CN109715761A

CN109715761A - Polymerizable liquid crystal compound and the optical film for using it

Info

Publication number: CN109715761A
Application number: CN201780054771.0A
Authority: CN
Inventors: 桑名康弘; 中田秀俊; 延藤浩一
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2016-09-09
Filing date: 2017-09-05
Publication date: 2019-05-03
Also published as: JP6590075B2; KR20190042046A; WO2018047806A1; KR102197550B1; JPWO2018047806A1

Abstract

Excitation purity and the excellent polymerizable liquid crystal compound of productivity can be improved by providing.Further, there is provided by by permeability obtained from polymerizable liquid crystal compound polymerization well and the optical film that improves of excitation purity, by stacked film made of the optical film and the stacking of other optical elements, and the image display device of aforementioned optical film, stacked film is used.The present invention provides a kind of polymerizable liquid crystal compound, contains the one kind or two or more polymerizable liquid crystal compound indicated by general formula (I-1) and the one kind or two or more polymerizable liquid crystal compound indicated by general formula (II-1)；The optical film as obtained from polymerizeing the polymerizable liquid crystal compound is also provided, by stacked film made of the optical film and the stacking of other optical elements, and has used the image display device of aforementioned optical film, stacked film.

Description

Polymerizable liquid crystal compound and the optical film for using it

Technical field

The present application is related to using in liquid crystal apparatus, display, optical component, colorant, safety mark, lasing fluorescence Optically anisotropic body used in the optical compensation of component or liquid crystal display etc., reflection-type polarization element, as composition The useful polymerizable liquid crystal compound of component, and the optical film comprising the composition, have used the image of the optical film to show Device.

Background technique

Polymerizable liquid crystal compound is useful, optically anisotropic body example as the member of formation of optically anisotropic body Such as light polarizing film, phase difference film optical film and be applied in various liquid crystal displays.Light polarizing film, phase difference film pass through as follows Method obtains: polymerizable liquid crystal compound being coated on substrate, after making solvent seasoning, makes polymerism liquid using alignment films etc. In the state of brilliant composition orientation, heats or irradiate active energy beam and solidify polymerizable liquid crystal compound.In addition, Know if can be obtained using the polymerism cholesteric liquid crystal composition for being added to chipal compounds in polymerizable liquid crystal compound Rotatory polarization resolution element, and studying and improving the application in film etc. in luminance.

In general, using in rotatory polarization resolution element made of polymerism cholesteric liquid crystal composition, select reflection wavelength (λ) with The relationship of screw pitch (p) is expressed as the relationship of λ=pN (mean refractive index that N is polymerism cholesteric liquid crystal composition), indicates choosing The width (Δ λ) for selecting the wavelength of reflection is expressed as birefringence anisotropy's (product of Δ n) and p of polymerizable liquid crystal compound.

So far, in order to improve the excitation purity of light source used in liquid crystal display element, proposition, which has used, has narrow choosing Select the optical film (patent document 1,2) of the polymerism cholesteric liquid crystal composition of reflective band domain.But it if attempts to carry out real Border research, then status is can not to obtain desired Δ λ, and excitation purity cannot be increased to the degree of expectation.In addition, permeability, life Also there is room for improvement for yield, becomes project.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2004-262884 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2008-129483 bulletin

Summary of the invention

Subject to be solved by the invention

A kind of it can be improved excitation purity and the excellent polymerizable liquid crystal of productivity the problem to be solved by the present invention is that providing Composition.Further, it provides by the way that permeability obtained from polymerizable liquid crystal compound polymerization is good and excitation purity improves Optical film, by stacked film obtained from the optical film and the stacking of other optical elements, and used aforementioned optical film, layer The image display device of folded film.

Means for solving the problems

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result develop containing specific there are many having The polymerizable liquid crystal compound of the polymerizable liquid crystal compound of structure.That is, the present invention provides a kind of polymerizable liquid crystal group Object is closed, the one kind or two or more polymerizable liquid crystal compound and one kind or two or more by leading to indicated by general formula (I-1) is contained The polymerizable liquid crystal compound that formula (II-1) indicates；The optics as obtained from polymerizeing the polymerizable liquid crystal compound is also provided Film by stacked film obtained from the optical film and the stacking of other optical elements, and has used the figure of aforementioned optical film, stacked film As display device.

The effect of invention

Polymerizable liquid crystal compound of the invention is characterized in that, and has used what general formula (I-1) indicated to have 2 polymerisms What the polymerizable liquid crystal compound and general formula (II-1) of functional group indicated is directly connected in 1 without interval base The polymerizable liquid crystal compound of the polymerizable functional group of cyclic group.When by polymerizable liquid crystal compound polymerization, each general formula institute table Some orientation is inconsistent in mesomorphic skeleton part present in the polymerizable liquid crystal compound shown, can obtain orientation order Low polymer, therefore can (Δ n) inhibits lower by birefringence anisotropy.As a result, it is possible to obtain permeability well simultaneously And the optically anisotropic body that excitation purity improves, thus it is useful on the way in the use of the optical materials such as optical film.

Specific embodiment

Illustrate the best mode of polymerizable liquid crystal compound according to the present invention below, in the present invention, polymerizable liquid crystal group Close object " liquid crystal " mean polymerizable liquid crystal compound be coated on matrix after, be in the state of eliminating organic solvent Existing liquid crystal liquid crystal property.In addition, " liquid crystal " of polymerizable liquid crystal compound is meant in the present invention, only with used polymerism liquid This kind of compound of brilliant compound and liquid crystal liquid crystal property is presented, or the presentation when mixing with other liquid-crystal compounds and mixture being made Liquid crystal liquid crystal property.It should be noted that polymerizable liquid crystal compound by using the irradiation of the light such as ultraviolet light, heating or they and be used into Row polymerization processing, thus allows for polymerization (membranization).

About polymerizable liquid crystal compound of the invention, by and with general formula (I-1) indicate there are 2 polymerism functions What the polymerizable liquid crystal compound and general formula (II-1) of group indicated is directly connected in ring-type without interval base with 1 The polymerizable liquid crystal compound of the polymerizable functional group of base, thus, (Δ n) becomes polymerizable liquid crystal to usual birefringence anisotropy The product of each Δ n possessed by each polymerizable liquid crystal compound in composition and ingredient ratio and, in contrast, when polymerization, is outstanding It is the polymerization for the polymerizable functional group for being directly connected in cyclic group without interval base with 1 that general formula (II-2) is indicated Property liquid-crystal compounds in mesomorphic skeleton part from the axis of orientation of script deviate, polymerize in this state, be thus orientated order Sequence specificity reduces.As a result, it is possible to reduce Δ n, it can reduce and be added to chipal compounds in polymerizable liquid crystal compound When selection reflection wavelength band domain (Δ λ)/selection reflection kernel wavelength (λ) value.

(2 function polymerizable liquid crystal compound)

(the 2 function polymerizable liquid crystal compounds that general formula (I-1) indicates)

It is characterized in that, contain in polymerizable liquid crystal compound of the invention has 2 polymerizable functional groups in the molecule Polymerizable liquid crystal compound (2 function polymerizable liquid crystal compound), it is therein one kind or two or more selected from the following general formula (I-1) table The polymerizable liquid crystal compound shown is as an essential component.

[changing 1]

(in formula, P¹¹¹And P¹¹²Polymerizable functional group is each independently represented,

Sp¹¹¹And Sp¹¹²The alkylidene or singly-bound of carbon atom number 1~18 are each independently represented, 1 in the alkylidene- CH₂Or 2 or more not adjacent-CH₂It can be replaced each independently by-COO- ,-OCO- or-OCO-O-, the alkylidene institute 1 had or 2 or more hydrogen atom can be replaced by halogen atom or CN base,

X¹¹¹And X¹¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、- S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH= CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、- CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N= N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound (wherein P¹¹¹-Sp¹¹¹、P¹¹²-Sp¹¹²、Sp¹¹¹-X¹¹¹And Sp¹¹²- X¹¹²In do not include that oxygen atom is mutual is directly connected to.),

Q111 and q112 each independently represents 0 or 1,

A¹¹And A¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- two Base, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, naphthane -2,6- diyl, decahydro Naphthalene -2,6- diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or be taken by 1 or more substituent group L Generation,

L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyano, isocyano group, amino, hydroxyl Base, sulfydryl, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl silyl, dimethyl methyl silicon Alkyl, thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can substituted cyclohexylalkyl or 1- CH₂Or 2 or more not adjacent-CH₂It each independently can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S- CO-、-O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH =CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰,-CH=N-N=CH- ,-CF=CF- or-C ≡ C- (in formula, R⁰ Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8.) replace carbon atom number 1 to 20 straight-chain or branch-like alkyl, the alkane Any hydrogen atom in base can be replaced by fluorine atoms, in compound L there are it is multiple when they can be the same or different, A¹¹It deposits They can be the same or different when multiple, A¹²There are it is multiple when they can be the same or different,

Z¹¹And Z¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、-CO-、-COO-、-OCO-、- CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O- NH-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH =CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO- CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N-N= CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z¹¹There are it is multiple when they can be the same or different, Z¹²There are it is multiple when it Can be the same or different,

M111 and m112 each independently represents 0~2 integer,

R¹And R²Each independently represent hydrogen atom, fluorine atom, cyano, hydroxyl, nitro, carbon atom number 1 to 10 alkyl, The alkoxy of carbon atom number 1 to 10, the acyl group of carbon atom number 2 to 10, the alkyl carbonyl oxy of carbon atom number 2 to 10, carbon atom number 2 To 10 alkoxy carbonyl or the aromatic series ring group of carbon number 5~12, R¹Or R²In either indicate hydrogen atom other than group, Or R²With adjacent existing A¹²Possessed substituent group L connection and indicate cyclic group.)

In above-mentioned general formula (I-1), P¹¹¹And P¹¹²Polymerizable functional group is each independently represented, is preferably indicated selected from following Formula (P-1) to formula (P-17) group,

[changing 2]

These polymerizable groups by free radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerisation come Polymerization.Especially carry out polymerizable ultraviolet as polymerization when, preferred formula (P-1), formula (P-2), formula (P-3), formula (P-4), Formula (P-8), formula (P-10), formula (P-12) or formula (P-15), more preferable formula (P-1), formula (P-2), formula (P-3), formula (P-4), formula (P-8) or formula (P-10), further preferred formula (P-1), formula (P-2) or formula (P-3), particularly preferred formula (P-1) or formula (P-2).

In above-mentioned general formula (I-1), q111 and q112 each independently represent 0 or 1, from can will use resulting polymerization Property liquid-crystal composition obtained from polymer birefringence anisotropy (Δ n) be suppressed to it is lower consider, particularly preferably indicate 1。

In above-mentioned general formula (I-1), Sp¹¹¹And Sp¹¹²The alkylidene or singly-bound of carbon atom number 1~18 are each independently represented, 1-CH in the alkylidene₂Or 2 or more not adjacent-CH₂It each independently can be by-COO- ,-OCO- or-OCO-O- Replace, 1 or 2 or more hydrogen atom can be by halogen atom (fluorine atom, chlorine atom, bromine atom, iodine original possessed by the alkylidene Son) or the substitution of CN base.In addition, Sp¹¹¹And Sp¹¹²The alkylidene of carbon atom number 1~12, the alkylene are more preferably indicated each independently 1-CH in base₂Or 2 or more not adjacent-CH₂It can be replaced each independently by-COO- ,-OCO- or-OCO-O-.Into One step, Sp¹¹¹And Sp¹¹²The alkylidene of carbon atom number 1~8 is particularly preferably indicated each independently.

In above-mentioned logical formula (I), X¹¹¹And X¹¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CO-、-COO-、- OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、- CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO- CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、- CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound.In addition, X¹¹¹And X¹¹²Respectively From independently more preferable expression-O- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-O-CO-O-、-CF₂O-、-OCF₂-、- CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、- CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-CF= CF- ,-C ≡ C- or singly-bound.Further, X¹¹¹And X¹¹²Particularly preferred expression-O- or singly-bound each independently.

In above-mentioned general formula (I-1), A¹¹And A¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, tetrahydro Naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or by 1 Above substituent group L replaces.From the viewpoint of the easiness, the being easy to get property of raw material and liquid crystal liquid crystal property of synthesis, A¹¹And A¹²Respectively 1,4- phenylene, the Asia the 1,4- hexamethylene can be unsubstituted from independently preferred expression or can replaced by 1 or more substituent group L Base, bicyclic [2.2.2] octane-Isosorbide-5-Nitrae-diyl, naphthalene -2,6- diyl or naphthalene-Isosorbide-5-Nitrae-diyl more preferably indicate to be selected from each independently Following formulas (A-1) to formula (A-16) group.

[changing 3]

Further also from refractive anisotrop it is low from the viewpoint of, existing A¹¹And A¹²It is further excellent each independently Choosing indicates to be selected from group of the above-mentioned formula (A-1) to formula (A-7) and formula (A-10), existing A¹¹And A¹²Each independently into one Step more preferably indicates to be selected from group of the above-mentioned formula (A-1) to formula (A-7), existing A¹¹And A¹²Each independently particularly preferably Indicate the group selected from above-mentioned formula (A-1) to formula (A-4).It should be noted that A¹¹There are it is multiple when they can it is identical can also With difference, A¹²There are it is multiple when they can be the same or different.

In above-mentioned general formula (I-1), L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyanogen Base, isocyano group, amino, hydroxyl, sulfydryl, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl first Silylation, dimetylsilyl, thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can be substituted Cyclohexylalkyl or 1-CH₂Or 2 or more not adjacent-CH₂Each independently can by-O- ,-S- ,-CO- ,-COO- ,- OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO- CH=CH- ,-OCO-CH=CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰,-CH=N-N=CH- ,-CF=CF- Or-C ≡ C- (in formula, R⁰Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8.) replace carbon atom number 1 to 20 straight-chain or Branch-like alkyl, any hydrogen atom in the alkyl can be replaced by fluorine atoms, in compound L there are it is multiple when they can be identical It can also be different.From the viewpoint of liquid crystal liquid crystal property, synthesis easiness, substituent group L preferably indicates fluorine atom, chlorine atom, five fluorine sulphur Alkyl, nitro, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl or any hydrogen atom can be by fluorine atoms Substitution and 1-CH₂Or 2 or more not adjacent-CH₂Can be selected from each independently-O- ,-S- ,-CO- ,-COO- ,- The straight-chain of the carbon atom number 1 to 20 of the group substitution of OCO- ,-O-CO-O- ,-CH=CH- ,-CF=CF- or-C ≡ C- is divided Branch shape alkyl, substituent group L more preferably indicates fluorine atom, chlorine atom or any hydrogen atom can be replaced by fluorine atoms and 1-CH₂- Or 2 or more not adjacent-CH₂It can be selected from the carbon atom number 1 that the group of-O- ,-COO- or-OCO- replace each independently To 12 straight-chain or branch-like alkyl, substituent group L further preferably indicates that fluorine atom, chlorine atom or any hydrogen atom can quilts The straight-chain or branch-like alkyl or alkoxy, substituent group L for the carbon atom number 1 to 12 that fluorine atom replaces particularly preferably indicate fluorine The straight chained alkyl or unbranched alkoxy of atom, chlorine atom or carbon atom number 1 to 8.

In above-mentioned general formula (I-1), Z¹¹And Z¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、- CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH- CO-NH-、-NH-O-、-O-NH-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH =CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N =CH- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z¹¹There are it is multiple when they can be the same or different, Z¹²There are it is multiple when they can be the same or different.Especially in the case where paying attention to orientation defect less, Z¹¹And Z¹²Respectively Independently preferably they can be the same or different and expression-OCH when there are multiple₂-、-CH₂O-、-CH₂CH₂-、- COO- ,-OCO- ,-CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-CH₂CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z¹¹With Z¹²More preferably they can be the same or different and expression-OCH when there are multiple each independently₂-、-CH₂O-、- COO- ,-OCO- ,-CO-NH- ,-NH-CO- ,-CH=CH-COO- ,-OCO-CH=CH- ,-CH=CH- ,-N=N- ,-CH=N-N =CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z¹¹And Z¹²Further preferably they can phase when there are multiple each independently With can also be different and expression-OCH₂-、-CH₂O- ,-COO- ,-OCO- ,-CO-NH- ,-NH-CO- or singly-bound, Z¹¹And Z¹²Respectively Independently particularly preferably they can be the same or different and expression-OCH when there are multiple₂-、-CH₂O-、-COO-、- OCO- or singly-bound.

In above-mentioned general formula (I-1), m111 and m112 each independently represent 0~2 integer, m111+m112 preferably 1 or 2, M111+m112 more preferable 2, any one of particularly preferred m111 and m112 are 1.

