CN109153857A

CN109153857A - Polarizing layer forms composition

Info

Publication number: CN109153857A
Application number: CN201780020939.6A
Authority: CN
Inventors: 伊藤潤; 菅野裕太; 稻見佳代; 畑中真
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-03-31
Filing date: 2017-03-30
Publication date: 2019-01-04
Anticipated expiration: 2037-03-30
Also published as: WO2017170947A1; TW201807116A; TWI752948B; CN109153857B; JPWO2017170947A1; KR20180132653A; KR102263428B1; JP7078903B2

Abstract

The present invention provides a kind of polymer composition that high dichromatic polarization element can be also obtained even without alignment film.The present invention provides a kind of polymer composition, contains side chain type macromolecule, (B) dichroism pigment and organic solvent that (A) has the structure for showing photoreactivity and the structure for showing liquid crystal liquid crystal property.By the manufacturing method for the step of including the steps that the step of forming film and being coated with the composition on substrate, irradiate the ultraviolet light through polarisation to film obtained and heating to film obtained, high dichromatic polarizing layer can be obtained.Using polymer composition polarization element obtained of the invention due to being not necessarily to alignment film, so being expected to realize the simplification of manufacture processing procedure and the reduction of component cost.

Description

Polarizing layer forms composition

Technical field

The present invention relates to a kind of polarizing layers to form composition.

Background technique

As polarizer used in liquid crystal display etc., generally used iodine as dichroism pigment in the past.However, iodine system There is heat resistance or light resistance equal difference in light polarizing film, therefore attempt to utilize organic system dichroic substance, i.e. dichroism pigment.

Before this, as dichroism pigment, in order to obtain high-caliber dichroism, use more with azo skeleton as The pigment (Patent Documents 1 to 2) of basic framework or the pigment with anthraquinone skeleton etc..

In addition, the manufacturing method as polarizer, in addition to will include that the polymer film of iodine or dichroism pigment etc. prolongs Other than the method stretched, it is also known that as application type polarizer, mixed in base plate coating to the liquid-crystal compounds for becoming material of main part The method (patent document 3) of liquid-crystal composition made of pigment as guest materials.In addition, it is also proposed that following method: for Offer more stable light polarizing film and the method (patent document for using the mixture of bridging property liquid crystal and polymerism dichroic dye 4)；The non-liquid crystal solvent of polymerism is added to polymerizable liquid crystal compound, the non-liquid crystal solvent of polymerism is made to remain in film and change The manufacturing method (patent document 5) of the optically anisotropic body of the adhesion of kind and other optical films etc.；And preparation is comprising poly- The polymerizable liquid crystal former base preparation of conjunction property mesogen based compound and dichroism pigment, using the polymerizable liquid crystal former base preparation, The method (patent document 6) of polaroid is be effectivelyed prepared in terms of time and cost.

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2011-213610 bulletin

Patent document 2: Japanese patent special table 2006-525382 bulletin

Patent document 3: Japanese patent special table 2008-547062 bulletin

Patent document 4: Japanese patent special table 2004-535483 bulletin

Patent document 5: Japanese Patent Laid-Open 2004-198480 bulletin

Patent document 6: Japanese patent special table 2006-161051 bulletin

Summary of the invention

[problems to be solved by the invention]

However, the application type polarizer comprising liquid-crystal compounds and dichroism pigment is necessary in order to show required characteristic Make liquid-crystal compounds orientation.In general, coating of liquid crystalline compound and two colors on the liquid crystal orienting film for being implemented with orientation processing Property pigment and control orientation, therefore there are problems that must thering is liquid crystal orienting film.

Under the background, the purpose of the present invention is to provide one kind can be made without liquid crystal orienting film with required spy Property application type polarizer polarizing layer formed composition.

[technical means to solve problem]

Present inventor et al. studies, in order to reach the project as a result, it has been found that invention below through great efforts.

A kind of polymer composition of 1 > of <, containing (A) has the structure for showing photoreactivity and shows liquid crystal liquid crystal property Structure side chain type macromolecule, (B) dichroism pigment and organic solvent.

The polymer composition that 2 > of < such as 1 > of < is recorded, wherein (A) ingredient, which has, can cause photo-crosslinking, photic different The photonasty side chain that structure or light Fu Lishi are reset is as the structure for showing photoreactivity.

