 s 201202278 (f) Solvent F-1 60.0 60.0 F-2 F-3 (g) Surfactant or polymer G-1 0.5 0.5 G-2 (h) Stabilizer H-1 0.08 0.08 H-2 [Table 3] Polymerizable liquid crystal composition Compound (9) (10) (Π) (12) (a) Formula (1) A-1 A-2 5.0 5.0 5.0 5.0 A-3 A-4 (b) {堇 has 1 aggregate Functional group liquid crystal compound B-1 8.8 8.7 8.5 8.4 B-2 (b) Formula (2) 'B-3 B-4 (8) Formula (3). B-5 17.6 17.5 17.1 16.9 B — 6 (〇 has Two or more liquid crystal compounds C-1 of polymerizable functional groups 26.4 26.2 34.1 25.3 C-2 35.2 34.9 25.6 33.8 C-3 C-4 (4) Optically active compound D-1 7.4 D-2 3.9 D-3 4.5 D — 4 6.4 (e) Polymerization initiator E-1 2.5 2.5 2.5 2.5 E-2 E-3 0.5 0.5 0.5 0.5 E-4 (f) Solvent F-1 30.0 30.0 30.0 30.0 F-2 30.0 F-3 30.0 30.0 30.0 (g ) Surfactant or polymer G-1 41 ll:: 201202278 G-2 0.1 0.1 0.1 0.1 (h) Stabilizer Hl H-2 0.05 0.05 0.05 0.05 [Table 4] Polymerizable liquid crystal composition compound (13) (14 (15) (16) (a) Formula (1) A-1 A-2 5.0 4.0 3.0 5.0 A — 3 A-4 (b) Liquid crystal compound B-1 having only one polymerizable functional group 8.4 6.4 8.6 10.8 B-2 (b) Formula (2) B-3 8.5 B-4 25.9 (b) Formula (3) B-5 16.9 14.9 8.6 15.1 B-6 8.6 (c) Two polymerizable functional groups Above liquid crystal compound C-1 25.3 23.5 21.6 21.6 C-2 33.8 32.0 21.6 30.2 C-3 C-4 (d) Optically active compound D-1 7.4 7.5 7.6 D-2 D-3 D-4 (e) Polymerization initiator E -1 2.8 2.5 2.5 2.5 E-2 E-3 0.5 0.5 0.5 E-4 0.2 (1) Solvent F-1 30.0 30.0 30.0 30.0 F-2 30.0 F-3 30.0 30.0 30.0 (g) Surfactant or polymer G-1 G-2 0.1 0.1 0.1 0.1 (8) Ruthenium H-1 H-2 0.05 0.05 0.05 s 201202278 [Table 5] Polymerizable liquid crystal composition Compound (17) (18) (19) (20) (a) (1) A·~ 1 A-2 5.0 5.0 5.0 2.0 A-3 A-4 (b) Liquid crystal compound B-1 having only one polymerizable functional group 6.3 8.4 8.4 B — 2 21.1 22.1 (8) Formula (2) B — 3 8.8 B — 4 22.1 (b) Formula (3) B-5 14.8 16.9 16.9 8.8 B-6 8.8 (c) Two or more liquid crystal compounds having a polymerizable functional group C-1 21.1 21.1 21.1 8.8 C A 2 21.1 29.5 29.5 8.8 C-3 8.4 C —4 8.4 (d) Optically active compound D — 1 7.4 7.4 7.4 D-2 5.2 D — 3 D-4 (e) Polymerization initiator E-1 2.5 2.5 2.5 4.0 E-2 E-3 0.5 0.5 0.5 0.3 E-4 (1) Solvent F-1 30.0 30.0 30.0 20.0 F — 2 30.0 30.0 F-3 30.0 40.0 (g) Surfactant or polymer G-1 G-2 0.1 0.1 0.1 0.1 (1) Stabilizer H-1 H -2 0.05 0.05 0.05 0.05 [Table 6] Compound (21) (22) (23) (24) (25) (a) Formula (1) A-1 A-2 43 201202278 A-3 A-4 (b Liquid crystal compound B-1 having only one polymerizable functional group 13.3 11.9 11.9 13.3 13.3 B-2 (b) Formula (2) B-3 B-4 (b) Formula (3) B - 5 13.3 11.9 11.9 13.3 13.3 B — 6 (c) Two or more liquid crystal compounds having a polymerizable functional group C-1 26.6 23.8 • 23.8 26.6 26.6 C-2 35.5 31.8 31.8 35.5 35.5 C-3 10.0 C-4 10.0 (d) Optical rotation Compound D-1 7.0 7.0 7.0 D-2 D-3 D — 4 (e) Polymerization initiator E-1 2.8 2.8 2.8 2.8 2.8 E-2 0.2 0.2 0.2 0.2 0.2 E-3 E-4 (1) Solvent F-1 60.0 30.0 30.0 60.0 60.0 F-2 30.0 30.0 F-3 (g) Surfactant or polymer G-1 0.5 0.5 0.5 0.5 0.5 G-2 (8) Stabilizer H-1 0.07 0.07 0.07 H-2 0.05 0.05 H- 3 7 H-4 7 The compounds shown in Tables 1 to 6 are as follows.