In above-mentioned general formula (I-1), R¹And R²It is former to each independently represent hydrogen atom, fluorine atom, cyano, hydroxyl, nitro, carbon The alkyl of subnumber 1 to 10, the alkoxy of carbon atom number 1 to 10, the acyl group of carbon atom number 2 to 10, carbon atom number 2 to 10 alkyl The aromatic series ring group of carbonyloxy group, the alkoxy carbonyl of carbon atom number 2 to 10 or carbon number 5~12, R¹Or R²In either indicate Group other than hydrogen atom.Preferred group here as other than hydrogen atom, more preferably expression fluorine atom, cyano, hydroxyl, nitre The alkoxy of base, the alkyl of carbon atom number 1 to 6 or carbon atom number 1 to 6, further preferably expression fluorine atom, carbon atom number 1 to 4 alkyl or the alkoxy of carbon atom number 1 to 4 particularly preferably indicate the alkyl or carbon atom number 1 to 4 of carbon atom number 1 to 4 Alkoxy.In addition, R¹Or R²In either indicate hydrogen atom other than group, preferably R¹And R²In a side indicate that hydrogen is former Son and another party indicate the group other than hydrogen atom.

Alternatively, R²It is preferred that with adjacent existing A¹²Possessed substituent group L connection and indicate cyclic group.

The 2 function polymerizable liquid crystal compounds that above-mentioned general formula (I-1) indicates can be used it is one kind or two or more, in order to special Property reduce Δ n, the total content for the 2 function polymerizable liquid crystal compounds that general formula (I-1) indicates is in polymerizable liquid crystal compound In the total amount of used polymerizable liquid crystal compound, 10~95 mass %, further preferably 20~90 matter are preferably comprised Measure %.In addition, in order to add in polymerizable liquid crystal compound be easy that twisted nematic or cholesteric phase is presented when chipal compounds, In the total amount of the polymerizable liquid crystal compound used in polymerizable liquid crystal compound, particularly preferably contain 30~85 matter Measure %.In addition, specifically, it is also preferred that containing the ratio when having used the following general formula (I-1-1)~general formula (I-1-23).

As the compound that general formula (I-1) is indicated, specifically, it is preferable that following formulas (I-1-1) is to formula (I-1-23) table The compound shown.

[changing 4]

[changing 5]

[changing 6]

[changing 7]

[changing 8]

(in above-mentioned general formula (I-1-1)~general formula (I-1-23), R^cIndicate fluorine atom, cyano, hydroxyl, nitro, carbon atom number 1 to 10 alkyl, the alkoxy of carbon atom number 1 to 10, the acyl group of carbon atom number 2 to 10, carbon atom number 2 to 10 alkyl oxycarbonyl oxygen The aromatic series ring group of base, the alkoxy carbonyl of carbon atom number 2 to 10 or carbon number 5~12, R^eAnd R^dEach independently represent hydrogen original Son or methyl, m1 and m2 each independently represent 0~8 integer, and n1 and n2 are indicated when each independently representing 0 or 1, m1=0 N2=0 is indicated when n1=0, m2=0.)

The compound that above-mentioned general formula (I-1-1)~general formula (I-1-23) indicates can more specifically illustrate below logical The compound that formula (I-1-1-1)~general formula (I-1-1-60) indicates, but it is not limited to these.

[changing 9]

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

(the 2 function polymerizable liquid crystal compounds that general formula (I-2) indicates)

In polymerizable liquid crystal compound of the invention, contain one kind or two or more 2 functions indicated by above-mentioned general formula (I-1) Polymerizable liquid crystal compound, can also be together with the 2 function polymerizable liquid crystal compounds that above-mentioned general formula (I-1) is indicated and with being selected from The one kind or two or more polymerizable liquid crystal compound for the 2 function polymerizable liquid crystal compounds that the following general formula (I-2) indicates.

[changing 21]

P¹²¹-(Sp¹²¹-X¹²¹)_q121-MG¹²¹-(X¹²²-Sp¹²²)_q122-P¹²² (I-2)

(in formula, P¹²¹And P¹²²Each independently represent polymerizable functional group, Sp¹²¹And Sp¹²²Each independently represent carbon original The alkylidene or singly-bound of subnumber 1~18,1-CH in the alkylidene₂Or 2 or more not adjacent-CH₂Each independently may be used To be replaced by-COO- ,-OCO- or-OCO-O-, 1 or 2 or more hydrogen atom possessed by the alkylidene can be by halogen atom (fluorine Atom, chlorine atom, bromine atom, iodine atom) or the substitution of CN base, X¹²¹And X¹²²Each independently represent-O- ,-S- ,-OCH₂-、- CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、- CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH-、-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂- COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound (wherein, P¹²¹- Sp¹²¹、P¹²²-Sp¹²²、Sp¹²¹-X¹²¹And Sp¹²²-X¹²²In, it is directly connected to not comprising hetero atom is mutual.), q121 and q122 are each From independently expression 0 or 1, MG¹²¹Indicate mesomorphic base.)

In above-mentioned general formula (I-2), P¹²¹And P¹²²Polymerizable functional group is each independently represented, is preferably indicated selected from following Formula (P-1) to formula (P-17) group,

[changing 22]

These polymerizable groups by free radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerisation come It is polymerize.When especially carrying out polymerizable ultraviolet as polymerization, preferred formula (P-1), formula (P-2), formula (P-3), formula (P- 4), formula (P-8), formula (P-10), formula (P-12) or formula (P-15), more preferable formula (P-1), formula (P-2), formula (P-3), formula (P-4), Formula (P-8) or formula (P-10), further preferred formula (P-1), formula (P-2) or formula (P-3), particularly preferred formula (P-1) or formula (P- 2)。

In above-mentioned general formula (I-2), Sp¹²¹And Sp¹²²The preferred alkylidene for indicating carbon atom number 1~15 each independently, should 1-CH in alkylidene₂Or 2 or more not adjacent-CH₂It can be taken each independently by-COO- ,-OCO- or-OCO-O- In generation, 1 or 2 or more hydrogen atom possessed by the alkylidene can be by halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) Or CN base replaces, Sp¹¹And Sp¹²More preferably indicate the alkylidene of carbon atom number 1~12 each independently, 1 in the alkylidene A-CH₂Or 2 or more not adjacent-CH₂It can be replaced each independently by-O- ,-COO- ,-OCO- or-OCO-O-.

In above-mentioned general formula (I-2), X¹²¹And X¹²²Preferred expression-O- ,-OCH each independently₂-、-CH₂O-、-CO-、- COO-、-OCO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CF₂O-、-OCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,- COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、- COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF= CF- ,-C ≡ C- or singly-bound, X¹²¹And X¹²²More preferable expression-O- ,-OCH each independently₂-、-CH₂O-、-CO-、-COO-、- OCO-、-O-CO-O-、-CF₂O-、-OCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH-、-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂- COO-、-CH₂- OCO- ,-CH=CH- ,-CF=CF- ,-C ≡ C- or singly-bound.

MG¹²²Indicate mesomorphic base, i.e. general formula (I-2-b).

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-(A1-Z1)_r1-A2-Z2-A3- (I-2-b)

In general formula (I-2-b), A1, A2 and A3 separately indicate Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-hexamethylene Alkenyl, oxinane -2,5- diyl, 1,3- bis-Alkane -2,5- diyl, tetrahydric thiapyran -2,5- diyl, Isosorbide-5-Nitrae-are bicyclic (2,2,2) Octamethylene, decahydronaphthalene -2,6- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, pyrazine -2,5- diyl, thiophene -2,5- bis- Base -, 1,2,3,4- naphthane -2,6- diyls, 2,6- naphthylene, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, 1,2, 3,4,4a, 9,10a- octahydro phenanthrene -2,7- diyls, Isosorbide-5-Nitrae-naphthylene, benzo [1,2-b:4,5-b '] Dithiophene -2,6- diyl, benzene And [1,2-b:4,5-b '] two selenophen -2,6- diyl, [1] benzothiophene simultaneously [3,2-b] thiophene -2,7- diyl, [1] benzo selenophen And [3,2-b] selenophen -2,7- diyl or fluorenes -2,7- diyl, Z1 and Z2 each independently represent-COO-,-OCO-, - CH₂CH₂-、-OCH₂-、-CH₂O- ,-CH=CH- ,-C ≡ C- ,-CH=CHCOO- ,-OCOCH=CH- ,-CH₂CH₂COO-、- CH₂CH₂OCO-、-COOCH₂CH₂-、-OCOCH₂CH₂,-C=N- ,-N=C- ,-CONH- ,-NHCO- ,-C (CF₃)₂, can have The alkyl or singly-bound of the carbon atom number 2~10 of halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), Z1 and Z2 are respectively independent Ground is preferably-COO- ,-OCO- ,-CH₂CH₂-、-OCH₂-、-CH₂O- ,-CH=CH- ,-C ≡ C- ,-CH=CHCOO- ,-OCOCH =CH- ,-CH₂CH₂COO-、-CH₂CH₂OCO-、-COOCH₂CH₂-、-OCOCH₂CH₂Or singly-bound, more preferably-COO- ,- OCO-、-OCH₂-、-CH₂O-、-CH₂CH₂O-、-CH₂CH₂OCO-、-COOCH₂CH₂-、-OCOCH₂CH₂Or singly-bound, r1 expression 0, 1,2 or 3, A1 and Z1 there are it is multiple when, respectively can be the same or different.Among this, A1, A2 and A3 are separately preferred Indicate Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, 2,6- naphthylene.

As the example of above-mentioned general formula (I-2), the compound of the following general formula (I-2-1)~(I-2-4) expression can be enumerated, but It is not limited to the following general formula.

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P¹²¹-(Sp¹²¹-X¹²¹)_q121-A2-Z2-A3-(X¹²²-Sp¹²²)_q122-P¹²² (I-2-1)

P¹²¹-(Sp¹²¹-X¹²¹)_q121-A11-Z11-A2-Z2-A3-(X¹²²-Sp¹²²)_q122-P¹²² (I-2-2)

P¹²¹-(Sp¹²¹-X¹²¹)_q121-A11-Z11-A12-Z12-A2-Z2-A3-(X¹²²-Sp¹²²)_q122-P¹²²

(I-2-3)

P¹²¹-(Sp¹²¹-X¹²¹)_q121-A11-Z11-A12-Z12-A13-Z13-A2-Z2-A3-(X¹²²-Sp¹²²)_q122-P¹²²

(1-2-4)

In formula, P¹²¹、Sp¹²¹、X¹²¹、q121、X¹²²、Sp¹²²、q122、P¹²²Respectively indicate the definition with above-mentioned general formula (I-2) Identical definition,

A11, A12, A13 and A2, A3 indicate definition identical with the definition of A1~A3 of above-mentioned general formula (I-2-b), respectively It can be the same or different,

Z11, Z12, Z13 and Z2 respectively indicate definition identical with the definition of Z1, Z2 of above-mentioned general formula (I-2-b), respectively It can be the same or different.

In the compound that above-mentioned general formula (I-2-1)~(I-2-4) is indicated, if using general formula (I-2-2)~(I-2-4) table That shows has the compound of 3 or more ring structures in compound, then the orientation of resulting optically anisotropic body becomes good Compound that is good thus preferred, particularly preferably being indicated using the general formula (I-2-2) in compound with 3 ring structures.

As above-mentioned general formula (I-2-1)~(I-2-4) indicate compound, can illustrate general formula below (I-2-1-1)~ The compound that general formula (I-2-1-36) indicates, but it is not limited to these.

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In general formula (I-2-1-1)~general formula (I-2-1-36), R^dAnd R^eEach independently represent hydrogen atom, fluorine atom, trifluoro Methyl or methyl,

Above-mentioned cyclic group can have 1 or more F, Cl, CF₃、OCF₃, CN base, the alkyl of carbon atom number 1~8, carbon it is former The alkoxy of subnumber 1~8, the alkanoyl of carbon atom number 1~8, the alkanoyloxy of carbon atom number 1~8, carbon atom number 1~8 alkane Epoxide carbonyl, the alkenyl of carbon atom number 2~8, the alkenyloxy group of carbon atom number 2~8, the enoyl- of carbon atom number 2~8, carbon atom The alkene acyloxy of number 2~8 as substituent group,

M1, m2, m3, m4 each independently represent 0~18 integer, each independently preferably 0~8 integer, n1, n2, N3, n4 each independently represent 0 or 1.

The 2 function polymerizable liquid crystal compounds that above-mentioned general formula (I-2) indicates can be used it is one kind or two or more, about general formula (I-2) total content of the 2 function polymerizable liquid crystal compounds indicated, the polymerism liquid used in polymerizable liquid crystal compound In the total amount of brilliant compound, 0~50 mass %, further preferably 0~30 mass % are preferably comprised.In addition, in order to polymerize Property liquid-crystal composition in be easy when being added to chipal compounds that twisted nematic is presented or cholesteric phase, the structure of preferred compound are Asymmetrical structure, or there is substituent group, the polymerism liquid used in polymerizable liquid crystal compound in mesomorphic skeleton part In the total amount of brilliant compound, particularly preferably contain 0~20 mass %.In addition, specifically, having used above-mentioned general formula (I- The compound that 2-1)~(I-2-4) indicates has further used what above-mentioned general formula (I-2-1-1)~general formula (I-2-1-36) indicated When compound, it is also preferred that containing the ratio.

The compound that above-mentioned general formula (I-2-1-1)~general formula (I-2-1-36) indicates can more specifically illustrate following The compound that indicates of general formula (I-2-2-1)~general formula (I-2-2-41), but be not limited to these.

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(simple function polymerizable liquid crystal compound)

(the simple function polymerizable liquid crystal compound that general formula (II-1) indicates)

It is characterized in that, in polymerizable liquid crystal compound of the invention, containing in the molecule with 1 polymerizable functional group Polymerizable liquid crystal compound (simple function polymerizable liquid crystal compound), it is therein one kind or two or more selected from the following general formula (I-1) The polymerizable liquid crystal compound of expression is as an essential component.

[changing 41]

(in general formula (II-1), P²¹¹Indicate polymerizable functional group,

A²¹¹And A²¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- two Base, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, naphthane -2,6- diyl, decahydro Naphthalene -2,6- diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or be taken by 1 or more substituent group L Generation,

L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyano, isocyano group, amino, hydroxyl Base, sulfydryl, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl silyl, dimethyl methyl silicon Alkyl, thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can substituted cyclohexylalkyl or 1- CH₂Or 2 or more not adjacent-CH₂It each independently can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S- CO-、-O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH =CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰,-CH=N-N=CH- ,-CF=CF- or-C ≡ C- (in formula, R⁰ Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8.) replace carbon atom number 1 to 20 straight-chain or branch-like alkyl, the alkane Any hydrogen atom in base can be replaced by fluorine atoms, in compound L there are it is multiple when they can be the same or different, A²¹² There are it is multiple when they can be the same or different,

Z²¹¹Expression-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、- O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O-NH-、-SCH₂-、- CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO- CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO- CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N-N=CH- ,-CF= CF- ,-C ≡ C- or singly-bound, Z²¹¹There are it is multiple when they can be the same or different,

M211 indicates 1~3 integer,

T²¹¹Indicate hydrogen atom ,-OH base ,-SH base ,-CN base ,-COOH base ,-NH₂Base ,-NO₂Base ,-COCH₃Base ,-O (CH₂)_nCH₃Or-(CH₂)_nCH₃, the integer of n expression 0~20.)

In above-mentioned general formula (II-1), P²¹¹It indicates polymerizable functional group, preferably indicates selected from following formula (P-1) to formula (P- 17) group,

[changing 42]

In above-mentioned general formula (II-1), A²¹¹And A²¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, tetrahydro Naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or by 1 Above substituent group L replaces.From the viewpoint of the easiness, the being easy to get property of raw material and liquid crystal liquid crystal property of synthesis, A²¹¹And A²¹² 1,4- phenylene that is unsubstituted or being replaced by 1 or more substituent group L, the Asia 1,4- hexamethylene are preferably indicated each independently Base, bicyclic [2.2.2] octane-Isosorbide-5-Nitrae-diyl, naphthalene -2,6- diyl or naphthalene-Isosorbide-5-Nitrae-diyl more preferably indicate to be selected from each independently Following formulas (A-1) to formula (A-16) group.

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Further also from refractive anisotrop it is low from the viewpoint of, further preferred A²¹¹And A²¹²In at least one table Show the group selected from above-mentioned formula (A-2) or formula (A-10), remaining is each independently represented selected from above-mentioned formula (A-1) to formula (A- 7) and the group of formula (A-10), even more preferably A²¹¹And A²¹²In at least one indicate the group that above-mentioned formula (A-2) indicates, Remaining each independently represents the group selected from above-mentioned formula (A-1) to formula (A-7), particularly preferred A²¹¹And A²¹²In at least 1 A group for indicating above-mentioned formula (A-2) and indicating, remaining each independently represents the base selected from above-mentioned formula (A-1) to formula (A-4) Group.It should be noted that A²¹²There are it is multiple when they can be the same or different.