The polymer composition that 3 > of < such as 2 > of < is recorded, wherein (A) ingredient have selected from by following formula (1)~ (6) any photonasty side chain in group composed by.

[changing 1]

In formula, A, B, D separately indicate singly-bound ,-O- ,-CH₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH =CH-CO-O- or-O-CO-CH=CH-；

S is the alkylidene of carbon number 1~12, and the hydrogen atom being bonded on these bases can be substituted by halogen；

T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom being bonded on these bases can be substituted by halogen；

Y₁In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or be identical or different 2~6 ring in these substituent groups via base made of bonding base B bonding, on these bases The hydrogen atom being bonded can separately be substituted by-COOR₀(in formula, R₀Indicate the alkane of hydrogen atom or carbon number 1~5 Base) ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

Y₂For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and this Base in group composed by the combination of a little rings, the hydrogen atom being bonded on these bases can separately be substituted by-NO₂、- CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y₁Identical definition；

X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH =CH-, when the quantity of X is 2, X can be the same or different each other；

Cou indicates Coumarin-6-base or coumarin-7-base, and the hydrogen atom being bonded on these bases can be separately It is substituted by-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxygen Base；

Q1 and q2 mono- for 1 and another is 0；

Q3 is 0 or 1；

P and Q respectively stand alone as selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 rouge Base in group composed by the combination of ring type hydrocarbon and these rings；It wherein, is-CH=CH-CO-O- ,-O-CO-CH=CH- in X In the case of, the P or Q for the side that-CH=CH- is bonded are aromatic rings；

L1 is 0 or 1；

The integer that l2 is 0~2；

When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；

When l1 is 1, B also illustrates that singly-bound when T is singly-bound；

H and I is respectively stood alone as in the combination of phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and these rings Base.

The polymer composition that any one of for example described 3 > of < 1 > to < of 4 > of < is recorded is selected from wherein (A) ingredient has Any liquid crystal liquid crystal property side chain in the group as composed by following formula (21)~(31).

[changing 2]

In formula, A, B, q1 and q2 have and the identical definition；

Y₃For selected from the ester ring type hydrocarbon by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 with And the base in group composed by the combination of these rings, the hydrogen atom being bonded on these bases can separately be substituted by- NO₂,-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

R₃Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the phenyl ring of 1 valence, naphthalene nucleus, biphenyl Ring, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy；

L indicate 1~12 integer, m indicate 0~2 integer, wherein in formula (25)~(26), all m add up to 2 with On, in formula (27)~(28), all m's adds up to 1 or more, and m1, m2 and m3 separately indicate 1~3 integer；

R₂Indicate hydrogen atom ,-NO₂,-CN, halogen, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon and alkyl or alkyl oxy；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

The polymer composition that any one of for example described 4 > of < 1 > to < of 5 > of < is recorded, it is characterised in that: containing following Compound represented by formula (c) is used as (C) ingredient.

[changing 3]

(in formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In wantonly three to five separately indicate be selected from hydrogen atom, halogen Plain atom, C₁~C₆Alkyl, C₁~C₆Alkylhalide group, C₁~C₆Alkoxy, C₁~C₆Alkyl groups in the halogenalkoxy, C₃~C₈Naphthenic base, C₃~C₈Halogen Naphthenic base, C₂~C₆Alkenyl, C₂~C₆Haloalkenyl, C₃~C₈Cycloalkenyl, C₃~C₈Halogen cycloalkenyl, C₂~C₆Alkynyl, C₂~C₆Halogen alkynes Base, C₁~C₆Alkoxy, C₁~C₆Alkyl groups in the halogenalkoxy, (C₁~C₆Alkyl) carbonyl, (C₁~C₆Alkylhalide group) carbonyl, (C₁~C₆Alcoxyl Base) carbonyl, (C₁~C₆Alkyl groups in the halogenalkoxy) carbonyl, (C₁~C₆Alkyl amino) carbonyl, (C₁~C₆Alkylhalide group) amino carbonyl, two (C₁ ~C₆Alkyl) substituent group in amino carbonyl, cyano and nitro, in R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In wantonly three to four In the case where the definition, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In it is remaining one or two indicate following formula (c-2)

[changing 4]

(in formula (c-2), dotted line indicates bonding key, R¹⁰⁶For the carbocyclic ring of the alkylidene of carbon number 1~30, phenylene or divalent Or heterocycle, the alkylidene, the carbocyclic ring of phenylene or divalent or one or more hydrogen atoms in heterocycle can be substituted by fluorine original Son or organic group.In addition, R¹⁰⁶In-CH₂CH₂- CH=CH-, R can be substituted by¹⁰⁶In-CH₂Asia can be substituted by The carbocyclic ring or heterocycle of phenyl or divalent, quilt in the case where alternatively, it is also possible to not adjoin each other in any one base being exemplified below It is substituted by these bases :-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-.R¹⁰⁷For hydrogen atom or first Base) represented by base, n indicates 0 or 1)

A kind of polarizing layer of 6 > of < forms composition, contains the polymerization recorded such as any one of described 5 > of < 1 > to < Compositions.