44 S 201202278

(B-5)

(C-3)

45 201202278

Cyclopentanone (F-2) toluene (F-3) polyacrylonitrile 4-methoxyphenol (H-2) having a mass average molecular weight of 2200;

(H-4) (Example 1) Using a spin coating, the coating was applied to the base material of the leg 7 of the material, and after 10 minutes of TC drying, it was passed for 200 minutes. The applied coating film is subjected to a rubbing treatment to serve as a base material for a cholesterol reflective film of the present invention. The rubbing treatment is carried out using a commercially available rubbing device. The rubbed film is coated with a bismuth (four) compliant liquid crystal.

S 46 201202278 2 V/at ·8°. . Dry for 2 minutes. The _coating film is placed on the thief's second, upper'. Use the filter H to adjust to the purple ι ί 丨 ^ ^ / 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 The f-pass filter was removed, and the UV-reflected film of the present invention was obtained by irradiating UV light at an intensity of 7 〇 mW/cm 2 for 20 seconds. Using a spectrophotometer (U-41 〇〇 "Hitachi Manufacturing Co., Ltd. = selective reflection wavelength of sterol reflection film, as shown in Fig. 1, the polarization reflection band is about 350 nm. (Examples 2 to 16) and Examples The cholesterol reflection film of Examples 2 to 16 was obtained in the same manner, and the polarized reflection band of the obtained cholesterol reflection film was 300 nm as shown in Table 7. Therefore, it is considered that the polymerizable liquid crystal composition of the present invention is used. The cholesterol reflection film is an excellent cholesterol reflection film that can reflect all visible light. ° Further, any step of coating, drying, and irradiating when preparing a cholesterol reflection film can be performed in a shorter time than conventionally, and we believe that the production is performed. It is also good. White [Table 7] Polymeric liquid crystal composition polarized reflection band Example 1 (2) 350 nm Example 2 (4) 360 nm Example 3 (6) 310 nm Example 4 ' (8) 305 nm Example 5 (9) 350 nm Example 6 (10) 355 nm Example 7 (11) 355 nm Example 8 (12) r ------ 320 run Example 9 (13) 340 nm Example 10 (14) 365 nm Example 11 :(15) 370nm Example 12 (16) 365nm Example 13 (17) Example Η 37〇nai embodiment 310iim (18) ------ 315nm Example 15 (19) 201 202 278

- (Comparative Examples 1 to 3) In addition to the use of the polymerizable liquid crystal compositions (8) to (9), the cholesterol reflection films of Comparative Examples 1 to 3 were used. The obtained reflection film has the first reflection band as shown in Table δ, and all of them are polarized reflection bands of the liquid crystal composition of the spoon. Comparative Example 1 (21) I40nm Comparative Example 2 Ratio: _ίΤ (22) ~ W - 150nm ~---- I45nm (Comparative Example 4~5) Extravagant P uses a polymerizable liquid crystal composition (24) and (25), and a cholesterol reflection film of 5, but the appearance is not good enough. A predetermined cholesterol reflective film. (Embodiment 17) '