In above-mentioned general formula (II-1), L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyanogen Base, isocyano group, amino, hydroxyl, sulfydryl, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl first Silylation, dimetylsilyl, thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can be substituted Cyclohexylalkyl or 1-CH₂Or 2 or more not adjacent-CH₂Each independently can by-O- ,-S- ,-CO- ,-COO- ,- OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO- CH=CH- ,-OCO-CH=CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰,-CH=N-N=CH- ,-CF=CF- Or-C ≡ C- (in formula, R⁰Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8.) replace carbon atom number 1 to 20 straight-chain or Branch-like alkyl, any hydrogen atom in the alkyl can be replaced by fluorine atoms, in compound L there are it is multiple when they can be identical It can also be different.From the viewpoint of liquid crystal liquid crystal property, synthesis easiness, substituent group L preferably indicates fluorine atom, chlorine atom, five fluorine sulphur Alkyl, nitro, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl or any hydrogen atom can be by fluorine atoms Substitution and 1-CH₂Or 2 or more not adjacent-CH₂Can be selected from each independently-O- ,-S- ,-CO- ,-COO- ,- The straight-chain of the carbon atom number 1 to 20 of the group substitution of OCO- ,-O-CO-O- ,-CH=CH- ,-CF=CF- or-C ≡ C- is divided Branch shape alkyl, substituent group L more preferably indicates fluorine atom, chlorine atom or any hydrogen atom can be replaced by fluorine atoms and 1-CH₂- Or 2 or more not adjacent-CH₂It can be selected from the carbon atom number 1 that the group of-O- ,-COO- or-OCO- replace each independently To 12 straight-chain or branch-like alkyl, substituent group L further preferably indicates that fluorine atom, chlorine atom or any hydrogen atom can quilts The straight-chain or branch-like alkyl or alkoxy, substituent group L for the carbon atom number 1 to 12 that fluorine atom replaces particularly preferably indicate fluorine The straight chained alkyl or unbranched alkoxy of atom, chlorine atom or carbon atom number 1 to 8.

In above-mentioned general formula (II-1), Z²¹²Expression-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、-CO-、-COO-、- OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH- O-、-O-NH-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,- COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、- COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N- N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z²¹²There are it is multiple when they can be the same or different.

In above-mentioned general formula (II-1), in the case where paying attention to orientation defect less, Z²¹²It is preferred that they can be with when there are multiple It is identical to can also be different and expression-OCH₂-、-CH₂O-、-CH₂CH₂-、-COO-、-OCO-、-CO-NH-、-NH-CO-、-CF₂O-、- OCF₂,-CH=CH-COO- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-CH₂CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH= N- ,-N=CH- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z²¹²More preferably they can be with when there are multiple It is identical to can also be different and expression-COO- ,-OCO- ,-CO-NH- ,-NH-CO- ,-CF₂O-、-OCF₂,-CH=CH-COO- ,- OCO-CH=CH- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z²¹²Further preferably They can be the same or different and expression-COO- ,-OCO- ,-CO-NH- ,-NH-CO- ,-CF when there are multiple₂O-、- OCF₂Or singly-bound, Z²¹²Particularly preferably when there are multiple they can be the same or different and expression-COO- ,-OCO- ,- CF₂O-、-OCF₂Or singly-bound.

In above-mentioned general formula (II-1), m211 indicates that 1~3 integer, m211 preferably indicate 1 or 2, and m211 preferably indicates 1.

In above-mentioned general formula (II-1), T²¹¹Indicate hydrogen atom ,-OH base ,-SH base ,-CN base ,-COOH base ,-NH₂Base ,-NO₂ Base ,-COCH₃Base ,-O (CH₂)_nCH₃Or-(CH₂)_nCH₃(n indicates 0~20 integer), T²¹¹More preferably indicate hydrogen atom ,-O (CH₂)_nCH₃Or-(CH₂)_nCH₃(n indicates 0~10 integer), T²¹¹Particularly preferred expression-O (CH₂)_nCH₃Or-(CH₂)_nCH₃(n Indicate 0~8 integer).

The simple function polymerizable liquid crystal compound that above-mentioned general formula (II-1) indicates can be used it is one kind or two or more, about logical The total content for the simple function polymerizable liquid crystal compound that formula (II-1) indicates polymerize used in polymerizable liquid crystal compound In the total amount of property liquid-crystal compounds, 5~85 mass %, further preferably 10~80 mass % are preferably comprised.In addition, in order to Making the polymerizable liquid crystal compound, by birefringence anisotropy, (Δ n) inhibits lower, in polymerizable liquid crystal compound when polymerizeing In the total amount of used polymerizable liquid crystal compound, particularly preferably contain 15~70 mass %.In addition, specifically, making With when the following general formula (II-1-1)~general formula (II-1-22) it is also preferred that contain the ratio.

As the compound that general formula (II-1) is indicated, specifically, it is preferable that following formulas (II-1-1) is to formula (II-1-22) The compound of expression.

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In general formula (II-1-1)~general formula (II-1-22), R^cIndicate hydrogen atom, fluorine atom, trifluoromethyl or methyl, about Above-mentioned cyclic group, as substituent group, indicates that 1 or more fluorine atom, chlorine is former in the case that hydrogen atom is substituted with a substituent Son, Pentafluorosulfanyl, nitro, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl or any hydrogen atom can It is replaced by fluorine atoms and 1-CH₂Or 2 or more not adjacent-CH₂Can be selected from each independently-O- ,-S- ,-CO- ,- The straight chain of the carbon atom number 1 to 20 of the group substitution of COO- ,-OCO- ,-O-CO-O- ,-CH=CH- ,-CF=CF- or-C ≡ C- Shape or branch-like alkyl, T^cIndicate hydrogen atom ,-OH base ,-SH base ,-CN base ,-COOH base ,-NH₂Base ,-NO₂Base ,-COCH₃Base ,- O(CH₂)_nCH₃Or-(CH₂)_nCH₃(n indicates 0~20 integer).

As the compound that general formula (II-1-1)~general formula (II-1-22) indicates, specifically, it is preferable that following formula (II- 1-1-1) to the compound that formula (II-1-1-31) is indicated.

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(the simple function polymerizable liquid crystal compound that general formula (II-2) indicates)

In polymerizable liquid crystal compound of the invention, contain the one kind or two or more single official indicated by above-mentioned general formula (II-1) Energy polymerizable liquid crystal compound can also be used in combination together with the simple function polymerizable liquid crystal compound that above-mentioned general formula (II-1) is indicated The one kind or two or more polymerizable liquid crystal chemical combination of the simple function polymerizable liquid crystal compound indicated selected from the following general formula (II-2) Object.

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P²²¹-Sp²²¹-X²²¹-MG²²¹-R²²¹ (II-2)

In formula, P²²¹Indicate polymerizable functional group, Sp²²¹Indicate the alkylidene or singly-bound of carbon atom number 1~18, the alkylidene In 1-CH₂Or 2 or more not adjacent-CH₂It can be replaced each independently by-O- ,-COO- ,-OCO- or-OCO-O-, 1 or 2 or more hydrogen atom can be by halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or CN possessed by the alkylidene Base replaces, X²²¹Expression-O- ,-S- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、- CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH- OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂- OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF =CF- ,-C ≡ C- or singly-bound (wherein, P²²¹-Sp²²¹And Sp²²¹-X²²¹In, it is mutual directly not comprising the hetero atom other than C, H Connection.), MG²²¹Indicate mesomorphic base, R²²¹Indicate hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano, The straight chain or branched alkyl groups of carbon atom number 1 to 12, the straight chain of carbon atom number 1 to 12 or branch's alkenyl, 1 in the alkyl and alkenyl A-CH₂Or 2 or more not adjacent-CH₂It each independently can be by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S- CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-NH-、-N(CH₃)-,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH =CH- ,-OCO-CH=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C- replace, 1 or 2 possessed by the alkyl and the alkenyl A above hydrogen atom can be replaced each independently by halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or cyano, when It can be the same or different respectively when replacing multiple.

In above-mentioned general formula (II-2), P²²¹It indicates polymerizable functional group, preferably indicates selected from following formula (P-1) to formula (P- 17) group,

[changing 55]

In above-mentioned general formula (II-2), Sp²²¹It is preferred that indicate the alkylidene of carbon atom number 1~15,1 in the alkylidene- CH₂Or 2 or more not adjacent-CH₂It can be replaced each independently by-O- ,-COO- ,-OCO- or-OCO-O-, the alkylidene Possessed 1 or 2 or more hydrogen atom can be taken by halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or CN base Generation, Sp²²More preferably indicate the alkylidene of carbon atom number 1~12,1-CH in the alkylidene₂Or not adjacent 2 or more- CH₂It can be replaced each independently by-O- ,-COO- ,-OCO- or-OCO-O-.

In above-mentioned general formula (II-2), X²²¹It is preferred that expression-O- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-O-CO- O-、-CO-NH-、-NH-CO-、-CF₂O-、-OCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO- CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO- CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, X²²¹More preferable expression-O- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-O-CO-O-、-CF₂O-、-OCF₂,-CH= CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、- CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-CF= CF- ,-C ≡ C- or singly-bound.

In above-mentioned general formula (II-2), MG²²¹Indicate mesomorphic base, i.e. general formula (II-2-b).

[changing 56]

-(A1-Z1)_r1-A2-Z2-A3- (II-2b)

(in formula, A1 and A2 separately indicate Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexenyl group, tetrahydro pyrrole It mutters -2,5- diyl, 1,3- bis-Bicyclic (2,2,2) octamethylene of alkane -2,5- diyl, tetrahydric thiapyran -2,5- diyl, 1,4-, decahydro Naphthalene -2,6- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, pyrazine -2,5- diyl, thiophene -2,5- diyl, 1,2,3,4- Naphthane -2,6- diyl, 2,6- naphthylene, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, 1,2,3,4,4a, 9,10a- Octahydro phenanthrene -2,7- diyl, 1,4- naphthylene, benzo [1,2-b:4,5-b '] Dithiophene -2,6- diyl, benzo [1,2-b:4,5-b '] two selenophen -2,6- diyls, [1] benzothiophene simultaneously [3,2-b] thiophene -2,7- diyl, [1] benzo selenophen simultaneously [3,2-b] selenophen - 2,7- diyls, fluorenes -2,7- diyl, cholest or cholesteric alkyl, as substituent group L², can have 1 or more F, Cl, CF₃、 OCF₃, CN base, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, the alkanoyl of carbon atom number 1~8, carbon atom The alkanoyloxy of number 1~8, the alkoxy carbonyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 2~8 alkene The alkene acyloxy of oxygroup, the enoyl- of carbon atom number 2~8, and/or carbon atom number 2~8, among this, A1~A3 is separately It is preferred that indicating can there is above-mentioned substituent group L²1,4- phenylene, 1,4- cyclohexylidene, 2,6- naphthylene.In addition, as substitution Base L², the alkoxy of preferably F, the alkyl of carbon atom number 1~8 or carbon atom number 1~8.

In above-mentioned general formula (II-2), R²²¹More preferably indicate that (fluorine atom, chlorine atom, bromine atom, iodine are former for hydrogen atom, halogen atom Son), cyano, the straight chain of carbon atom number 1 to 8 or branched alkyl groups, the straight chain of carbon atom number 1 to 8 or branch's alkenyl, the alkyl and alkene 1-CH in base₂Or 2 or more not adjacent-CH₂It each independently can be by-O- ,-CO- ,-COO- ,-OCO- ,-O-CO- O- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-CH=CH- or-C ≡ C- replace, 1 or 2 or more hydrogen atom possessed by the alkyl and the alkenyl each independently can be by halogen atom (fluorine atom, chlorine atom, bromine Atom, iodine atom) or cyano replace, whens multiple substitutions, can be the same or different respectively.

As the example of general formula (II-2), the compound of the following general formula (II-2-1)~(II-2-4) expression can be enumerated, but It is not limited to following general formulas.

[changing 57]

P²²¹-Sp²²¹-X²²¹-A2-Z2-A3-R²²¹ (II-2-1)

P²²¹-Sp²²¹-X²²¹-A11-Z11-A2-Z2-A3-R²²¹ (II-2-2)

P²²¹-Sp²²¹-X²²¹-A11-Z11-A12-Z12-A2-Z2-A3-R²²¹ (II-2-3)

P²²¹-Sp²²¹-X²²¹-A11-Z11-A12-Z12-A13-Z13-A2-Z2-A3-R²²¹ (Il-2-4)

In formula, p²²¹、Sp²²¹、X²²¹And R²²¹Definition identical with the definition of above-mentioned general formula (II-2) is respectively indicated,

A11, A12, A13, A2, A3 indicate definition identical with the definition of A1~A3 of above-mentioned general formula (II-2-b), respectively It can be the same or different,

Z1I, Z12, Z13, Z2 indicate identical with the definition of Z1~Z3 of above-mentioned general formula (II-2-b) definition, and distinguishing can be with It is identical to can also be different,

As the compound that above-mentioned general formula (II-2-1)~(II-2-4) is indicated, general formula below (II-2-1-1) can be illustrated The compound that~general formula (II-2-1-26) indicates, but it is not limited to these.

[changing 58]

[changing 59]

[changing 60]

[changing 61]

[changing 62]

In above-mentioned general formula (II-2-1-1)~general formula (II-2-1-26), R^cIndicate that hydrogen atom or methyl, m indicate 1~18 Integer, n indicate 0 or 1, R²²¹Indicate definition identical with above-mentioned general formula (the II-2-1)~definition of (II-2-4), R²²¹It is preferred that table Show hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano, 1-CH₂Can by-O- ,-CO- ,- The straight chained alkyl for the carbon atom number 1 to 6 that COO- ,-OCO- replace or the straight-chain alkenyl of carbon atom number 1 to 6.

In above-mentioned general formula (II-2-1-1)~general formula (II-2-1-26), cyclic group can have 1 or more F, Cl, CF₃、 OCF₃, CN base, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, the alkanoyl of carbon atom number 1~8, carbon atom The alkanoyloxy of number 1~8, the alkoxy carbonyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 2~8 alkene Oxygroup, the enoyl- of carbon atom number 2~8, carbon atom number 2~8 alkene acyloxy as substituent group.

The simple function polymerizable liquid crystal compound that above-mentioned general formula (II-2) indicates can be used it is one kind or two or more, about general formula (II-2) total content of the simple function polymerizable liquid crystal compound indicated, the polymerism used in polymerizable liquid crystal compound In the total amount of liquid-crystal compounds, 0~40 mass %, further preferably 0~35 mass % are preferably comprised.In addition, in order to make By birefringence anisotropy, (Δ n) inhibits lower, in polymerizable liquid crystal compound institute when the polymerizable liquid crystal compound polymerize In the total amount of the polymerizable liquid crystal compound used, particularly preferably contain 0~30 mass %.In addition, specifically, using When above-mentioned general formula (II-2-1)~general formula (II-2-4), above-mentioned general formula (II-2-1-1)~general formula (II-2-1- is further used 26) when, it is also preferred that containing the ratio.

(multifunctional polymerizable liquid crystal compound)

In polymerizable liquid crystal compound of the invention, in the range of not damaging physical property, it can also contain and have in the molecule There is the polymerizable liquid crystal compound of 3 or more polymerizable functional groups.As in the molecule with 3 or more polymerizable functional groups Polymerizable liquid crystal compound can illustrate the following general formula (III-1), the compound that general formula (III-2) indicates.

[changing 63]

(in formula, P³¹~P³⁵Each independently represent polymerizable functional group, Sp³¹~S³⁵Each independently represent carbon atom number 1~18 alkylidene or singly-bound, 1-CH in the alkylidene₂Or 2 or more not adjacent-CH₂Each independently can by- O- ,-COO- ,-OCO- or-OCO-O- replace, and 1 or 2 or more hydrogen atom can be by halogen atom (fluorine original possessed by the alkylidene Son, chlorine atom, bromine atom, iodine atom) or the substitution of CN base, X³¹~X³⁵Each independently represent-O- ,-S- ,-OCH₂-、- CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、- CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH-、-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂- COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound (wherein, P³¹- Sp³¹、P³²-Sp³²、P³³-Sp³³、P³⁴-Sp³⁴、P³⁵-Sp³⁵、Sp³¹-X³¹、Sp³²-X³²、Sp³³-X³³、Sp³⁴-X³⁴And Sp³⁵-X³⁵In It is directly connected to not comprising oxygen atom is mutual.), q31, q32, q34, q35, q36, q37, q38 and q39 each independently represent 0 Or 1, j3 indicates 0 or 1, MG³¹Indicate mesomorphic base.)

In above-mentioned general formula (III-1)~general formula (III-2), P³¹~P³⁵It is preferred each independently to indicate from following formula (P- 2-1) the substituent group selected in the polymerizable group indicated to formula (P-2-20).

[changing 64]

In these polymerizable functional groups, from the viewpoint of improving polymerism, preferred formula (P-2-1), (P-2-2), (P-2- 7), (P-2-12), (P-2-13), more preferable formula (P-2-1), (P-2-2).