[The effect of invention]

According to the present invention it is possible to provide a kind of suitable for obtaining the novel polymerization with the polarizer of high-level polarizing properties Compositions.

Specific embodiment

Present inventor studies through great efforts, as a result obtains opinion below, thereby completing the present invention.

Polymer composition used in the manufacturing method of the present invention have can show the photosensitive of liquid crystal liquid crystal property Side chain type macromolecule (hereinafter also referred to as side chain type macromolecule) and dichroism pigment, are obtained using the polymer composition Film be with the high molecular film of photosensitive side chain type of liquid crystal liquid crystal property can be shown.For the film, without friction It handles and orientation processing is carried out by polarisation irradiation.In addition, after polarisation irradiation, by heating the side chain type polymeric membrane Step, and become the film (hereinafter also referred to polarizing layer) with polarizing properties.At this point, being shown by polarisation irradiation light Micro- anisotropy becomes driving force (driving force), and side chain type macromolecule of liquid crystal liquid crystal property itself has by self assembly Efficient orientation again.As a result realize that the efficient orientation as polarizing layer is handled.Herein, contain two by polymer composition Color pigment can obtain the polarizing layer with high dichroic ratio.Therefore, polymer composition of the invention is as polarizing layer shape It is useful at composition.

Hereinafter, implementation form of the invention is described in detail.

< < (A) has the side chain type macromolecule > > of the structure for showing photoreactivity and the structure for showing liquid crystal liquid crystal property

(A) ingredient is the side chain type macromolecule with the structure for showing photoreactivity and the structure for showing liquid crystal liquid crystal property, The photosensitive side chain type macromolecule of liquid crystal liquid crystal property can as be shown.

(A) side chain type macromolecule preferably carries out reaction under the light of the wave-length coverage of 250nm~400nm and 60 DEG C~300 Liquid crystal liquid crystal property is shown within the temperature range of DEG C.

(A) side chain type macromolecule, which preferably has, to be reacted photosensitive under the light of the wave-length coverage of 250nm~400nm Property side chain.

(A) side chain type macromolecule preferably has liquid crystal former base, so that showing liquid within the temperature range of 60 DEG C~300 DEG C Crystalline substance.

(A) side chain type macromolecule is bonded with photosensitive side chain on main chain, can be incuded light and be caused crosslinking anti- It answers, isomerization reaction or light Fu Lishi are reset.Structure with photosensitive side chain is not particularly limited, it is generally desirable to incude light And the structure for causing cross-linking reaction or light Fu Lishi to be reset, it may be more desirable to cause the structure of cross-linking reaction.In the case, i.e., Just it is exposed under the external stresses such as heat, can also keep realized polarizing properties steadily in the long term.In addition, just by the side chain type Macromolecule can obtain the aspect of stable polarizing properties when polarizing layer is made for, rigidity is included preferably in side-chain structure Mesogen based component.

The high molecular structure for example can be set to following structures: with main chain and the side chain for being bonded in main chain, the side chain With mesogens based components such as xenyl, terphenyl base, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzenes and it is bonded in end The induction light of end and the photonasty base for causing cross-linking reaction or isomerization reaction；Or with main chain and the side for being bonded in main chain Chain, the side chain have the phenylamino benzoic acid ester group for being not only mesogen based component and causing scholar's rearrangement reaction in light husband.As energy The more specific structural example of the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property is enough shown, preferably such as flowering structure: by being selected from By hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, benzene At least one in group composed by the radically polymerizable groups such as ethylene, ethylene, maleimide, norbornene and siloxanes On the constituted main chain of kind, it is bonded with photosensitive side chain and with the side chain of liquid crystal liquid crystal property.

As with photosensitive side chain, preferably there is the knot comprising at least one side chain in following formula (1)~(6) Structure.