The treated polymerizable liquid crystal composition (4) was applied by a bar coating method and dried at 90 ° C for 2 minutes. The obtained coating film was kept at 6 〇: 3 waver and adjusted to obtain only ultraviolet light in the vicinity of 365. (UV followed by silver lamp 'irradiation of UV light at an intensity of 15 mW/cm 2 for 1 sec., wave device, The cholesterol reflection film of Example 17 was obtained by irradiating the paw light with an intensity of 7 〇mW/cm 2 . Similarly, the selective reflection wavelength of the bili 射 film was obtained, and the result is the same as that of the embodiment 2 J. No, the polarized light reflection band is about 36 〇 nm. (Examples 18 to 32) The same as in Example 17 was obtained, and the cholesterol reflection films of Examples 18 to 32 were obtained. As shown in Fig. 9, all of them are polarized reflection bands of melon-polymeric liquid crystal composition (2) 350nm ^^577 s 48 201202278 腑 腑 τ τ—~ (4) 37〇nm Example 19 (6) 310nm Example 20 Implementation Example 21 (8) 305 ηηι (9) 350 ηη Example 22 Implementation ___ (10) 355 nm (11) 355 nm Example 24 Implementation Γ __ (12) 320 iirn (13) 340 nm Example 26 (14) 365 nm Example 27 L (15) 370 nm Example 28 (16) 365 nm Example 29 Example 30 Implementation (17) 370 nm __ (18) 315 nm (19) 310 nm Example 32 (20) 400n m Ϊ Ϊ Ϊ ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The cloth method was applied to the film of Example 1 and dried for 2 minutes. The obtained coating film was subjected to a thick "treatment. The rubbing treatment was carried out using a commercially available friction device. A liquid crystal composition (product name: υν hardened eight UCL-〇17) manufactured by DIC Co., Ltd.) in a toluene solution (solids formed at a cutting rate of 20%), which was applied to the above-mentioned rubbed treatment by a spin coating method. The base was dried for 2 minutes at 80 C. The resulting polarizing plate of Example 33 was obtained by irradiating UV light with 3 〇mW/cm 2 for 15 seconds using a high pressure mercury lamp. Using a spectrophotometer (U) -4100 "manufactured by Hiroshi Seisakusho Co., Ltd.") The spectral characteristics of the obtained reflective polarizing plate were measured, and a commercially available linear polarizing plate was placed between the reflective polarizing plate of Example 33 " The reflective polarizing plate of Example 33 and each of the commercially available linear polarizing plates In the case where the polarization direction is parallel 49201202278 (parallel polarization; parallel nicol) case of perpendicular (orthogonal polarization; cr〇ssnic〇1) determining transmittance. In the case of parallel polarized light, the transmittance is in the visible light range of 9 〇 % or more. In the case of orthogonal polarization, the transmittance is almost 〇% in the visible range. (Example 34) The toluene solution of UCL-017 used in Example 33 was applied to a surface rubbed poly(ethylene) cellulose film, and dried at 6 (TC for 3 minutes. Using a high pressure mercury lamp at 30 mW/ The intensity of Cm2 was irradiated with W light for 15 seconds on the obtained coating film to obtain a retardation film composed of a polymerizable liquid crystal composition. The peeling layer on one side of a commercially available transparent double-sided adhesive tape was peeled off, and the obtained phase was attached. On the poor film, the peeling layer on the other side was peeled off, and then bonded to the cholesterol reflecting film of Example 17, to obtain a reflective polarizing plate of Example 34. The spectral characteristics of the obtained reflective polarizing plate were compared with Examples The measurement was carried out in the same manner as in Example 33, and the same polarizing characteristics as in Example 33 were obtained. (Example 35) The polyvinyl condensate solution of Example 33 was applied to the reflection of Example 33 by a spin coating method. On a polarizing plate, it is dried for 2 minutes. Next, a xylene solution (solid content of a polymerizable liquid crystal composition for a retardation film (product name: uv hardened heterocrystal "UCL-018" DIC Co., Ltd.)) Ratio: 25%), by rotation The coating method was applied to the above and dried at 8 Torr for 2 minutes. The resulting coating film was obtained by using a high pressure mercury lamp at 3 GmW 々 m2 = UV* 20 seconds to obtain a reflection type of Example 35 (Example 36) The xylene solution of UCL-G18 used in Example 35 was applied to the surface of the surface, and dried at 6 (rc for 3 minutes. Using a high pressure mercury lamp, the uv light was irradiated at an intensity of 30 mW/cm for 2 seconds. A retardation film composed of a polymerizable liquid crystal composition was obtained on the obtained coating film, and the peeling layer on the surface of the belt was peeled off, and then attached to the obtained retardation film, and the layer was peeled off and attached to the reading _ 34 __ On the reverse, 彳 copper = column =