In above-mentioned general formula (III-1)~general formula (III-2), Sp³¹~Sp³⁵It is preferred each independently indicate carbon atom number 1~ 15 alkylidene, 1-CH in the alkylidene₂Or 2 or more not adjacent-CH₂Each independently can by-O- ,-COO- ,- OCO- or-OCO-O- replace, 1 or 2 or more hydrogen atom possessed by the alkylidene can by halogen atom (fluorine atom, chlorine atom, Bromine atom, iodine atom) or the substitution of CN base, Sp³¹~Sp³⁵The alkylidene of carbon atom number 1~12 is more preferably indicated each independently, 1-CH in the alkylidene₂Or 2 or more not adjacent-CH₂It each independently can be by-O- ,-COO- ,-OCO- or-OCO- O- replaces.

In above-mentioned general formula (III-1)~general formula (III-2), X³¹~X³⁵Preferred expression-O- ,-OCH each independently₂-、- CH₂O-、-CO-、-COO-、-OCO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CF₂O-、-OCF₂,-CH=CH-COO- ,-CH =CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N-N= CH- ,-CF=CF- ,-C ≡ C- or singly-bound, X³¹~X³⁵More preferable expression-O- ,-OCH each independently₂-、-CH₂O-、-CO-、- COO-、-OCO-、-O-CO-O-、-CF₂O-、-OCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO- CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO- CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-CF=CF- ,-C ≡ C- or singly-bound.

In above-mentioned general formula (III-1)~general formula (III-2), MG³¹It indicates mesomorphic base, is indicated by general formula (III-A).

[changing 65]

-(A1-Z1)_r1-A2-Z2-A3- (III-A)

In formula, A1, A2 and A3 separately indicate Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexenyl group, tetrahydro Pyrans -2,5- diyl, 1,3- bis-Bicyclic (2,2,2) octamethylene of alkane -2,5- diyl, tetrahydric thiapyran -2,5- diyl, 1,4-, ten Hydrogen naphthalene -2,6- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, pyrazine -2,5- diyl, thiophene -2,5- diyl -, 1,2,3, 4- naphthane -2,6- diyl, 2,6- naphthylene, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, 1,2,3,4,4a, 9, 10a- octahydro phenanthrene -2,7- diyl, 1,4- naphthylene, benzo [1,2-b:4,5-b '] Dithiophene -2,6- diyl, benzo [1,2-b: 4,5-b '] two selenophen -2,6- diyls, simultaneously [3,2-b] thiophene -2,7- diyl, [1] benzo selenophen be simultaneously [3,2-b] for [1] benzothiophene Selenophen -2,7- diyl or fluorenes -2,7- diyl, can have 1 or more F, Cl, CF₃、OCF₃, CN base, carbon atom number 1~8 Alkyl, the alkoxy of carbon atom number 1~8, the alkanoyl of carbon atom number 1~8, the alkanoyloxy of carbon atom number 1~8, carbon atom The alkoxy carbonyl of number 1~8, the alkenyl of carbon atom number 2~8, the alkenyloxy group of carbon atom number 2~8, carbon atom number 2~8 alkene acyl Base, and/or the alkene acyloxy of carbon atom number 2~8 are deposited as substituent group when forming the structure that above-mentioned general formula (III-1) indicates Any one of A1, A2 and A3 there is-(X³³)_q35-(Sp³³)_q34-P³³Base.Z1 and Z2 each independently represent-COO- ,- OCO-、-CH₂CH₂-、-OCH₂-、-CH₂O- ,-CH=CH- ,-C ≡ C- ,-CH=CHCOO- ,-OCOCH=CH- ,- CH₂CH₂COO-、-CH₂CH₂OCO-、-COOCH₂CH₂-、-OCOCH₂CH₂,-C=N- ,-N=C- ,-CONH- ,-NHCO- ,-C (CF₃)₂, can have halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) carbon atom number 2~10 alkyl or singly-bound, Z1 and Z2 is preferably-COO- ,-OCO- ,-CH each independently₂CH₂-、-OCH₂-、-CH₂O- ,-CH=CH- ,-C ≡ C- ,-CH= CHCOO- ,-OCOCH=CH- ,-CH₂CH₂COO-、-CH₂CH₂OCO-、-COOCH₂CH₂-、-OCOCH₂CH₂Or singly-bound, r1 are indicated 0,1,2 or 3, A1 and Z1 there are it is multiple when, respectively can be the same or different.).Among this, A1, A2 and A3 are separately It is preferred that indicating 1,4- phenylene, 1,4- cyclohexylidene, 2,6- naphthylene.

As the example of logical formula (III), the following general formula (III-1-1)~general formula (III-1-8), general formula (III- can be enumerated 2-1)~general formula) III-2-2) compound that indicates, but it is not limited to following general formulas.

[changing 66]

[changing 67]

In formula, P³¹~P³⁵、Sp³¹~Sp³⁵、X³¹~X³⁵, q31~q39MG³¹Respectively indicate with above-mentioned general formula (III-1)~ The identical definition of definition of general formula (III-2),

A11, A12, A13 and A2, A3 respectively indicate definition identical with the definition of A1~A3 of above-mentioned general formula (III-A), It can be the same or different respectively,

Z11, Z12, Z13 and Z2 respectively indicate definition identical with the definition of Z1, Z2 of above-mentioned general formula (III-A), respectively It can be the same or different.

It is indicated as above-mentioned general formula (III-1-1)~general formula (III-1-8), general formula (III-2-1), general formula (III-2-2) Compound, the compound of general formula below (III-9-1)~(III-9-6) expression can be illustrated, but be not limited to these.

[changing 68]

[changing 69]

[changing 70]

In above-mentioned general formula (III-9-1)~(III-9-6), R^f、R^gAnd R^hEach independently represent hydrogen atom or methyl, Rⁱ、 R^jAnd R^kEach independently represent hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carbon number 1~6 alkyl, Alkoxy, the cyano of carbon number 1~6 can be with when the alkoxy of alkyl or carbon number 1~6 that these groups are carbon number 1~6 Whole is unsubstituted or is replaced by 1 or 2 or more halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), above-mentioned Cyclic group can have 1 or more F, Cl, CF₃、OCF₃, CN base, the alkyl of carbon atom number 1~8, carbon atom number 1~8 alkane Oxygroup, the alkanoyl of carbon atom number 1~8, the alkanoyloxy of carbon atom number 1~8, the alkoxy carbonyl of carbon atom number 1~8, carbon The alkenyl of atomicity 2~8, the alkenyloxy group of carbon atom number 2~8, the enoyl- of carbon atom number 2~8, carbon atom number 2~8 alkene acyl Oxygroup is as substituent group.

M4~m9 each independently represents 0~18 integer, and n4~n10 each independently represents 0 or 1.

Multifunctional polymerizable liquid crystal compound with 3 or more polymerizable functional groups can be used one kind or two or more.

There is total content of the multifunctional polymerizable liquid crystal compound of 3 polymerizable functional groups about intramolecular, poly- In the total amount of polymerizable liquid crystal compound used in conjunction property liquid-crystal composition, 0~20 mass % is preferably comprised, is more preferably contained There is 0~10 mass %, particularly preferably contains 0~5 mass %.

Polymerizable liquid crystal compound of the invention passes through and the general formula (I-1) in above-mentioned polymerizable liquid crystal compound is used to indicate 2 function polymerizable liquid crystal compounds and general formula (II-1) indicate simple function polymerizable liquid crystal compound, can obtain two-fold Penetrate rate it is poor (Δ n) be 0.1 optical film below.

In addition, 2 function polymerizable liquid crystal compounds that polymerizable liquid crystal compound of the invention is indicated with general formula (I-1) and The simple function polymerizable liquid crystal compound that general formula (II-1) indicates is essential component, is gathered used in polymerizable liquid crystal compound In the total amount of conjunction property liquid-crystal compounds, which preferably comprises 60~100 mass %, further preferably 70~100 Quality % particularly preferably contains 75~100 mass %.

Further, aftermentioned chipal compounds are added in polymerizable liquid crystal compound, and twisted nematic or cholesteric is presented Xiang Shi, by containing 30~85 mass % in the total amount of the polymerizable liquid crystal compound used in polymerizable liquid crystal compound The 2 function polymerizable liquid crystal compounds indicated by general formula (I-1), so as to obtain selection reflection wavelength band domain (Δ λ)/selection The value of reflection kernel wavelength (λ) is 0.1 optical film below, and the permeability of the resulting optical film is excellent.

Selection reflection wavelength band domain (Δ λ)/selection reflection kernel wavelength (λ) about aforementioned optical film of the invention Value, can be suitable for the general formula (II-1) adjusted in polymerizable liquid crystal compound of the invention by technical field according to the present invention The weight rate of the polymerizable liquid crystal compound of expression is to apply, in aforementioned selection reflection wavelength band domain (Δ λ)/selection reflection Cardiac wave grows the value more preferable 0.010 or more 0.095 of (λ) hereinafter, further preferred 0.020 or more 0.090 hereinafter, particularly preferably 0.030 or more 0.080 or less.

(other liquid-crystal compounds)

In addition, can also being added in polymerizable liquid crystal compound of the invention without polymerizable group and contain mesomorphic base Compound, it is (thin that common liquid crystal apparatus, such as STN (super twisted nematic) liquid crystal, TN (twisted-nematic) liquid crystal, TFT can be enumerated Film transistor) compound used in liquid crystal etc..

Specifically general formula (5) preferably below indicates for compound without polymerizable functional group containing mesomorphic base Compound.

[changing 71]

R⁵¹-MG3-R⁵² (5)

Mesomorphic base represented by MG3 or mesomorphism support base that can enumerate the compound of general formula (5-b) expression.

[changing 72]

-ZO^d-(A1^d-Z1^d)_ne-A2^d-Z2^d-A3^d-Z3^d- (5-b)

(in formula, A1^d、A2^dAnd A3^dSeparately indicate 1,4- phenylene, 1,4- cyclohexylidene, 1,4- cyclohexenyl group, Oxinane -2,5- diyl, 1,3- bis-Bicyclic (2,2,2) Ya Xin of alkane -2,5- diyl, tetrahydric thiapyran -2,5- diyl, 1,4- Base, decahydronaphthalene -2,6- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, pyrazine -2,5- diyl, thiophene -2,5- diyl -, 1,2,3,4- naphthane -2,6- diyl, 2,6- naphthylene, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, 1,2,3,4, 4a, 9,10a- octahydro phenanthrene -2,7- diyl, 1,4- naphthylene, benzo [1,2-b:4,5-b '] Dithiophene -2,6- diyl, benzo [1, 2-b:4,5-b '] two selenophen -2,6- diyls, [1] benzothiophene simultaneously [3,2-b] thiophene -2,7- diyl, [1] benzo selenophen simultaneously [3, 2-b] selenophen -2,7- diyl or fluorenes -2,7- diyl, it can have 1 or more F, Cl, CF₃、OCF₃, CN base, carbon atom number 1 ~8 alkyl, alkoxy, alkanoyl, alkanoyloxy, the alkenyl of carbon atom number 2~8, alkenyloxy group, enoyl-, alkene acyloxy are made For substituent group,

Z0^d、Z1^d、Z2^dAnd Z3^dEach independently represent-COO- ,-OCO- ,-CH₂CH₂-、-OCH₂-、-CH₂O- ,-CH= CH- ,-C ≡ C- ,-CH=CHCOO- ,-OCOCH=CH- ,-CH₂CH₂COO-、-CH₂CH₂OCO-、-COOCH₂CH₂-、- OCOCH₂CH₂,-CONH- ,-NHCO-, carbon number 2~10 there is halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) Alkylidene or singly-bound,

n^eIndicate 0,1 or 2,

R⁵¹And R⁵²Each independently represent hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano Or the alkyl of carbon atom number 1~18, the alkyl can be by 1 or more halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) Or CN replaces, 1 CH being present in the group₂Base or 2 or more not adjacent CH₂Base can respectively independently of each other with The form that oxygen atom is not bound directly mutually is by-O- ,-S- ,-NH- ,-N (CH₃)-、-CO-、-COO-、-OCO-、-OCOO-、- SCO- ,-COS- or-C ≡ C- replace.)

Specifically, being shown in hereinafter, but being not limited to these.

[changing 73]

Ra and Rb each independently represents hydrogen atom, the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, carbon number 1~6 Alkenyl, cyano, when these groups be carbon number 1~6 alkyl or carbon number 1~6 alkoxy when, can all it is unsubstituted, Or it can be replaced by 1 or 2 or more halogen atom.

The total content of compound with mesomorphic base relative to the total amount of polymerizable liquid crystal compound be preferably 0 mass % with Upper 20 mass % is hereinafter, in the case where use, preferably 1 mass % or more, preferably 2 mass % or more, preferably 5 mass % More than, additionally, it is preferred that being 15 mass % hereinafter, preferably 10 mass % or less.

(organic solvent)

Organic solvent can be added in polymerizable liquid crystal compound of the invention.As organic solvent used without spy It does not limit, preferred polymeric liquid-crystal compounds shows the organic solvent of good dissolubility, is preferably able in 100 DEG C of temperature below Spend dry organic solvent.As such solvent, it can be mentioned, for example the aromatic series such as toluene, dimethylbenzene, isopropylbenzene, mesitylene It is the ester series solvents such as hydrocarbon, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone (MEK), methyl-isobutyl The ether series solvents such as the ketone series solvents such as ketone (MIBK), cyclohexanone, cyclopentanone, tetrahydrofuran, 1,2- dimethoxy-ethane, methyl phenyl ethers anisole, The acid amides series solvents such as N,N-dimethylformamide, n-methyl-2-pyrrolidone, propylene glycol monomethyl ether, diethylene glycol Monomethyl ether acetate, gamma-butyrolacton and chlorobenzene etc..These can be used alone, and two or more mixing can also be used, From from the viewpoint of stability of solution, it is preferable to use in ketone series solvent, ether series solvent, ester series solvent and aromatic hydrocarbon series solvent Any a kind or more.

If composition used in the present invention to be made to the solution for having used organic solvent, substrate can be applied Cloth, the ratio of organic solvent used in polymerizable liquid crystal compound as long as long as the state after significantly damage coating without special It limits, the total amount of organic solvent contained in polymerizable liquid crystal compound is preferably 10~95 mass %, further preferably For 12~90 mass %, particularly preferably 15~85 mass %.

When polymerizable liquid crystal compound is dissolved in organic solvent, in order to make it dissolve uniformly, heating stirring is preferably carried out. As long as heating temperature when heating stirring considers that used composition suitably adjusts the dissolubility of organic solvent , from the viewpoint of productivity, preferably 15 DEG C~110 DEG C, more preferable 15 DEG C~105 DEG C, further preferred 15 DEG C~100 DEG C, particularly preferably it is set as 20 DEG C~90 DEG C.

Additionally, it is preferred that being stirred mixing using dispersator when adding solvent.As dispersator, it is specific and Disperser, propeller, the dispersion machine with stirring wings such as turbo blades, paint shaker, planetary stirring dress can be used in speech It sets, bobbing machine, vibrating machine or rotary evaporator etc..In addition to this it is possible to use ultrasonic wave irradiation device.

Agitation revolution when adding solvent is preferably suitable for adjustment according to used agitating device, uniform poly- in order to be made Conjunction property liquid-crystal composition solution, is preferably set as 10rpm~1000rpm for agitation revolution, is more preferably set as 50rpm~800rpm, Particularly preferably it is set as 150rpm~600rpm.

(polymerization inhibitor)

It is preferred that adding polymerization inhibitor in polymerizable liquid crystal compound of the invention.As polymerization inhibitor, phenol system chemical combination can be enumerated Object, oxime-based compound, amine compound, thioether based compound, nitroso compound etc..

As phenol system compound, p methoxy phenol, cresols, tert-butyl catechol, 3,5- di-t-butyl -4- can be enumerated Hydroxy-methylbenzene, 2,2'- methylene two (4- methyl-6-tert-butylphenol), (4- ethyl -6- tert-butyl benzene of 2,2'- methylene two Phenol), 4,4'- thio two (3 methy 6 tert butyl phenol), 4- methoxyl group -1- naphthols, 4,4 '-dialkoxies -2,2 '-connection -1- Naphthols etc..

As oxime-based compound, quinhydrones, methylnaphthohydroquinone, tert-butyl hydroquinone, 1,4-benzoquinone, methyl -1,4-benzoquinone, tertiary fourth can be enumerated Base -1,4-benzoquinone, 2,5- diphenyl-benzoquinone, 2 hydroxy 1,4 naphthoquinone (lawsone), 1,4- naphthoquinones, 2,3 dichlro 1,4 naphtho quinone, anthraquinone, biphenyl Quinone etc..