[changing 5]

Q1 and q2 mono- for 1 and another is 0；

Q3 is 0 or 1；

L1 is 0 or 1；

The integer that l2 is 0~2；

When l1 is 1, B also illustrates that singly-bound when T is singly-bound；

Side chain is suitably any photonasty side chain in the group as composed by following formula (7)~(10).

In formula, A, B, D, Y₁、X、Y₂And R has and the identical definition；

L indicates 1~12 integer；

M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；

N indicates 0~12 integer (wherein, B is singly-bound when n=0).

[changing 6]

Side chain is suitably any photonasty side chain in the group as composed by following formula (11)~(13).

In formula, A, X, l, m and R have and the identical definition.

[changing 7]

Side chain is suitably photonasty side chain represented by following formula (14) or (15).

In formula, A, Y₁, X, l, m1 and m2 have and the identical definition.

[changing 8]

Side chain is suitably photonasty side chain represented by following formula (16) or (17).

In formula, A, X, l and m have and the identical definition.

[changing 9]

In addition, side chain is suitably photonasty side chain represented by following formula (18) or (19).

In formula, A, B, Y₁, q1, q2, m1 and m2 have and the identical definition.

R₁Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, carbon number 1~5 alkyl or carbon number 1~5 alkyl oxy.

[changing 10]

Side chain is suitably photonasty side chain represented by following formula (20).

In formula, A, Y₁, X, l and m have and the identical definition.

[changing 11]

It is suitably selected from any one of group as composed by following formula (21)~(31) as the side chain with liquid crystal liquid crystal property Liquid crystal liquid crystal property side chain.

In formula, A, B, q1 and q2 have and the identical definition；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

[changing 12]

The high molecular preparation method > > of the photosensitive side chain type of < <

The photosensitive side chain type macromolecule that can show liquid crystal liquid crystal property can be by making have the photonasty side The photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer of chain are polymerize and are obtained.

[photoreactivity side chain monomer]

So-called photoreactivity side chain monomer refers in the case where forming high molecular situation, can be formed in high molecular side chain portion Position has the high molecular monomer of photonasty side chain.

As photoreactivity base possessed by side chain, preferably following structures and its derivative.

[changing 13]

It, should preferably with the structure of polymerism base and photonasty side chain as the more specific example of photoreactivity side chain monomer Polymerism base is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-methylene The radically polymerizable groups such as base-gamma-butyrolacton, styrene, ethylene, maleimide, norbornene and siloxanes institute group At the polymerism base that constitutes of at least one of group, which is at least one comprising the formula (1)~(6) Photonasty side chain, preferably for example comprising at least one photonasty side chain in the formula (7)~(10), comprising the formula (11)~ (13) photonasty side chain represented by least one photonasty side chain, the formula (14) or (15), the formula (16) or (17) photonasty side chain represented by the photonasty side chain, the formula (18) or (19) represented by, represented by the formula (20) Photonasty side chain.

As this photoreactivity side chain monomer, such as can enumerate selected from following formula M1-1~M1-7 and M1-17~M1-20 In monomer.

[changing 14]

[changing 15]

[changing 16]

(in formula, M1 is hydrogen atom or methyl, and s1 indicates the quantity of methylene, is 2~9 natural number)

[changing 17]

(in formula, R is OH or NH₂, it is 2~9 natural number that M1, which is hydrogen atom or methyl, and s1 indicates the quantity of methylene)

It as the monomer with light regiospecific base represented by the formula (1), such as can enumerate: 4- (6- methacryl Oxygroup hexyl -1- oxygroup) cinnamic acid, 4- (6- acryloxy hexyl -1- oxygroup) cinnamic acid, 4- (3- methacryloxy Propyl -1- oxygroup) cinnamic acid, 4- (4- (6- Methacryloxyhexyl -1- oxygroup) benzoyloxy) cinnamic acid equation (1) In R be OH monomer and 4- (6- Methacryloxyhexyl -1- oxygroup) cinnamamide, 4- (6- acryloxy oneself Base -1- oxygroup) cinnamamide, the R in 4- (3- methacryloxypropyl -1- oxygroup) cinnamamide equation (1) be NH₂'s Monomer etc..

[liquid crystal liquid crystal property side chain monomer]

So-called liquid crystal liquid crystal property side chain monomer refers to that the high molecular form from the monomer reveals liquid crystal liquid crystal property, which can be in side The monomer of chain position formation liquid crystal former base.