50 201202278 Reflective polarizer. (Example 37) The peeling layer on one surface of a commercially available transparent double-sided adhesive tape was peeled off, and it adhered to the cholesterol reflection film of Example 17, and peeling off the peeling layer of the other surface, and it adhered to the cholesterol reflection film of the Example. The cholesterol reflective film of Example 37 was obtained. The selective reflection wavelength of the cholesterol reflection film of Example 37 was measured, and as a result, the polarized reflection band was about 4 mn as in the second embodiment. Furthermore, the transmittance is approximately 50% or less over the entire visible light range. (Example 38) - A cholesterol reflecting film of Example 38 was obtained by irradiating a krypton ray of 5 kGy at room temperature to a cholesterol reflecting film of Example 17 using a commercially available X-ray irradiation apparatus. The evaluation of the adhesion of the obtained cholesterol reflective film was carried out by a cross-cut test by Κ5400. For the cross-cut test, cut the vertical and horizontal cuts at intervals of 2 mm using a cutter to make 25 grids. Adhesive tape was adhered to the grid, and the number of lattices at the time of stripping was counted, and as a result, 24 pieces remained. (Example 39) A commercially available electron beam irradiation apparatus was irradiated with an electron beam of 10 kGy at room temperature in the cholesterol reflection film of Example 17, to obtain a cholesterol reflection film of Example 39. The adhesion was evaluated in the same manner as in Example 38, and as a result, 2 blocks were left. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a polarization reflection band of a cholesterol reflection film produced in Example 1. _ , Fig. 2 is a view showing a polarized reflection band of the cholesterol reflection film produced in the example. [Main component symbol description] 钲 51

Claims (1)