As amine compound, p-phenylenediamine, 4- amino-diphenyl-amine, N, N'- diphenyl-p-phenylenediamine, N- can be enumerated Isopropyl-N'- phenyl-pphenylenediamine, N- (1,3- dimethylbutyl)-N'- phenyl-pphenylenediamine, N, bis- -2- naphthalene of N'--right Phenylenediamine, diphenylamine, N- phenyl-β-naphthylamine, 4,4'- dicumyl-diphenylamine, 4,4'- dioctyl-diphenylamine etc..

As thioether based compound, phenthazine, distearyl thiodipropionate etc. can be enumerated.

As nitroso based compound, N- nitrosodiphenylamine int he, N- nitroso phenyl naphthyl amines, N- nitroso can be enumerated Dinaphthyl amine, p-Nitrosophenol, nitrosobenzene, to nitrosodiphenylamine int he, alpha-nitroso-beta-naphthol etc., N, N- dimethyl To nitrosoaniline, to nitrosodiphenylamine int he, to nitroso dimethyl amine, accelerine, N- diethylamide, N- nitroso Ethanol amine, N- nitroso di-n-butyl amine, N- nitroso-N- normal-butyl -4- butanolamine, N- nitroso-diisopropanolamine (DIPA), N- are sub- Nitro-N- ethyl -4- butanolamine, 5- nitroso -8-hydroxyquinoline, N-nitrosomorpholine, N- nitroso-N- phenylhydroxylamine ammonium Salt, nitrosobenzene, 2,4,6- tri-tert nitrosobenzene, N- nitroso-N- methyl-p-toluenesulfonamide, N- nitroso-N- second Aminocarbamic acid ester, N- nitroso-N- n-propyl amino formic acid esters, 1-Nitroso-2-naphthol, 2- nitroso -1- naphthols, 1- are sub- Nitro-beta naphthal -3,6- sodium sulfonate, 2- nitroso-Neville acid sodium, 2- nitroso -5- methylaminophenol hydrochloric acid Salt, 2- nitroso -5- methylaminophenol hydrochloride etc..

About the additive amount of polymerization inhibitor, relative to polymerizable liquid crystal compound, preferably 0.01~1.0 mass % is more excellent It is selected as 0.05~0.5 mass %.

(Photoepolymerizationinitiater initiater)

Polymerizable liquid crystal compound of the invention preferably comprises Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater preferably comprises at least 1 kind or more.Specifically, " Irgacure 651 " of BASF AG, " Irgacure 184 ", " Darocur can be enumerated 1173”、“Irgacure 907”、“Irgacure 127”、“Irgacure 369”、“Irgacure 379”、“Irgacure 819”、“Irgacure 2959”、“Irgacure 1800”、“Irgacure 250”、“Irgacure 754”、“Irgacure 784”、“Irgacure OXE01”、“Irgacure OXE04”、“Lucirin TPO”、“Darocur 1173”、“Darocur MBF ", " the Esacure 1001M " of LAMBSON company, " Esacure KIP150 ", " Speedcure BEM ", “Speedcure BMS”、“Speedcure MBP”、“Speedcure PBZ”、“Speedcure ITX”、“Speedcure DETX ", " Speedcure EBD ", " Speedcure MBB ", " Speedcure BP ", Japanese chemical drug corporation " TAZ-A " of " Kayacure DMBI ", Japan's Siber Hegner corporation (existing DKSH company), ADEKA corporation “Adeka Optomer SP-152”、“Adeka Optomer SP-170”、“Adeka Optomer N-1414”、“Adeka Optomer N-1606 ", " Adeka Optomer N-1717 ", " Adeka Optomer N-1919 ", UCC corporation " Cyracure UVI-6990 ", " Cyracure UVI-6974 ", " Cyracure UVI-6992 ", Asahi Electro-Chemical Co. Ltd's system " Adeka Optomer SP-150, SP-152, SP-170, SP-172 ", Rhodia " PHOTOINITIATOR2074 ", " Irgacure 250 " of BASF AG, " UV-9380C " of GE Silicons corporation, Midori chemical company " DTS-102 " etc..

About the usage amount of Photoepolymerizationinitiater initiater, relative to polymerizable liquid crystal contained in polymerizable liquid crystal compound Close 100 mass parts of content of object, preferably 0.1~10 mass parts, particularly preferably 0.5~7 mass parts.It is each in order to improve optics The curability of anisotropy body, 100 mass parts of content relative to polymerizable liquid crystal compound are, it is preferable to use more than 3 mass parts Photoepolymerizationinitiater initiater.These can be used alone, and two or more mixing can also be used, furthermore it is also possible to add sensitization Agent etc..

(thermal polymerization)

In polymerizable liquid crystal compound of the invention, together with Photoepolymerizationinitiater initiater and thermal polymerization can be used.Make For thermal polymerization, known usual thermal polymerization can be used, can be used such as acetyl peroxide methyl acetate, Dicumyl peroxide, benzoyl peroxide, two (4- tert-butylcyclohexyl) peroxy dicarbonates, the tertiary fourth of perbenzoic acid Ester, methyl-ethyl-ketone peroxide, (tert-hexyl peroxide) 3,3,5- of 1,1- bis- trimethyl-cyclohexane, to amyl peroxy hydrogen, Tert-butyl hydroperoxide, cumyl peroxide, isobutyl peroxide, two (3- methyl -3- methoxybutyl) peroxidating two Organic peroxides, 2,2 '-azodiisobutyronitriles, the 2,2 '-azos two such as carbonic ester, 1,1- bis- (tert-butyl hydroperoxide) hexamethylene The azos amidines such as azonitrile compounds such as (2,4- methyl pentane nitriles), 2,2 '-azo two (the third amidine of 2- Methyl-N-phenyl) dihydrochlorides The azos amide compounds such as compound, 2,2 ' azos two { 2- methyl-N- [(the hydroxymethyl) -2- of 1,1- bis- hydroxyethyl] propionamide } Alkyl azo-compounds such as object, 2,2 ' azos two (2,4,4- trimethylpentane) etc..Specifically, can enumerate and Wako Pure Chemical Industries " V-40 " of Co. Ltd. system, " VF-096 ", NOF Corp (existing Japan Oil Co) " Perhexyl D ", " Perhexyl I " etc..

About the usage amount of thermal polymerization, relative to polymerizable liquid crystal contained in polymerizable liquid crystal compound Close 100 mass parts of content of object, preferably 0.1~10 mass parts, particularly preferred 0.5~5 mass parts.These can be used alone, Two or more mixing can also be used.

(surfactant)

Film thickness when being made optically anisotropic body in order to reduce is uneven, and polymerizable liquid crystal compound of the invention can be with Surfactant containing at least one or more.As the surfactant contained, alkyl carboxylate, alkyl phosphoric acid can be enumerated Salt, alkylsulfonate, fl muoroalkyl's salt, Fluoalkyl phosphate, fluoroalkyl sulfonate, polyoxyethylene deriv, fluoroalkyl oxygen Change ethene derivatives, polyethyleneglycol derivative, alkylammonium salt, fluoroalkyl ammonium salt class etc., particularly preferred fluorine system, acrylic acid series surface Activating agent.

Specifically, can enumerate " MEGAFACE F-251 ", " MEGAFACE F-444 ", " MEGAFACE F-477 ", “MEGAFACE F-510”、“MEGAFACE F-552”、“MEGAFACE F-553”、“MEGAFACE F-554”、“MEGAFACE F-555”、“MEGAFACE F-556”、“MEGAFACE F-557”、“MEGAFACE F-558”、“MEGAFACE F-559”、 “MEGAFACE F-560”、“MEGAFACE F-561”、“MEGAFACE F-562”、“MEGAFACE F-563”、“MEGAFACE F-565”、“MEGAFACE F-567”、“MEGAFACE F-568”、“MEGAFACE F-569”、“MEGAFACE F-570”、 “MEGAFACE F-571”、“MEGAFACE R-40”、“MEGAFACE R-41”、“MEGAFACE R-43”、“MEGAFACE R- 94”、“MEGAFACE RS-72-K”、“MEGAFACE RS-75”、“MEGAFACE RS-76-E”、“MEGAFACE RS-90” (above, Dainippon Ink Chemicals's system),

“Ftergent 100”、“Ftergent 100C”、“Ftergent 110”、“Ftergent 150”、 “Ftergent150CH”、“Ftergent A”、“Ftergent 100A-K”、“Ftergent 501”、“Ftergent 300”、 “Ftergent 310”、“Ftergent 320”、“Ftergent 400SW”、“FTX-400P”、“Ftergent 251”、 “Ftergent 215M”、“Ftergent 212MH”、“Ftergent 250”、“Ftergent 222F”、“Ftergent 212D”、“FTX-218”、“FTX-209F”、“FTX-213F”、“FTX-233F”、“Ftergent 245F”、“FTX-208G”、 “FTX-240G”、“FTX-206D”、“FTX-220D”、“FTX-230D”、“FTX-240D”、“FTX-207S”、“FTX-211S”、 “FTX-220S”、“FTX-230S”、“FTX-750FM”、“FTX-730FM”、“FTX-730FL”、“FTX-710FS”、“FTX- 710FM”、“FTX-710FL”、“FTX-750LL”、“FTX-730LS”、“FTX-730LM”、“FTX-730LL”、“FTX- 710LL " (above, Co., Ltd.'s NEOS system),

“BYK-300”、“BYK-302”、“BYK-306”、“BYK-307”、“BYK-310”、“BYK-315”、“BYK- 320”、“BYK-322”、“BYK-323”、“BYK-325”、“BYK-330”、“BYK-331”、“BYK-333”、“BYK-337”、 “BYK-340”、“BYK-344”、“BYK-370”、“BYK-375”、“BYK-377”、“BYK-350”、“BYK-352”、“BYK- 354”、“BYK-355”、“BYK-356”、“BYK-358N”、“BYK-361N”、“BYK-357”、“BYK-390”、“BYK-392”、 " BYK-UV3500 ", " BYK-UV3510 ", " BYK-UV3570 ", " BYK-Silclean3700 " (above, BYK Japanese firm System),

“TEGO Rad2100”、“TEGO Rad2200N”、“TEGO Rad2250”、“TEGORad2300”、“TEGO Rad2500”、“TEGO Rad2600”、“TEGO Rad2700”、“TEGOFlow300”、“TEGO Flow370”、“TEGO Flow425 ", " TEGO Flow ATF2 ", " TEGOFlow ZFS460 " (above, Evonik Industries corporation)

The examples such as " N215 ", " N535 ", " N605K ", " N935 " (above, Solvay Solexis corporation).

Surfactant is not essential component in the present invention, when being added, the additive amount of surfactant relative to 100 mass parts of content of polymerizable liquid crystal compound contained in polymerizable liquid crystal compound are preferably 0.01~2 mass parts, More preferably 0.05~0.5 mass parts.

In addition, optics can be made in polymerizable liquid crystal compound of the invention by using above-mentioned surfactant When anisotropic body, the inclination angle of Air Interface is effectively reduced.

Polymerizable liquid crystal compound of the invention, which has, effectively reduces Air Interface when optically anisotropic body is made The effect at inclination angle, as the substance other than above-mentioned surfactant, can enumerate the following general formula (7) expression with repetitive unit The compound that weight average molecular weight is 100 or more.

[changing 74]

In formula, R¹¹、R¹²、R¹³And R¹⁴The alkyl for separately indicating hydrogen atom, halogen atom or carbon atom number 1~20, should Hydrogen atom in alkyl can be replaced by 1 or more halogen atom.

As the suitable compound that general formula (7) indicate, it can be mentioned, for example polyethylene, polypropylene, polyisobutene, paraffin, liquid Body paraffin, chlorinated polypropylene, chlorinated paraffin, chlorination atoleine etc..

About the additive amount for the compound that general formula (7) indicate, relative to polymerization contained in polymerizable liquid crystal compound 100 mass parts of content of property liquid-crystal compounds, preferably 0.01~1 mass parts, more preferably 0.05~0.5 mass parts.

(the non-liquid crystal property compound with polymerizable group)

Polymerizable composition, polymerizable composition of the invention can also add with polymerizable group but be not the compound of liquid-crystal compounds. As such compound, as long as it is considered as usually the object of polymerizable monomer or polyreactive oligomers in the technical field Matter can then use without particular limitation.About the additive amount of the non-liquid crystal property compound with polymerizable group, relative to 100 mass parts of content of polymerizable liquid crystal compound contained in polymerizable liquid crystal compound, preferably 0.01~5 mass Part, more preferably 0.05~1 mass parts, particularly preferably 0.05~0.5 mass parts.

Specifically, (methyl) methyl acrylate, (methyl) ethyl acrylate, acrylic acid 2- hydroxy methacrylate, (first can be enumerated Base) propyl acrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (first Base) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid 2- second The own ester of base, (methyl) dodecylacrylate, (methyl) stearyl acrylate, (methyl) cyclohexyl acrylate, (methyl) third Two cyclopentyloxy ethyl ester of olefin(e) acid, (methyl) isobomyl acrylate base oxygroup ethyl ester, (methyl) isobornyl acrylate, (methyl) third Olefin(e) acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid dimethyladamantane ester, (methyl) dicyclopentanyl acrylate, two ring of (methyl) acrylic acid Amylene ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) methoxyethyl acrylate, ethyl carbitol (methyl) third Olefin(e) acid ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, 2- phenoxy group Diethylene glycol (methyl) acrylate, ω-carboxyl-polycaprolactone (n ≒ 2) mono acrylic ester, acrylic acid 2- hydroxyl -3- phenoxy group Propyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy ethyl, (methyl) acrylic acid (2- methyl -2- ethyl -1,3- dioxolanes - 4- yl) methyl esters, (methyl) acrylate (3- Ethyloxetane -3- base) methyl esters, (methyl) acrylic acid o-phenyl phenol second Oxygroup ester, (methyl) acrylate ester, (methyl) acrylic acid diethyl amino base ester, (methyl) acrylic acid 2,2,3,3, Five fluorine propyl ester of 3-, (methyl) acrylic acid 2,2,3,4,4,4- hexafluoro butyl ester, seven fluorine fourth of (methyl) acrylic acid 2,2,3,3,4,4,4- Ester, (methyl) acrylic acid 2- (perfluoro butyl) ethyl ester, (methyl) acrylic acid 2- (perfluoro hexyl) ethyl ester, (methyl) acrylic acid 1H, 1H, 3H- tetrafluoro propyl ester, (methyl) acrylic acid 1H, 1H, 5H- octafluoro pentyl ester, ten difluoro heptyl ester of (methyl) acrylic acid 1H, 1H, 7H-, (methyl) acrylic acid 1H-1- (trifluoromethyl) trifluoro ethyl ester, (methyl) acrylic acid 1H, 1H, 3H- hexafluoro butyl ester, (methyl) propylene Sour 1,2,2,2- tetra- fluoro- 1- (trifluoromethyl) ethyl ester, 15 fluorine monooctyl ester of (methyl) acrylic acid 1H, 1H-, (methyl) acrylic acid 1H, Ten trifluoro monooctyl ester of 1H, 2H, 2H-, phthalic acid 2- (methyl) acryloyloxyethyl ester, hexahydrophthalic acid 2- (methyl) third Alkene acyloxy ethyl ester, (methyl) glycidyl acrylate, phosphoric acid 2- (methyl) acryloyloxyethyl ester, acryloyl morpholine, two Methacrylamide, dimethylaminopropylacryl amide, N-isopropylacrylamide, acrylamide, hydroxyethyl third Single (methyl) acrylate, two (first of 1,4- butanediol such as acrylamide, N- acryloyl-oxyethyl hexahydrophthalic phthalimide Base) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, two (first of diethylene glycol Base) acrylate, triethylene glycol two (methyl) acrylate, ethylene-oxide-modified bisphenol-A two (methyl) acrylate, the tricyclic last of the ten Heavenly stems Alkane dimethanol two (methyl) acrylate, 9,9- bis- [4- (2- acryloyloxyethoxy) phenyl] fluorenes, two (methyl) acrylic acid The acrylic acid addition of glyceride, methacrylic acid 2- hydroxyl -3- acryloxy propyl ester, 1,6 hexanediol diglycidylether The diacrylates, trimethylolpropane tris (methyl) propylene such as acrylic acid adduct of object, 1,4- butanediol diglycidyl ether The modified three-(2- third of acid esters, ethoxylation isocyanuric acid triacrylate, pentaerythrite three (methyl) acrylate, 6-caprolactone Alkene trimethylammonium) three (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trihydroxy methyls such as isocyanuric acid ester Four (methyl) acrylate such as propane four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, oligomeric (methyl) acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidylether, diethyl Hexanediol diglycidyl ether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, 1,6-HD 2-glycidyl The epoxides such as ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, maleimide etc..These can individually make With, can also by it is two or more mixing and use.

(chain-transferring agent)

Polymerizable liquid crystal group when optically anisotropic body is made in order to more improve and the adaptation of substrate, in the present invention Chain-transferring agent can also be added by closing object.As chain-transferring agent, preferably mercaptan compound, more preferably list mercaptan, two mercaptan, trithio Alcohol, four mercaptan compounds, even more preferably three mercaptan compounds.Specifically preferred the following general formula (8-1)~(8-13) table The compound shown.