As liquid crystal former base possessed by side chain, it can individually become liquid crystal former base for xenyl or phenylamino benzoic acid ester group etc. The base of structure, or carrying out hydrogen bonding each other by side chain as benzoic acid etc. becomes the base of mesogen based structures. As liquid crystal former base possessed by side chain, preferably following structures.

[changing 18]

As the more specific example of liquid crystal liquid crystal property side chain monomer, preferably such as flowering structure: having by selected from by hydrocarbon, (methyl) acrylic acid Ester, itaconate, fumarate, maleate, alpha-methylene-gamma-butyrolactone, styrene, ethylene, maleic two The polymerism that at least one of group composed by the radically polymerizable groups such as acid imide, norbornene and siloxanes is constituted Base and include at least one side chain in the formula (21)~(31).

Among this liquid crystal liquid crystal property monomer, as the monomer with carboxyl, also it can be used selected from by following formula M2-1~M2- Monomer represented by formula in group composed by 9.

[changing 19]

[changing 20]

In addition, an example as the other monomers, choosing is also can be used in the monomer with substituent group for showing liquid crystal liquid crystal property Monomer represented by formula in group composed by free following formula M2-10~M2-16.

[changing 21]

(A) side chain type macromolecule can pass through the copolymerization of the photoreactivity side chain monomer for showing liquid crystal liquid crystal property And it obtains.Furthermore it is possible to by do not show liquid crystal liquid crystal property photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer combined polymerization, Or it shows the combined polymerization of the photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer of liquid crystal liquid crystal property and obtains.In addition, can be lossless In the range of the performance energy of liquid crystal liquid crystal property and other monomers carry out combined polymerization.

As other monomers, for example, can enumerate can be obtained by industrial means be able to carry out Raolical polymerizable Monomer.

It as the concrete example of other monomers, can enumerate: unsaturated carboxylic acid, acrylate compounds, methacrylated Close object, maleimide compounds, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..

It as the concrete example of unsaturated carboxylic acid, can enumerate: acrylic acid, methacrylic acid, itaconic acid, maleic acid, anti- Butene dioic acid etc..

It as acrylate compounds, such as can enumerate: methyl acrylate, ethyl acrylate, isopropyl acrylate, propylene Acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxy triethylene third Olefin(e) acid ester, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- gold Rigid Arrcostab, acrylic acid 2- propyl -2- adamantane esters, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- ethyl -8- three Ring last of the ten Heavenly stems ester etc..

It as methacrylate compound, such as can enumerate: methyl methacrylate, ethyl methacrylate, methyl Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- gold Rigid Arrcostab, methacrylic acid 2- propyl -2- adamantane esters, methacrylic acid 8- methyl -8- tricyclodecyl and metering system Sour 8- ethyl -8- tricyclodecyl etc..

It as vinyl compound, such as can enumerate: vinethene, ethylene methacrylic ether, benzyl ethylene ether, 2- hydroxyethyl second Alkene ether, phenylvinyl ether and propyl vinyl ether etc..

It as distyryl compound, such as can enumerate: styrene, methyl styrene, chlorostyrene, bromstyrol etc..

As maleimide compounds, such as can enumerate: maleimide, N- methyl maleoyl- are sub- Amine, N- phenylmaleimide and N- cyclohexylmaleimide etc..

About the content of the photoreactivity side chain in side chain type macromolecule of the invention, with regard to LCD alignment aspect and Speech, preferably 10 moles of %~100 mole %, more preferable 20 moles of %~95 mole %, further preferred 30 moles of %~90 are rubbed You are %.

About the content of the liquid crystal liquid crystal property side chain in side chain type macromolecule of the invention, for the aspect of LCD alignment, It is preferred that 90 moles of % are hereinafter, more preferable 5 moles of %~80 mole %, further preferred 10 moles of %~70 mole %.

Side chain type macromolecule of the invention contains other sides other than the photoreactivity side chain and liquid crystal liquid crystal property side chain Chain.The content of other side chains the content of the photoreactivity side chain and liquid crystal liquid crystal property side chain it is total not up to 100% in the case where For the remainder.