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 With hf = (, hydration S energy base 2 ^ on the optical rotation (four) on the two: = with on, poly-compound; starter 1 or more; 3 with e) t 5 R1 - Z "B-A-B-Z2-R2 (!) (wherein RjR2 is independent of each other, and represents a fluorine atom, a filament having 1 to 12 chlorine atoms, or an alkenyl group having 2 to 12 carbon atoms, and is contained in the earth ^ ί Atom, one or more of the recordable atoms; Ζι丝单键Ί二^; C〇nC〇0:, —〇C〇—, —〇CH2—, —CH=CH—-CH=C; , or -0C0-CH=CH— ; &amp; represents a single bond, —〇_, _s_, n~〇C^7'~CH2° CH=CH—CH=CH-COC :, or —OCO-CHCH- A means - try -, -c = n -, -n -, or -C = NN = C-, or any of the following ring structures; A carbon having a carbon number of 1 to 6 represents a fluorine atom, a gas atom, an alkyloxy group having 1 to 6 carbon atoms, or a cyano group; and B represents the following ring structure; S· 52 201202278 ~ WR4 indicates a fluorine atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, a decyloxy group having 1 to 6 carbon atoms, or a cyano group. The polymerizable liquid crystal composition of claim J, wherein the content of the compound represented by the formula U) is from 01 to 20% by mass. 3. The polymerizable liquid crystal composition according to claim </RTI> or 2, wherein a) the liquid crystal compound 2 represented by the formula (1) is contained in an amount of 2 or more. 4. The polymerizable liquid crystal composition of claim 2, wherein the δ has two or more liquid crystal compounds having two polymerizable luminescent groups. /, 5·^α, the polymerizable liquid crystal composition of the above-mentioned item of the fourth to fourth aspect of the patent, wherein the liquid crystal compound having only one polymerizable functional group is represented by the formula (2); L Η, Γ^, Γ 0—Sp__x—Gi— ii Yi } 2 (2) (wherein B represents a hydrogen atom or a sulfhydryl group; Sp represents a single bond or a carbon number i~1〇, and X represents a single The bond, -〇---S-, -COO-, -OCO-, -〇ch2 -,:CH=CH-, -CH=CH-COO- or -oco-CH=CH-; 2 is not a single bond, 1,4—phenylene, naphthalene-2,6-diyl or anthracene, 4—cyclohexylene, but one or more hydrogen atoms in the group of 1 may be fluorine atoms or gas. The original f, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having a carbon number of 1 to fluorene or a cyano group; M represents a soap bond, -0-, -S-, a coo-, an OCO-, a 〇CIi2 -, a CH 2 CH CH=CH-COO- or a 〇c〇-CH=CH-, but when expressing a single bond, Μ represents a single bond, Gi represents 1,4 —phenylene, naphthalene-2,6 — When dibasic or i,4 is extended to cyclohexyl, 'Μ denotes one 〇—, one S—, — c〇0 —, one OCO —, one 〇 CH 2 CH=CH CH=CH- COO Or -oco - CH=CH :&amp; represents a hydrogen atom, a phenyl group, a cyclohexyl group, a naphthyl group, an alkyl group of a carbon number, a carbon, an alkoxy group of 1 to 10, a carboxyl group, an amine sulfhydryl group, a cyanium group a nitro group or a halogen atom, but the hydrogen atom in the phenyl group, cyclohexyl group or naphthyl group may not be substituted, or one or more halogen atoms, an alkyl group having 1 to 6 carbon atoms, and a carbon number The alkoxy group or the cyano group of 丨~6 may be substituted, and the hydrogen atom in the carboxy or amine fluorenyl group may be unsubstituted or substituted by an alkyl group having a carbon number of i 53 201202278 to 10; 丫! and 丫2 are each independently 'Expresss a hydrogen atom, a halogen atom, a nitrogen group, a nitro group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). 6. The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein the content of the compound of the formula (2) is 5 to 80% by mass. 7. The polymerizable liquid crystal composition according to any one of claims 1 to 6, wherein the liquid crystal compound having only one polymerizable functional group is represented by the formula (3); (wherein, L represents a hydrogen atom or a fluorenyl group; SP1 represents a single bond or a carbon number i to a mercapto group, and X] and X2 are each independently, and represent a single bond, —, —s—, ____—0C— _〇ch2---CH=CH——CH=CI-I-COO- or —, = f ; I, Y4, Y5 and Y6 are each fused, indicating a hydrogen atom, carbon 凄 = a carbon dioxide of 2, carbon a number of 6 oxy, carboxy, amine A, nitrogen, ίίΐΐ Xuan, but the hydrogen source of the ship-based or silk-based towel is not one or two ΐϊΐ Γ Γ ' 织 或 or the hydrogen atom in the amine sl group may not be Instead, it can be replaced by an alkyl group of 1 to 10). Further, the content of the polymerizable liquid crystal composition of any one of the first to seventh items, and the content of the octa- 4-initiator is ≤ 〇 by mass%. Among them, there are two or more types of polymerizable liquid crystal compositions of any of the above-mentioned items. The polymerizable liquid crystal composition of any one of the polymerizable liquids 1 to 1G. The polymerizable liquid crystal composition contains a) one of the liquid crystal compounds S 54 201202278 or One or more liquid crystal compounds containing b) only one polymerizable functional group, or two or more liquid crystal compounds having two or more polymerizable functional groups, and containing d) polymerized One or more kinds of optically active compounds or more than two or more, and e) a polymerization initiator, or two or more types; R!—Α—Β—A—B—Z2-R2 (1) &quot; Two 111 and two feet are independent, indicating chaotic atoms, chlorine atoms, cyano groups, carbon shields ~1 Ιΐί : or alkenyl groups having a carbon number of f 12 and 4 or 8 of the hydrogen atoms contained in the groups The above may be substituted by a fluorine atom; z] represents a single bond, -s COO OCO---〇CH2 - CH=CH - CH=CH-COO-, or -OCO-CH=CH-. 7 志一细-coo——oco___Ch2〇—,: early key S_, -, — CH=CH—, — CH=CH-COO A represents an OC—, a C two N—, an N—, or an OCO-CH=CH =N—, or —C=N—N=C— Or any of the following - a ring structure; Pu, Oxygen group, carbon TM R4 represents a fluorine atom, a gas κ, an oxy group, or a cyano group. , an acyl group of ~6, an alkane with a carbon number of 1 to 6. 13. For example, Shen 5 Fen patent range skirt 1 q g 阗弟12 item of cholesterol reflection film, of which, polarized reflection 55 201202278 The band is above 300nm. 14. The bile radical reflective film of the 12th or 13th j ^ ^ hh ΙΪ 1 ^ M # rb member of the patent application is a reversed surface of a biliary substrate containing a substrate, and the towel is made of a film. 15·- a kind of reflective polarizing plate is a reflective type of polarizing film of a sequential substrate retardation film, which is characterized in that: Tcan®&quot;' reflective film and the cholesterol reflective film are as claimed in the scope of the invention. Sterol reflective film. M m 16.- a reverse (four) polarizing plate, which is a reflective polarizing plate of a sequential four-layer substrate, a cholesterol reflective film, a retardation film, and a linear polarizing film, wherein the cholesterol reflective film is as claimed in the patent application. The sterol reflective film according to any one of items 12 to 14. The reflective polarizing plate of the fifteenth or sixteenth aspect of the invention, wherein the reflective polarizing plate contains two or more retardation films, and the retardation film contains a retardation film having a different phase difference. . 18. The cholesterol reflective film according to any one of claims 12 to 14, wherein the X-ray irradiation treatment or the electron beam irradiation treatment is performed. 19. The reflective polarizing plate according to any one of the above claims, wherein the substrate is a light diffusing film. Eight 'pattern: 56 S