[changing 75]

[changing 76]

[changing 77]

In formula, R⁶⁵Indicate the alkyl of carbon atom number 2~18, which can may be branch for straight chain, in the alkyl 1 or more methylene can in such a way that oxygen atom and sulphur atom are mutually not directly connected by oxygen atom, sulphur atom ,- CO- ,-OCO- ,-COO- or-CH=CH- replace, R⁶⁶The alkylidene for indicating carbon atom number 2~18,1 in the alkylidene with On methylene can in such a way that oxygen atom and sulphur atom are mutually not directly connected by oxygen atom, sulphur atom ,-CO- ,- OCO- ,-COO- or-CH=CH- replace.

About the additive amount of chain-transferring agent, relative to polymerizable liquid crystal compound contained in polymerizable liquid crystal compound 100 mass parts of content, preferably 0.5~10 mass parts, more preferably 1.0~5.0 mass parts.

(pigment)

In polymerizable liquid crystal compound of the invention, it can according to need containing pigment.Used pigment is not special It limits, known usual pigment can be contained in the range of not upsetting orientation.

As aforementioned pigment, it can be mentioned, for example 2 color pigments, fluorchromes etc..As such pigment, it can be mentioned, for example Polyazo pigment, anthraquinone pigment, anthocyanidin, phthalocyanine dye, pigment, pyrene ketone pigment, the sour cyanines pigment in side etc., from the sight of addition Point considers that aforementioned pigment is preferably the pigment that liquid crystal liquid crystal property is presented.Can be used such as No. 2,400,877 bulletins of U.S. Patent No., DreyerJ.F.,Phys.and Colloid Chem.,1948,52,808.,"The Fixing of Molecular Orientation (fixation of molecularly oriented) ", Dreyer J.F., Journal de Physique, 1969,4,114., " Light Polarization from Films of Lyotropic Nematic Liquid Crystals is (from molten cause nematic The film of liquid crystal it is Light polarizing) " and J.Lydon, " Chromonics " in " Handbook of Liquid Crystals Vol.2B:Low Molecular Weight Liquid Crystals II " (" the 2B volumes of liquid crystal handbook: combinations of low molecular weight liquid crystals " color development " in II "), D.Demus, J.Goodby, G.W.Gray, H.W.Spiessm, V.Vill ed, Willey-VCH, P.981-1007 (2 colors of liquid crystal display contaminate by (1998), Dichroic Dyes for Liquid Crystal Display Material) A.V.lvashchenko CRC Press, 1994, and " new development in functional pigmented market ", chapter 1, page 1, 1994, CMC Co., Ltd. shine etc. records pigment.

As 2 color pigments, it can be mentioned, for example formula below (d-1)~formulas (d-8).

[changing 78]

[changing 79]

About the additive amount of the pigments such as aforementioned 2 color pigment, relative to polymerizable liquid crystal chemical combination contained by powder mixture 100 mass parts of total amount of object, preferably 0.001~10 mass parts, more preferably 0.01~5 mass parts.

(filler)

In polymerizable liquid crystal compound of the invention, it can according to need containing filler.Filler used does not limit especially It is fixed, known usual filler can be used in the range of the thermal conductivity of resulting polymer does not reduce.Specifically, can enumerate The inorganic filling materials such as aluminium oxide, titanium white, aluminium hydroxide, talcum, clay, mica, barium titanate, zinc oxide, glass fibre, silver The metal powders such as powder, copper powder, aluminium nitride, boron nitride, silicon nitride, gallium nitride, silicon carbide, magnesia (aluminum oxide), oxidation Aluminium (aluminum oxide), dissolves the conducting fillers, silver nanoparticle such as silica (silica) at crystallinity silica (silica) Particle etc..

(chipal compounds)

In order to make resulting optical film that there is cholesteric liquid crystal, can also contain in polymerizable liquid crystal compound of the invention Liquid crystal liquid crystal property can be presented or also it is the chipal compounds of non-liquid crystal property, it is in chipal compounds, it is preferable to use poly- with polymerism Conjunction property chipal compounds.

Polymerizable chiral compound used in the present invention, preferably with 1 or more polymerizable functional group.As Such compound, it can be mentioned, for example Japanese Unexamined Patent Publication 11-193287 bulletins, Japanese Unexamined Patent Publication 2001-158788 bulletin, day Ben Tebiao 2006-52669 bulletin, Japanese Unexamined Patent Publication 2007-269639 bulletin, Japanese Unexamined Patent Publication 2007-269640 bulletin, 2009-84178 bulletin etc. record such carbohydrate chiral comprising isobide, different mannitol, glucoside etc. and With the rigid position such as 1,4- phenylene, 1,4- cyclohexylidene and vinyl, acryloyl group, (methyl) acryloyl group, in addition and also Polymerizable chiral compound with polymerizable functional group as dimaleoyl imino；Japanese Unexamined Patent Publication 8-239666 bulletin Record such polymerizable chiral compound comprising terpene derivant；VOL35 page 467~469 (1995 of NATURE (nature) Distribution on November 30), NATURE (nature) VOL392 page 476~479 (distribution on April 2nd, 1998) etc. wraps as recording The polymerizable chiral compound of base containing mesomorphic and the interval base with chiral position；Or Japanese Unexamined Patent Application Publication 2004-504285 public affairs Report, Japanese Unexamined Patent Publication 2007-248945 bulletin record such polymerizable chiral compound comprising binaphthyl.Among this, spiral shell It is preferred in polymerizable liquid crystal compound of the invention to revolve distortion power (HTP) big chipal compounds.

In chipal compounds, the chipal compounds big as helical twisting power (HTP), can enumerate the following general formula (3-1)~ General formula (3-4) is selected from general formula (3-1)~general formula more preferably using the chipal compounds for being selected from general formula (3-1)~general formula (3-3) In the chipal compounds of (3-3), particularly preferably using the polymerizable chiral for the polymerizable group that there is the following general formula (3-a) to indicate Compound.

[changing 80]

In formula, Sp^3aAnd Sp^3bEach independently represent the alkylidene of carbon atom number 0~18, the alkylidene can by 1 with On halogen atom, CN base or the carbon atom number 1~8 with polymerizable functional group alkyl replace, 1 be present in the group A CH₂Base or 2 or more not adjacent CH₂The form that base mutually can not be bound directly respectively with oxygen atom independently of each other By-O- ,-S- ,-NH- ,-N (CH₃)-,-CO- ,-COO- ,-OCO- ,-OCOO- ,-SCO- ,-COS- or-C ≡ C- replace,

A1, A2, A3, A4, A5 and A6 each independently represent 1,4- phenylene, 1,4- cyclohexylidene, 1,4- cyclohexenyl group, Oxinane -2,5- diyl, 1,3- bis-Bicyclic (2,2,2) Ya Xin of alkane -2,5- diyl, tetrahydric thiapyran -2,5- diyl, 1,4- Base, decahydronaphthalene -2,6- diyl, pyridine -2,5- diyl, pyrimidine -2,5- diyl, pyrazine -2,5- diyl, thiophene -2,5- diyl -, 1,2,3,4- naphthane -2,6- diyl, 2,6- naphthylene, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, 1,2,3,4, 4a, 9,10a- octahydro phenanthrene -2,7- diyl, 1,4- naphthylene, benzo [1,2-b:4,5-b '] Dithiophene -2,6- diyl, benzo [1, 2-b:4,5-b '] two selenophen -2,6- diyls, [1] benzothiophene simultaneously [3,2-b] thiophene -2,7- diyl, [1] benzo selenophen simultaneously [3, 2-b] selenophen -2,7- diyl or fluorenes -2,7- diyl, it can have 1 or more F, Cl, CF₃、OCF₃, CN base, carbon atom number 1 ~8 alkyl, the alkoxy of carbon atom number 1~8, the alkanoyl of carbon atom number 1~8, the alkanoyloxy of carbon atom number 1~8, carbon The alkoxy carbonyl of atomicity 1~8, the alkenyl of carbon atom number 2~8, the alkenyloxy group of carbon atom number 2~8, carbon atom number 2~8 Enoyl-, and/or the alkene acyloxy of carbon atom number 2~8 are as substituent group.A1, A2, A3, A4, A5 and A6 are preferred each independently Indicate that Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene or 2,6- naphthylene can have 1 or more F, CN base, carbon atom number 1~8 Alkyl, carbon atom number 1~8 alkoxy as substituent group.

N, l, k and s each independently represent 0 or 1,

Z0, Z1, Z2, Z3, Z4, Z5 and Z6 each independently represent-COO- ,-OCO- ,-CH₂CH₂-、-OCH₂-、- CH₂O- ,-CH=CH- ,-C ≡ C- ,-CH=CHCOO- ,-OCOCH=CH- ,-CH₂CH₂COO-、-CH₂CH₂OCO-、- COOCH₂CH₂-、-OCOCH₂CH₂,-CONH- ,-NHCO-, carbon number 2~10 the alkyl or singly-bound with halogen atom,

N5 and m5 each independently represents 0 or 1,

R^3aAnd R^3bIndicate the alkyl of hydrogen atom, halogen atom, cyano or carbon atom number 1~18, which can be by 1 or more Halogen atom or CN replace, 1 CH being present in the group₂Base or 2 or more not adjacent CH₂Base difference is mutually indepedent It ground can be in form that oxygen atom is not bound directly mutually by-O- ,-S- ,-NH- ,-N (CH₃)-、-CO-、-COO-、-OCO-、- OCOO- ,-SCO- ,-COS- or-C ≡ C- replace,

Or R^3aAnd R^3bFor general formula (3-a).

[changing 81]

-P^3a (3-a)

(in formula, P^3aIndicate polymerizable functional group.)

P^3aIt is preferred that indicating the substituent group of the polymerizable group indicated selected from following formulas (P-1) to formula (P-20).

[changing 82]

From the viewpoint of improving polymerism and storage stability, in these polymerizable functional groups, preferred formula (P-1) or formula (P-2), (P-7), (P-12), (P-13), more preferable formula (P-1), (P-7), (P-12).

As the concrete example of polymerizable chiral compound, compound (3-5)~(3-24) compound can be enumerated, but unlimited Due to following compounds.

[changing 83]

[changing 84]

[changing 85]

[changing 86]

[changing 87]

In formula, m, n, k, l each independently represent 1~18 integer, R¹~R⁴Each independently represent hydrogen atom, carbon number 1 Alkoxy, carboxyl, the cyano of~6 alkyl, carbon number 1~6.When the alkyl or carbon number 1~6 that these groups are carbon number 1~6 It, can be all unsubstituted or replaced by 1 or 2 or more halogen atom when alkoxy.

In the polymerizable chiral compound that above-mentioned general formula (3-5)~general formula (3-24) indicates, as helical twisting power (HTP) Big chipal compounds particularly preferably use general formula (3-5)~general formula (3-9), general formula (3-12)~general formula (3-14), general formula The polymerizable chiral compound that (3-16)~general formula (3-18) indicates.

The use level of polymerizable chiral compound needs according to the spiral induction force of compound to be suitable for adjustment, in polymerism liquid In brilliant composition, 0~25 mass %, further preferably 0~20 mass % are preferably comprised, particularly preferably contains 0~15 mass %.

In order to make resulting optical film that there is cholesteric and obtain the good optical film of permeability, polymerism of the invention It is aforementioned relative to total 100 mass parts of polymerizable liquid crystal compound used in polymerizable liquid crystal compound in liquid-crystal composition It is preferable to use 0.5~20 mass parts for chipal compounds, more preferably use 1~15 mass parts, particularly preferably use 1.5~10 mass Part.

(other addition drug)

In order to further adjust physical property, can according to purpose, add the significantly reduced degree of alignment capability of liquid crystal Add polymer compound, thixotropic agent, ultraviolet absorbing agent, infrared absorbent, the antioxidant, surface treatment of not liquid crystal liquid crystal property The additives such as agent.

(manufacturing method of optically anisotropic body)

(optically anisotropic body)

The use of the optically anisotropic body that polymerizable liquid crystal compound of the invention makes is by substrate, as needed takes It is stacked gradually to the polymer of film and polymerizable liquid crystal compound.

(substrate)

Substrate used in optically anisotropic body of the invention is liquid crystal apparatus, in display, optical component, optical film Usually used substrate, as long as in the drying after polymerizable liquid crystal compound of the invention is coated with tolerable heating The material of heat resistance, then be not particularly limited.As such substrate, can enumerate glass baseplate, metal base, ceramic base material, The organic materials such as plastic basis material.Especially when substrate is organic material, cellulose derivative, polyolefin, polyester, poly- carbon can be enumerated Acid esters, polyacrylate (acrylic resin), polyarylate, polyether sulfone, polyimides, polyphenylene sulfide, polyphenylene oxide, nylon or poly- Styrene etc..Wherein, preferably polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, poly- carbonic acid The plastic basis materials such as ester, the substrates such as further preferred polyacrylate, polyolefin, cellulose derivative particularly preferably use COP (cyclic olefin polymer) is used as polyolefin, uses TAC (triacetyl cellulose) as cellulose derivative, uses PMMA (poly- first Base methyl acrylate) it is used as polyacrylate.As the shape of substrate, other than it can be plate, it is possible to have curved surface. These substrates can also have electrode layer, anti-reflective function, reflection function as needed.

In order to improve coating, the cementability of polymerizable liquid crystal compound of the invention, the table of these substrates can be carried out Surface treatment.As surface treatment, ozone treatment, corona treatment, sided corona treatment, silane coupled processing etc. can be enumerated.In addition, In order to adjust transmitance, the reflectivity of light, the methods of vapor deposition setting organic film, inorganic oxide can be passed through in substrate surface Film, metallic film etc., or in order to assign optical surcharge, substrate can for pickup lens, rod-shaped lens, CD, Phase difference film, optical diffusion film, colour filter etc..Wherein the higher pickup lens of preferred surcharge, phase difference film, optical diffusion film, Colour filter.

(orientation process)

In addition, as above-mentioned base material, according to the polymerism liquid when polymerizable liquid crystal compound of the invention is coated with dry The mode that brilliant composition is orientated can be equipped with alignment films for individual glass baseplate or on substrate.As orientation position Reason, can enumerate extension processing, friction treatment, polarisation UV, visible light photo-irradiation treatment, Ion Beam Treatment etc..Use the feelings of alignment films Under condition, known usual alignment films are can be used in alignment films.As such alignment films, can use polyimides, polyamide, Lecithin contains hydroxyl, carboxylic acid group or sulfonic hydrophilic polymer and hydrophilic inorganic compound, optical alignment film Deng.As hydrophilic polymer, polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polymethylacrylic acid, polyalginic acid can be enumerated Sodium, poly- carboxy methyl cellulose sodium salt, pulullan polysaccharide, polystyrolsulfon acid.In addition, as hydrophilic inorganic compound, The inorganic compounds such as oxide, the fluoride of Si, Al, Mg, Zr etc. can be enumerated.Hydrophilic substrate is just in order to make optics respectively to different Property body optic axis be basically parallel to the normal direction orientation of substrate for be effective, therefore in order to obtain the optics of positive c plate It is preferred when anisotropic body, due to playing the role of when having carried out friction treatment to hydrophilic substrate as horizontal alignment film, Therefore in hydrophilic polymer layer, friction treatment can cause adverse effect to vertical orientation, therefore in order to obtain positive c plate It is not preferred when optically anisotropic body.

(coating)

As the rubbing method for obtaining optically anisotropic body of the invention, applicator method, stick coating method, rotation can be carried out Coating, rolling method, direct gravure coating process, reversed gravure coating process, soft version rubbing method, ink-jet method, die coating method, lid coating, leaching Customary way known in coating, slot coated method etc..After being coated with polymerizable liquid crystal compound, as needed by polymerizable liquid crystal group Close the solvent heat drying contained by object.

(polymerization process)

About the converging operation of polymerizable liquid crystal compound of the invention, pass through the liquid crystal in polymerizable liquid crystal compound Compound is orientated in the state of (planar orientation) relative to substrate in horizontal alignment, vertically oriented or hybrid orientation or cholesteric The irradiation of the light such as ultraviolet light or heating are usually carried out, to carry out.By illumination inject row polymerization when, specifically preferably according to 390nm ultraviolet light below is penetrated, the light of 250~370nm wavelength is most preferably irradiated.But when because of 390nm ultraviolet light meeting below Whens causing polymerizable liquid crystal compound decomposition etc., sometimes it is also preferred that the ultraviolet light using 390nm or more carries out polymerization processing.The light Preferably spread light and the not light of polarisation.

(polymerization)

As the method for polymerizeing polymerizable liquid crystal compound of the invention, the side of irradiation active energy beam can be enumerated Method, thermal polymerization etc., irradiate the method for active energy beam due to do not need heating and room temperature react thus preferably, In, from consideration easy to operate, the preferably method of the light such as irradiation ultraviolet light.