The high molecular manufacturing method of side chain type about this implementation form, is not particularly limited, using in industrial operation General method.Specifically, the sun using liquid crystal liquid crystal property side chain monomer or the vinyl of photoreactivity side chain monomer can be passed through Ionic polymerization or free radical polymerization, anionic polymerisation and manufacture.Among these, for reacting the viewpoints such as property easy to control, especially It is preferred that free radical polymerization.

As the polymerization initiator of free radical polymerization, radical polymerization initiator can be used or reversible addition-is split Compound well known to solution type chain tra nsfer (RAFT) polymerization agent etc..

Free radical thermal polymerization is the compound generated free radicals and being heated to decomposition temperature or more.As this Kind free radical thermal polymerization, such as can enumerate: peroxidating ketone (methyl ethyl ketone peroxide, cyclohexanone peroxide etc.), Peroxidating two acyl base class (acetyl peroxide, benzoyl peroxide etc.), hydroperoxide kind (the tertiary fourth of hydrogen peroxide, hydroperoxidation Base, cumene hydroperoxide etc.), dialkyl class (di-t-butyl peroxide, cumyl peroxide, peroxidating February Osmanthus acyl etc.), peroxy ketal class (dibutyl cyclohexane peroxide etc.), alkyl peroxyesters class (new peroxide tert-butyl caprate, mistake Aoxidize the pivalic acid tert-butyl ester, peroxidating 2- cyclohexyl acid tert-pentyl ester etc.), persulfuric acid salt (potassium peroxydisulfate, sodium peroxydisulfate, mistake Ammonium sulfate etc.), azo compound (azodiisobutyronitrile and 2,2'- bis- (2- hydroxyethyl) azodiisobutyronitrile etc.).It is this Free radical thermal polymerization can be used alone, or two or more can also be applied in combination.

As long as radical photopolymerization initiator is the compound for causing free radical polymerization by light irradiation, without especially limit It is fixed.It as this radical photopolymerization initiator, can enumerate: bis- (diethylaminos) two of benzophenone, meter Qi Le ketone, 4,4'- Benzophenone, xanthone, thioxanthones, isopropyl xanthone, 2,4- diethyl thioxanthone, 2- ethyl hydrazine, acetophenone, 2- hydroxyl Base -2- methyl phenyl ketone, 2- hydroxy-2-methyl -4'- cumene acetone, 1- hydroxycyclohexylphenylketone, isopropyl styrax Ether, isobutyl group benzoin ether, 2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, camphorquinone, benzanthracene Ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinopropane-1- ketone, 2- benzyl-2- dimethylamino-1- (4- morpholine Base phenyl)-butanone -1, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, bis- (tert-butyl of 4,4'- Cross oxygen carbonyl) benzophenone, 3,4,4'- tri- (t-butyl peroxy carbonyl) benzophenone, 2,4,6- trimethyl benzoyl diphenyl Base phosphine oxide, bis- (trichloromethyl) s-triazine of 2- (4'- methoxyl-styrene) -4,6-, 2- (3', 4'- dimethoxy styrene Base) bis- (trichloromethyl) s-triazine of -4,6-, bis- (trichloromethyl) s-triazine of 2- (2', 4'- dimethoxy-styryl) -4,6-, Bis- (trichloromethyl) s-triazine of 2- (2'- methoxyl-styrene) -4,6-, 2- (4'- amyl phenyl ether vinyl) -4,6- bis- (three Chloromethyl) s-triazine, 4- [to N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl) s-triazine, the bis- (trichlorines of 1,3- Methyl) -5- (2'- chlorphenyl) s-triazine, bis- (trichloromethyl) -5- (4'- methoxyphenyl) s-triazine of 1,3-, 2- is (to diformazan Base aminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'- Carbonyl bis- (7- diethyl amino coumarins), 2- (Chloro-O-Phenyl) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxaline, 2,2'- are bis- (2- chlorphenyl) -4,4', 5,5'- tetra- (4- carboethoxyphenyl) -1,2'- bisglyoxaline, 2,2'- bis- (2,4 dichloro benzene bases) - 4,4', 5,5'- tetraphenyl -1,2'- bisglyoxaline, 2,2' bis- (2,4- dibromo phenyl) -4,4', 5,5'- tetraphenyl -1,2'- join miaow Bis- (2,4,6- trichlorophenyl) -4,4', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of azoles, 2,2'-, 3- (2- methyl -2- dimethylamino Base propiono) carbazole, 3,6- bis- (2- methyl -2- morpholinyl propiono) -9- dodecyl carbazoles, 1- hydroxycyclohexylphenyl Ketone, bis- (5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base)-phenyl) titaniums, 3,3', 4,4'- tetra- (t-butyl peroxy carbonyl) benzophenone, 3,3', 4,4'- tetra- (tertiary hexyl crosses oxygen carbonyl) benzophenone, bis- (methoxyl group of 3,3'- Carbonyl) -4,4'- two (t-butyl peroxy carbonyl) benzophenone, two (t-butyl peroxy of 3,4'- bis- (methoxycarbonyl) -4,3'- Carbonyl) benzophenone, 4,4'- bis- (methoxycarbonyl) -3,3'- two (t-butyl peroxy carbonyl) benzophenone, 2- (3- methyl - 3H- benzothiazole -2- subunit) -1- naphthalene -2- base-ethyl ketone or 2- (3- methyl-1,3- benzothiazole -2 (3H)-subunit) -1- (2- Benzoyl) ethyl ketone etc..These compounds may be used alone, can also be 2 or more kinds in combination.