Temperature when irradiation is set as the temperature that polymerizable liquid crystal compound of the invention is able to maintain liquid crystalline phase, in order to avoid The thermal polymerization for inducing polymerizable liquid crystal compound, is preferably set as 30 DEG C or less as far as possible.Wherein, liquid-crystal composition is usually heating up Phase transition occurs according to the sequence of Cr (crystallization)-N (nematic)-I (isotropic liquid) in the process and presents only nematic Liquid crystalline phase, but in the case where polymerizable liquid crystal compound of the invention, due to having the feature that smectic liquid crystal is presented, In temperature-rise period, the phase transition of Cr (crystallization)-Sm (smectic)-N (nematic)-I (isotropic liquid) is shown, therefore present close Crystal phase and nematic phase both liquid crystalline phases.On the other hand, in temperature-fall period, due to obtaining thermodynamics nonequilibrium condition, Sometimes do not occur to crystallize and protect below Cr (crystallization)-N (nematic) or Cr (crystallization)-Sm (smectic) transition temperature yet Hold nematic liquid crystal state or smectic liquid crystal state.The state is known as supercooling state.In the present invention, it is in supercooling state Liquid-crystal composition be also contained in keep liquid crystalline phase state in.Smectic phase with layer structure due to thus having than nematic phase more Close to the structure of crystallization, so, compared with irradiating the obtained optically anisotropic body of ultraviolet light in the state of nematic phase, The obtained optically anisotropic body of ultraviolet light is irradiated in the state of smectic phase becomes the optics with the structure closer to crystallization Anisotropic body, therefore it is orientated order and/or heat resistance raising, thus preferably.Smectic phase is according to molecular long axis relative to layer method Line is vertical or inclination and style is two classes.The known molecular long axis smectic phase vertical relative to layer normal has smectic C (SmA), smectic B (SmB), molecular long axis have smectic C phase (SmC), smectic F phase relative to the smectic phase of layer normal slope (SmF), smectic G phase (SmG), smectic I phase (SmI), smectic J phase (SmJ).From molecular long axis along polyimides in homogeneous orientation When phase transition has occurred towards smectic phase in the nematic phase of the frictional direction orientation of alignment films, molecular long axis is hung down relative to layer normal Straight smectic phase, specifically for smectic C (SmA), smectic B (SmB), since the molecular long axis being located in layer is along friction side To orientation, thus the generation for being orientated defect is few, becomes good orientation, therefore preferably.

The method for irradiating the light such as ultraviolet light specifically preferably irradiates 390nm ultraviolet light below, most preferably irradiate 250~ The light of 370nm wavelength.But when cause because of 390nm ultraviolet light below polymerizable composition, polymerizable composition decompose etc. whens, sometimes it is also preferred that Polymerization processing is carried out with the ultraviolet light of 390nm or more.The light preferably spreads light and the not light of polarisation.Ultraviolet irradiation intensity is excellent Select 0.05kW/m²~10kW/m²Range.Particularly preferred 0.2kW/m²~2kW/m²Range.Uitraviolet intensity is less than 0.05kW/m²When, a large amount of time is needed in order to complete to polymerize.On the other hand, for more than 2kW/m²Intensity when, have polymerization Property liquid-crystal composition in liquid crystal molecule the tendency of photodegradation occurs, have it is a large amount of generate heat of polymerizations and the temperature in polymerizeing rise, The S order parameter of polymerizable liquid crystal changes, a possibility that chaotic occurs for the delay of film after polymerization.

Using mask and by ultraviolet light irradiation only make it is specific it is partially polymerized after, applying electric field, magnetic field or temperature etc. makes The state of orientation of the unpolymerized part changes, and when then making this unpolymerized partially polymerized, can also obtain with differently- oriented directivity not The optically anisotropic body of same multiple regions.

In addition, using mask and when only making specific partially polymerized by ultraviolet light irradiation, in advance to unpolymerized state Polymerizable liquid crystal compound applies electric field, magnetic field or temperature etc. and limits orientation, keeps the state and irradiation light makes from mask It polymerize, so that the optically anisotropic body with the different multiple regions of differently- oriented directivity can also be obtained.

The optically anisotropic body obtained from polymerizeing polymerizable liquid crystal compound of the invention, can shell from substrate It is used as optically anisotropic body from and with monomer, optically anisotropic body can not also be directly used as from strippable substrate.Especially Be be used as tegillum laminated substrate or be bonded with other substrates and in use, due to other components not easy to pollute, thus it is useful.

(optical film)

About optical film (phase difference film) of the invention, grasped in the same manner as the manufacturing method of common optically anisotropic body Make and makes.Resulting phase difference film can be used as the use such as various birefringent films.According to liquid crystal apparatus, liquid crystal display, have The devices such as machine El element, organic el display, quantum dot El element, quantum dot EL display, miniature LED or display, optics The purposes such as element, optical component, colorant, safety mark, lasing fluorescence component, optical film and compensation film, are formed as The form being adapted with purposes.

As such phase difference film, such as rod-shaped liquid crystalline compound can be applicable in and taken relative to the substantial level of substrate To negative A plate relative to the vertical uniaxial orientation of substrate of positive a plate, discotic liquid crystalline compound, rod-shaped liquid crystalline compound phase The positive c plate of orientation substantially perpendicular for substrate, rod-shaped liquid crystalline compound is orientated relative to substrate cholesteric or discoid liquid Crystalline compound is mixed relative to substrate relative to the negative C plate, biaxiality plate, rod-shaped liquid crystalline compound of the horizontal uniaxial orientation of substrate Conjunction to alignment mode relative to the negative O plate of substrate hybrid orientation of positive O plate, discotic liquid crystalline compound.For liquid crystal When display element, as long as improving viewing angle dependency, it will be able to be not particularly limited to be applicable in various alignment modes.

Can be used such as positive a plate, negative A plate, positive c plate, negative C plate, biaxiality plate, positive O plate, negative O plate alignment mode.This Among, it is preferable to use positive a plate and negative C plate.Further, more preferably by positive a plate and negative C board stacking.

Here, so-called positive a plate is optically anisotropic body obtained by instigating polymerizable liquid crystal compound homogeneous to be orientated.Separately Outside, so-called negative C plate is optically anisotropic body obtained by instigating polymerizable liquid crystal compound cholesteric to be orientated.

In the liquid crystal cells that phase difference film is utilized, the angle of visibility in order to compensate for polarizing axis orthogonality relies on and expands view Wild angle, as the 1st phase separation layer, it is preferable to use positive a plate.Here, about positive a plate, by the refractive index of slow-axis direction in the face of film When the refractive index for being set as fast axis direction in the face of nx, film is set as ny, the refractive index of thickness direction of film is set as nz, become " nx > The relationship of ny=nz ".As positive a plate, phase difference value is the range of 30~500nm in the face at optimal wavelength 550nm.In addition, Thickness direction phase difference value is not particularly limited.Nz coefficient is preferably 0.9~1.1 range.

In addition, in order to offset the birefringent of liquid crystal molecule itself, as the 2nd phase separation layer, it is preferable to use having negative folding Penetrate the anisotropic so-called negative C plate of rate.Alternatively, it is also possible to which negative C plate is laminated in positive a plate.

It here, is that the refractive index of slow-axis direction in the face by phase separation layer is set as the face of nx, phase separation layer about negative C plate As " nx=ny > nz " when the refractive index of interior fast axis direction is set as ny, the refractive index of thickness direction of phase separation layer is set as nz The phase separation layer of relationship.The thickness direction phase difference value of negative C plate is preferably the range of 20~400nm.

It should be noted that the refractive anisotrop of thickness direction thickness direction phase difference as defined in following formula (2) Value Rth is indicated.About thickness direction phase difference value Rth, phase difference value R in face can be used₀, using slow axis as tilting axis 50 ° and measure phase difference value R₅₀, the thickness d of film, film mean refractive index n₀, number is passed through by formula (1) and following formula (4)~(7) Value calculating finds out nx, ny, nz, substitutes them in formula (2) and calculates.In addition, Nz coefficient can be calculated from formula (3).Hereinafter, at this It is also the same in other records of specification.

R₀=(nx-ny) × d (1)

Rth=[(nx+ny)/2-nz] × d (2)

Nz coefficient=(nx-nz)/(nx-ny) (3)

R₅₀=(nx-ny ') × d/cos (φ) (4)

(nx+ny+nz)/3=n0 (5)

Here,

φ=sin^-1[sin(50°)/n₀] (6)

Ny '=ny × nz/ [ny²×sin²(φ)+nz²×cos²(φ)]^1/2 (7)

For commercially available measuring difference of phases device, carries out numerical value shown here automatically in the device mostly and calculate, and And phase difference value R in automatic display surface₀, thickness direction phase difference value Rth etc..As such measurement device, it can be mentioned, for example RETS-100 (big tomb chemical (strain) system).

Optical film of the invention uses depending on the application, and no matter excessively thin the film thickness of aforementioned optical film is or blocked up, applies passing through Cloth and when being manufactured, be all difficult to control orientation, therefore from the viewpoint of orientation, preferably 0.05 μm or more 20 μm with Under, further preferred 0.1 μm or more 12 μm hereinafter, particularly preferred 0.2 μm or more 6 μm or less.

(phase difference patterned film)

Optical film of the invention can be also used for phase difference patterned film.Phase difference patterned film by substrate, alignment films with And the polymer of polymerizable liquid crystal compound stacks gradually, in polymerization process, according to the different phase difference in acquisition part Mode patterned.Patterning also has linear patterning, the patterning of clathrate, the patterning of round shape, polygon The case where different directions such as the patterning of shape.According to liquid crystal apparatus, display, optical element, optical component, colorant, safety It is applied with the purposes of mark, lasing fluorescence component, optical film and compensation film etc..

As the method for obtaining the different phase difference in part, alignment films are set to substrate, it will when carrying out orientation process When polymerizable liquid crystal compound of the invention is coated with dry, in such a way that polymerizable liquid crystal compound carries out patterned orientation into Row processing.Such orientation process can enumerate fine friction treatment, the polarisation UV, visible light photo-irradiation treatment, micro- across photomask Thin shape processing processing etc..Alignment films use known usual alignment films.As such alignment films, can enumerate polyimides, Polysiloxanes, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene oxide, polyarylate, polyethylene terephthalate Ester, polyether sulfone, epoxy resin, Epocryl, acrylic resin, coumarin compound, chalcone compound, meat The compounds such as cinnamic acid ester compounds, fulgide compounds, anthraquinone compounds, azo-compound, aryl ethylene compound.It utilizes The compound that fine friction carries out orientation process preferably pass through orientation process or increase after orientation process heating process to Promote the crystallization of material., it is preferable to use light orientation material in the compound of orientation process other than being rubbed.

(luminance raising film)

Optical film of the invention can be used for luminance and improve film.Luminance of the invention improves film and is characterized in that, is With λ/luminance of 4 plates and reflective polarizer galvanometer improves film, reflective polarizer galvanometer is successively anti-comprising the first light since the plate of λ/4 side Penetrate layer, the second reflection layer and third reflection layer, the first reflection layer, the second reflection layer and third reflection layer be by Reflection layer made of cholesteric liquid crystal is mutually fixed, in the first reflection layer, the second reflection layer and third reflection layer, any one For the blue reflection layer at the peak with 380~499nm of reflection kernel wavelength and half breadth 100nm reflectivity below, appoint One is the green reflection layer at the peak with 500~599nm of reflection kernel wavelength, half breadth 200nm reflectivity below, Any one is the red reflective at the peak with 600~750nm of reflection kernel wavelength, half breadth 150nm reflectivity below Layer, the Rth (550) of the first reflection layer and the symbol of Rth (550) of the second reflection layer are opposite.By such composition, originally The luminance of invention improves film when being assembled in liquid crystal display device, and luminance is high, is able to suppress oblique tone variations.

(color compensation film)

Optical film of the invention can be used for color compensation film.Color compensation film is the white that will be issued from back light Light is that the wavelength of the colour mixture part of the colour mixture light of blue, green, red filters out the film of (カット).The case where common white light Under, 570~620nm is nearby divided into green, red respective color using colour filter, but by using attached in 570~620nm The nearly color compensation film with selection reflection wavelength, can be improved color reprodubility.

(cholesteric reflectance coating)

Cholesteric reflectance coating of the invention is characterized in that, for by the solidfied material of the polymerizable liquid crystal compound through planar orientation The cholesteric reflectance coating of composition, which, which contains, one kind or two or more only has 1 polymerizable functional group simultaneously And the liquid-crystal compounds with tolans skeleton, contain the one kind or two or more liquid with 2 or more polymerizable functional groups Brilliant compound containing the one kind or two or more chipal compounds with 1 or more polymerizable functional group, and contains a kind or 2 Kind or more polymerization initiator.

(antireflection film)

Antireflection film of the invention is the circular polarizer obtained from further laminated phase-difference plate on polarizer.By straight line When polarisation becomes rotatory polarization or rotatory polarization is become linear polarization or changes the polarization direction of linear polarization, phase difference is used Plate etc..Especially as linear polarization is become rotatory polarization or rotatory polarization is become to the phase plate of linear polarization, use is so-called 1/4 wavelength plate (plate of also referred to as λ/4).1/2 wavelength plate (plate of also referred to as λ/2) is commonly used in changing the polarization direction of linear polarization The case where.

Circular polarizer is efficiently used for for example becoming image the image of the reflection-type liquid-crystal display device of colored display The case where tone is adjusted etc., in addition, also having the function of antireflection.As above-mentioned phase plate, polymerizable mesogenic can be enumerated The alignment films of object support structure made of the oriented layer of liquid crystal polymer etc. with film.Phase plate for example can be using respectively Kind of wavelength plate, liquid crystal layer it is birefringent have to correspond to compensating phase plate for the purpose of coloring, visual angle etc. etc. use purpose Proper phase difference phase plate, be also possible to for phase plate of more than two kinds to be laminated and control the optical characteristics such as phase difference Phase plate etc..

(view angle compensation film)

Optical film of the invention is also used as view angle compensation film.View angle compensation film of the invention is for according to i.e. It also can be more brightly when making the picture of liquid crystal display device from being not orthogonal to picture but the direction that is slightly tilted See that the mode of image expands the film of angle of visibility.As such view angle compensation film, such as by phase difference film, liquid crystal polymer etc. Alignment films, the structure of oriented layer for supporting liquid crystal polymer etc. over the transparent substrate etc. constitute.Common phase plate uses There is birefringent polymer film, through the liquid crystalline polymer film of uniaxial orientation through uniaxial extension on its face direction, with this phase It is right, for the phase plate used as view angle compensation film, using such as two-fold through having for twin shaft extension in the surface direction The polymer film penetrated, or uniaxial extension, the refraction for also extending in a thickness direction and controlling thickness direction in the surface direction Rate has two-way stretched PTFE film as birefringent polymer, tilted alignment film etc..As tilted alignment film, it can be mentioned, for example Enable the alignment films of liquid crystal polymer tilted alignment, pass through ultraviolet light isoreactivity in the state of making polymerizable liquid crystal tilted alignment The polymer film etc. measuring ray and polymerizeing.It uses the suitable film for the purpose of following: being based on liquid crystal cells bring phase difference, Prevent from colouring caused by the variation because of visuognosis angle etc., expand good angle of visibility of visuognosis etc..

In addition, from realize the viewpoint etc. of the good wide angle of visibility of visuognosis consider, it is preferable to use with optical film support by Optical compensation phase plate made of the optical anisotropic layer that the tilted alignment film of liquid crystal polymer is constituted.

(reflection-type polarizer)

Optical film of the invention is also used as reflection-type polarizer.Reflection-type polarizer of the invention is reflected by cholesteric Reflection-type polarizer made of film, adhesion coating, linear polarization film stack gradually, the cholesteric reflectance coating use aforementioned gallbladder of the invention Steroid reflectance coating.In addition, there is 1 or more phase difference film, in addition, phase can be used in the phase difference film in reflection-type polarizer The different phase difference film of difference.The stacking of phase difference film obtains as follows: being bonded bonding agent or adhesive film to resulting phase difference film Afterwards, cholesteric reflectance coating and Such phase differences film of the invention are bonded by bonding agent or adhesive film.Using bonding agent or In the case where adhesive film, bonding agent, adhesive film use the known usual material of optical film purposes.

Embodiment

Illustrate the present invention following with synthesis example, embodiment and comparative example, but the present invention is not limited to these certainly. It should be noted that unless otherwise specified, then " part " and " % " is quality criteria.

(modulation of polymerizable liquid crystal compound)

Relative to formula shown in 1~table of table 5 (A-1)~formula (A-8), formula (B-1)~formula (B-11), formula (C-1)~formula (C- 2) 100 mass parts of compound total amount indicated, respectively with ratio shown in 1~table of table 4 (mass parts) formula (D-1)~formula (D-3) chemical combination that the compound, (E-1)~(E-4) as organic solvent of expression, the formula (F-1) as antioxidant indicate Object, (G-1) as polymerization inhibitor, (H-1) as polymerization initiator~(H-2), as (I-1) of chain-transferring agent, as tool There are the formula (I-2) of the non-liquid crystal property compound of polymerizable group and (J-1)~(J-3) as surfactant, modulation is poly- Conjunction property liquid-crystal composition (1)~(28).

(modulation of polymerizable liquid crystal compound (1))

As shown in table 1,40 mass of compound indicated relative to formula (A-1) 40 mass parts of compound, formula (A-2) indicated 100 mass parts of aggregate value for 20 mass parts of compound that part, formula (B-1) indicate, 4.2 matter of compound for using formula (D-1) to indicate Measure part, (G-1) 0.1 mass parts, (H-1) 3 mass parts, (J-2) 0.2 mass parts and (E-3) 100 mass as organic solvent Part, (E-4) 200 mass parts, use the agitating device with agitating auger paddle, 60 DEG C of low whipping speed 500rpm, solution temperature Under conditions of stir 1 hour after, with 0.2 μm of membrane filter, obtain polymerizable liquid crystal compound (1).

(polymerizable liquid crystal compound (2)~(33) are compared with polymerizable liquid crystal compound (34)~(38) modulation)

In the same manner as the modulation of polymerizable liquid crystal compound (1) of the invention, relative to formula shown in 1~table of table 5 (A-1) 100 mass parts of compound total amount that~formula (A-8), formula (B-1)~formula (B-11), formula (C-1)~formula (C-2) indicate, by formula (D-1) compound, (E-1)~(E-4) as organic solvent, formula (F-1) table as antioxidant of~formula (D-3) expression The compound that shows, (G-1) as polymerization inhibitor, (H-1) as polymerization initiator~(H-2), as the (I- of chain-transferring agent 1), as the formula (I-2) of the non-liquid crystal property compound with polymerizable group and as (J-1)~(J-3) of surfactant Each ingredient be changed to ratio shown in 1~table of table 5 respectively, in addition to this, according to the modulation with polymerizable liquid crystal compound (1) Identical condition, respectively obtain polymerizable liquid crystal compound (2)~(33), compare with polymerizable liquid crystal compound (34)~ (38)。

Polymerizable liquid crystal compound of the invention (1)~(33) are shown in 1~table of table 5, compares and is combined with polymerizable liquid crystal Object (34)~(38) concrete composition.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[changing 88]

[changing 89]

[changing 90]

[changing 91]

[changing 92]

Cyclopentanone (E-1)

Methyl iso-butyl ketone (MIBK) (E-2)

Methyl ethyl ketone (E-3)

Toluene (E-4)

[changing 93]

P methoxy phenol (G-1)

Irgacure 907(H-1)

Lucirin TPO(H-2)

Trimethylolpropane tris (3-thiopropionate) (I-1)

Acrylic acid 2- hydroxyl -3- phenoxy-propyl (I-2)

MEGAFACE R-40(J-1)

Polypropylene (Mw=1960) (J-2)

ZFS460 (Evonik Industries corporation) (J-3)

(embodiment 1)

(orientation)

On having glass substrate of the rubbed horizontal alignment with polyimides (Nissan Chemical corporation SE-6414), The polymerizable liquid crystal compound (1) of modulation is coated with 20 seconds with the rotation speed of 100rpm using spin-coating method in room temperature (25 DEG C), It after 70 DEG C 2 minutes dry, placed at 25 DEG C 1 minute, then uses high-pressure mercury-vapor lamp, in the UV light 30 of room temperature irradiation 30mW Second, to obtain the film of embodiment 1.Resulting film is evaluated according to the following conditions.

〇: absolutely not defect when visually, with polarized light microscope observing also absolutely not defect.

△: there is no defect when visually, but there are non-oriented parts in a part with when polarized light microscope observing.

×: a part produces defect when visually, with also there is non-oriented part when polarized light microscope observing on the whole.

(mist degree measurement)

Film obtained in the test of above-mentioned orientation is used to the nephelometer NDH2000 of Nippon Denshoku Industries Co., Ltd. 3 point measurements are carried out, and evaluate average value.

(λ、Δλ)

Use film obtained in the above-mentioned orientation test of spectrophotometer (Japan light splitting corporation, V-560) measurement Reflection kernel wavelength (λ) and maximum reflectivity are selected, the wavelength band of the reflectivity of the half with aforementioned maximum reflectivity is found out Field width degree alternatively reflection wavelength band domain (Δ λ).

Resulting result is shown in table below.

[table 6]

	Composition	Orientation	Mist degree	λ(nm)	Δλ/λ(-)
						Embodiment 1	Composition (1)	○	0.3	590	0.098
Embodiment 2	Composition (2)	○	0.1	582	0.097
						Embodiment 3	Composition (3)	○	0.2	600	0.096
Embodiment 4	Composition (4)	○	0.2	597	0.099
						Embodiment 5	Composition (5)	○	0.2	598	0.096
Embodiment 6	Composition (6)	○	0.2	599	0.096
						Embodiment 7	Composition (7)	○	0.1	596	0.099
Embodiment 8	Composition (8)	○	0.2	589	0.095
						Embodiment 9	Composition (9)	○	0.1	597	0.098
Embodiment 10	Composition (10)	○	0.3	595	0.093
						Embodiment 11	Composition (11)	○	0.3	603	0.091
Embodiment 12	Composition (12)	○	0.3	602	0.091
						Embodiment 13	Composition (13)	○	0.3	585	0.095
Embodiment 14	Composition (14)	○	0.3	593	0.097
						Embodiment 15	Composition (15)	○	0.2	599	0.096
Embodiment 16	Composition (16)	○	0.2	586	0.097
						Embodiment 17	Composition (17)	○	0.2	593	0.095
Embodiment 18	Composition (18)	○	0.2	598	0.092
						Embodiment 22	Composition (22)	○	0.1	458	0.083
Embodiment 23	Composition (23)	○	0.2	463	0.075
						Embodiment 24	Composition (24)	○	0.2	446	0.052
Embodiment 25	Composition (25)	○	0.2	580	0.096
						Embodiment 26	Composition (26)	○	0.2	577	0.095
Embodiment 27	Composition (27)	○	0.2	572	0.077
						Embodiment 28	Composition (28)	○	0.2	582	0.080
Embodiment 29	Composition (29)	○	0.2	584	0.079
						Embodiment 30	Composition (30)	○	0.2	585	0.065
Embodiment 31	Composition (31)	○	0.2	579	0.061
						Comparative example 1	Composition (34)	○	0.2	580	0.123
Comparative example 2	Composition (35)	△	3.5	585	0.145
						Comparative example 3	Composition (36)	×	8.5	Undetermined	Undetermined

[table 7]

	Composition	Orientation	Mist degree	λ(nm)	Δλ/λ(-)
						Embodiment 19	Composition (19)	○	0.2	600	0.096
Embodiment 20	Composition (20)	○	0.2	590	0.091
						Embodiment 21	Composition (21)	○	0.3	586	0.092

[table 8]

	Composition	Orientation	Mist degree	Δn
					Embodiment 32	Composition (32)	○	0.1	0.090
Embodiment 33	Composition (33)	○	0.1	0.050

[table 9]

	Composition	Orientation	Mist degree	Δn
					Comparative example 4	Composition (37)	〇	0.1	0.171
Comparative example 5	Composition (38)	〇	0.2	0.105

(embodiment 2~33, the Comparative Examples 1 to 5)

Using polymerizable liquid crystal compound (2)~(31), (34)~(38), film, measurement orientation, mist degree measurement are made As a result, λ, Δ λ.Using result as embodiment 2~31, the Comparative Examples 1 to 5, it is shown in above-mentioned table.

It should be noted that 2~embodiment of embodiment 18,22~embodiment of embodiment 31, embodiment 32, embodiment 33 and ratio Compared in 1~comparative example of example 5, the substrate of use etc. is evaluated as orientation, similarly to Example 1, using with rubbed water The glass substrate of flat orientation polyimides (Nissan Chemical corporation SE-6414), coating, the solidification of polymerizable liquid crystal compound Condition is set as identical as the condition of embodiment 1.

On the other hand, in 19~embodiment of embodiment 21, as the substrate of orientation evaluation use etc., using PET, in room temperature It is coated in PET base material using stick coating method, at 60 DEG C after dry 2 minutes, using the high-pressure mercury-vapor lamp of conveyor type, according to Accumulated light becomes 900mJ/cm²Mode be configured and irradiate UV light.

In addition, the embodiment 32 of polymerizable liquid crystal compound (32) and (33) has been used, in embodiment 33, due to polymerism Above-mentioned (D-1)~(D-3) ingredient is free of in liquid-crystal composition, therefore measures Δ n.About Δ n, phase difference film, optics material are utilized Expect the phase difference (Re) at check device RETS-100 (great Zhong Electronics Co., Ltd system) measurement 550nm, utilizes contact pin type shape Measurement device DEKTAK (Bruker corporation) measures film thickness (d), calculates Δ n by the relationship of Re=Δ n × d.As a result, real The Δ n for applying film obtained in example 22 is 0.090, and the Δ n of film obtained in embodiment 23 is 0.050.

According to the above results, the polymerism containing general formula (I-1) expression of the invention that formula (A-1)~formula (A-8) indicates The polymerizable liquid crystal chemical combination that the general formula (II-1) of the invention that liquid-crystal compounds and formula (B-1)~formula (B-11) indicate indicates The polymerizable liquid crystal compound (1~embodiment of embodiment 33) of object, with the polymerism indicated without containing general formula (I-1) of the invention The polymerizable liquid crystal compound for the polymerizable liquid crystal compound that liquid-crystal compounds or general formula of the invention (II-1) indicate (compares 1~comparative example of example 5) it compares, it can obtain that orientation is good, selection reflection wavelength band domain (Δ λ)/selection reflection kernel wavelength The value of (λ) and the optical film that the value of Δ n is low and permeability is excellent.

Claims

1. a kind of polymerizable liquid crystal compound contains the one kind or two or more polymerizable liquid crystal indicated by the following general formula (I-1) Compound and the one kind or two or more polymerizable liquid crystal compound indicated by the following general formula (II-1),

[changing 1]

In formula, P¹¹¹And P¹¹²Polymerizable functional group is each independently represented,

Sp¹¹¹And Sp¹¹²Each independently represent the alkylidene or singly-bound of carbon atom number 1~18,1-CH in the alkylidene₂Or Not 2 or more adjacent-CH₂It can be replaced each independently by-COO- ,-OCO- or-OCO-O-, possessed by the alkylidene 1 or 2 or more hydrogen atom can be replaced by halogen atom or CN base,

X¹¹¹And X¹¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CO-、-COO-、-OCO-、-CO-S-、-S- CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH- COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂- COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH= N-N=CH- ,-CF=CF- ,-C ≡ C- or singly-bound, wherein P¹¹¹-Sp¹¹¹、P¹¹²-Sp¹¹²、Sp¹¹¹-X¹¹¹And Sp¹¹²-X¹¹²In do not wrap It is directly connected to containing oxygen atom is mutual,

Q111 and q112 each independently represents 0 or 1,

A¹¹And A¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- diyl, pyrrole Pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, naphthane -2,6- diyl, decahydronaphthalene -2,6- Diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or can be replaced by 1 or more substituent group L,

L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyano, isocyano group, amino, hydroxyl, mercapto Base, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl silyl, dimetylsilyl, Thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can substituted cyclohexylalkyl or 1-CH₂- Or 2 or more not adjacent-CH₂Each independently can by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,- O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰, the carbon that replaces of-CH=N-N=CH- ,-CF=CF- or-C ≡ C- it is former The straight-chain or branch-like alkyl of subnumber 1 to 20, in formula, R⁰Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8, the straight-chain Or any hydrogen atom in branch-like alkyl can be replaced by fluorine atoms, in compound L there are it is multiple when they can it is identical can also With difference, A¹¹There are it is multiple when they can be the same or different, A¹²There are it is multiple when they can be identical or not Together,

Z¹¹And Z¹²Each independently represent-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、-CO-、-COO-、-OCO-、-CO- S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O- NH-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH =CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO- CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N-N= CH- ,-CF=CF- ,-C ≡ C- or singly-bound, Z¹¹There are it is multiple when they can be the same or different, Z¹²There are it is multiple when it Can be the same or different,

M111 and m112 each independently represents 0~2 integer,

R¹And R²It is former to each independently represent hydrogen atom, fluorine atom, cyano, hydroxyl, nitro, the alkyl of carbon atom number 1 to 10, carbon The alkoxy of subnumber 1 to 10, the acyl group of carbon atom number 2 to 10, the alkyl carbonyl oxy of carbon atom number 2 to 10, carbon atom number 2 to 10 Alkoxy carbonyl or carbon number 5~12 aromatic series ring group, R¹Or R²In either indicate hydrogen atom other than group, or R²With adjacent existing A¹²Possessed substituent group L connection and indicate cyclic group,

[changing 1]

In formula, P²¹¹Indicate polymerizable functional group,

A²¹¹And A²¹²Each independently represent 1,4- phenylene, 1,4- cyclohexylidene, bicyclic [2.2.2] octane -1,4- diyl, pyrrole Pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- diyl, naphthalene -1,4- diyl, naphthane -2,6- diyl, decahydronaphthalene -2,6- Diyl or 1,3- bis-Alkane -2,5- diyl, these groups can be unsubstituted or be replaced by 1 or more substituent group L,

L indicates fluorine atom, chlorine atom, bromine atom, iodine atom, Pentafluorosulfanyl, nitro, cyano, isocyano group, amino, hydroxyl, mercapto Base, methylamino, dimethylamino, diethylamino, diisopropylaminoethyl, trimethyl silyl, dimetylsilyl, Thio isocyano group, can substituted phenyl, can substituted phenylalkyl, can substituted cyclohexylalkyl or 1-CH₂- Or 2 or more not adjacent-CH₂Each independently can by-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-CO-S- ,-S-CO- ,- O-CO-O-、-CO-NR⁰-、-NR⁰- CO- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH- ,-CH=CH- ,-N=N- ,-CR⁰=N- ,-N=CR⁰, the carbon that replaces of-CH=N-N=CH- ,-CF=CF- or-C ≡ C- it is former The straight-chain or branch-like alkyl of subnumber 1 to 20, in formula, R⁰Indicate the alkyl of hydrogen atom or carbon atom number 1 to 8, the straight-chain Or any hydrogen atom in branch-like alkyl can be replaced by fluorine atoms, in compound L there are it is multiple when they can it is identical can also With difference, A²¹²There are it is multiple when they can be the same or different,

Z²¹¹Expression-O- ,-S- ,-OCH₂-、-CH₂O-、-CH₂CH₂-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO- O-、-CO-NH-、-NH-CO-、-OCO-NH-、-NH-COO-、-NH-CO-NH-、-NH-O-、-O-NH-、-SCH₂-、-CH₂S-、- CF₂O-、-OCF₂-、-CF₂S-、-SCF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH= CH-、-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂- COO-、-CH₂- OCO- ,-CH=CH- ,-N=N- ,-CH=N- ,-N=CH- ,-CH=N-N=CH- ,-CF=CF- ,-C ≡ C- Or singly-bound, Z²¹¹There are it is multiple when they can be the same or different,

M211 indicates 1~3 integer,

T²¹¹Indicate hydrogen atom ,-OH base ,-SH base ,-CN base ,-COOH base ,-NH₂Base ,-NO₂Base ,-COCH₃Base ,-O (CH₂)_nCH₃ Or-(CH₂)_nCH₃, the integer of n expression 0~20.

2. polymerizable liquid crystal compound according to claim 1, as the polymerizable liquid crystal compound, using combining The polymerizable liquid crystal that general formula (I-1) in whole polymerizable liquid crystal compounds contained in object containing 10~95 mass % indicates The polymerizable liquid crystal compound of compound.

3. polymerizable liquid crystal compound according to claim 1 or 2, as the polymerizable liquid crystal compound, using The polymerism that general formula (II-1) in whole polymerizable liquid crystal compounds contained in composition containing 5~85 mass % indicates The polymerizable liquid crystal compound of liquid-crystal compounds.

4. a kind of optical film has used polymerizable liquid crystal compound according to any one of claims 1 to 3.

5. optical film according to claim 4, birefringence difference Δ n is 0.1 or less.

6. polymerizable liquid crystal compound described in any one of claim 1 to 3, further contains chipal compounds.

7. a kind of optical film has used polymerizable liquid crystal compound as claimed in claim 6.

8. optical film according to claim 7, select reflection wavelength band domain Δ λ/the select value of reflection kernel wavelength X for 0.1 or less.

9. a kind of stacked film, by by optical film as claimed in claim 4 and/or optical film as claimed in claim 7 and other Optical element stacking obtains.

10. a kind of image display device has used optical film as claimed in claim 4 and/or optics as claimed in claim 7 Film.