There is no particular restriction for radical polymerization, can use emulsion polymerization method, suspended polymerization, dispersion copolymerization method, sink Shallow lake polymerization, blocky polymerization, solution polymerization process etc..

As organic solvent used in the high molecular polymerization reaction of photosensitive side chain type of liquid crystal liquid crystal property can be shown, As long as macromolecule dissolution generated can be made, it is not particularly limited.It is exemplified below the concrete example of organic solvent.

It can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl -2- Pyrrolidones, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-Ding Nei Ester, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl Ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, acetic acid methyl cellosolve, acetic cellosolve, butyl card must Alcohol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, acetic acid 3- methyl -3- methoxybutyl, Tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyric acid fourth Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, normal octane, diethyl ether, Cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propyleneglycolmethyletheracetate monoethyl ether ester, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-c acid methyl second Ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxypropionic acid fourth Ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..

These organic solvents can be used alone, and can also be used in mixed way.Alternatively, it is also possible to will be unable to make height generated The solvent of molecular melting is used in mixed way in the range of macromolecule generated will not be precipitated with the organic solvent.

In addition, the oxygen in organic solvent will lead to polymerization reaction and be obstructed, therefore organic solvent is preferred in free radical polymerization Use solvent degassed as much as possible.

Polymerization temperature when free radical polymerization can choose 30 DEG C~150 DEG C of arbitrary temp, preferably 50 DEG C~100 DEG C Range.In addition, reaction can carry out under any concentration, but if concentration is too low, then it is difficult to obtain the polymer of high molecular weight, If excessive concentration, the viscosity of reaction solution becomes excessively high and is difficult to uniform stirring, therefore monomer concentration preferably 1 mass %~50 Quality %, the more preferable 5 mass mass of %~30 %.Initial reaction stage can carry out in higher concentrations, hereafter add organic solvent again.

In the Raolical polymerizable, if the ratio of radical polymerization initiator is on the high side for monomer, High molecular molecular weight obtained becomes smaller, if on the low side, high molecular molecular weight obtained becomes larger, therefore relative to making Polymerization monomer, the ratio of radical initiator preferably 0.1 mole of %~10 mole %.In addition, can also be added when polymerization Various monomer components or solvent, initiator etc..

[recycling of polymer]

From passing through the reaction photosensitive side chain type high molecular reaction obtained that can show liquid crystal liquid crystal property When recycling macromolecule generated in solution, as long as putting into reaction solution into poor solvent, make these polymer precipitating i.e. It can.It as the poor solvent for precipitating, can enumerate: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, Methylethyl Ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, diethyl ether, Methyl ether, water etc..The polymerization precipitated after putting into poor solvent Object can carry out air drying or heat drying under normal or reduced pressure after filtering and being subject to recycling.In addition, if making to precipitate The polymer of recycling is dissolved in organic solvent again, carries out precipitating recycling again, is repeated the operation 2 times~10 times, then can Enough reduce the impurity in polymer.As poor solvent at this time, such as alcohols, ketone, hydrocarbon can be enumerated etc., it is preferable to use being selected from 3 kinds or more of poor solvent in these solvents, can so further increase purification efficiency.

About the high molecular molecular weight of (A) side chain type of the invention, painting film strength obtained, film shape are being considered At when workability and film uniformity in the case where, pass through GPC (Gel Permeation Chromatography, gel Permeation chromatography) weight average molecular weight preferably 2000~1000000, more preferable 5000~100000 measured by method.

< (B) dichroism pigment >

So-called dichroism pigment refers to the absorbance in absorbance and short-axis direction on the long axis direction with molecule not The pigment of same property.

Dichroism pigment, which preferably has in the range of 300~700nm, absorbs very big wavelength (λ MAX) person.As this two Color pigment, such as can enumerate: acridine pigment, oxazines pigment, anthocyanidin, naphthalene pigment, azopigment and anthraquinone pigment etc., In, preferred azopigment.It as azopigment, can enumerate: monoazo pigment, bisazo pigment, trisazo- pigment, four azo colors Element and Stilbene-azopigment etc., preferably bisazo pigment and trisazo- pigment.

As azopigment, such as compound represented by formula (b) can be enumerated and (be known as " compound below according to situation (b)」)。

A¹(- N=N-A²)_p- N=N-A³ (b)

[in formula (b),

A¹And A³It is mutually indepedent to indicate to can have the phenyl of substituent group, can have the naphthalene of substituent group or can have The heterocycle of 1 valence of substituent group.A²Expression can have the 1,4- phenylene of substituent group, can have the naphthalene -1,4- of substituent group Diyl or can have substituent group divalent heterocycle.P indicates 1~4 integer.It is more in the case where p is 2 or more integer A A²Independently of each other, it can be the same or different]

As the heterocycle of 1 valence, can enumerate from quinoline, thiazole, benzothiazole, thieno thiazole, imidazoles, benzimidazole, The heterocyclic compounds such as oxazole and benzoxazoles remove 1 hydrogen atom base obtained.As the heterocycle of divalent, can enumerate from institute It states heterocyclic compound and removes 2 hydrogen atom bases obtained.

As A¹And A³In phenyl, naphthalene and 1 valence heterocycle and A²In to phenylene, naphthalene -1,4- diyl and 2 The substituent group that the heterocycle of valence arbitrarily has can be enumerated: the alkyl of carbon number 1~4；The carbon such as methoxyl group, ethyoxyl and butoxy The alkoxy of number 1~4；The fluorinated alkyl of the carbon numbers such as trifluoromethyl 1~4；Cyano；Nitro；Halogen atom；Amino, diethyl amino (the so-called amino being substituted refers to 1 or 2 carbon numbers 1~6 amino that base and pyrrolidinyl etc. are substituted or are unsubstituted Alkyl amino or 2 replace alkyl to be mutually bonded and formed the amino of the alkane diyl of carbon number 2~8.The ammonia being unsubstituted Base refers to-NH₂)。

As the alkyl of carbon number 1~6, it can be arbitrarily straight-chain or branched, can enumerate: methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1,1- bis- Methyl-propyl, 2,2- dimethyl propyl, n-hexyl, 1- methyl amyl, 2- methyl amyl, 1,1- dimethylbutyl, 1- ethyl fourth Base, 1,1,2- thmethylpropyl etc..

Among compound (b), formula (2-1) preferably below~represented compound of formula (2-6) difference.

[changing 22]

[changing 23]

[in formula (2-1)~(2-6),

B¹~B²⁰It is mutually indepedent to indicate hydrogen atom, the alkyl of carbon number 1~6, the alkoxy of carbon number 1~4, cyano, nitro, warp Amino (amino being substituted and the amino being unsubstituted are as defined above), chlorine atom or the trifluoro for replacing or being unsubstituted Methyl.

N1~n4 indicates 0~3 integer independently of each other.

In the case where n1 is 2 or more, multiple B²Independently of each other, it can be the same or different,

In the case where n2 is 2 or more, multiple B⁶Independently of each other, it can be the same or different,

In the case where n3 is 2 or more, multiple B⁹Independently of each other, it can be the same or different,

In the case where n4 is 2 or more, multiple B¹⁴Independently of each other, it can be the same or different]

Compound represented by the anthraquinone pigment preferred formula (2-7).

[changing 24]

[in formula (2-7),

R¹~R⁸It is mutually indepedent to indicate hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

R^xIndicate the alkyl of carbon number 1~4 or the aryl of carbon number 6~12]

Compound represented by the evil ketone pigment preferred formula (2-8).

[changing 25]

[in formula (2-8),

R⁹~R¹⁵It is mutually indepedent to indicate hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

R^xIndicate the alkyl of carbon number 1~4 or the aryl of carbon number 6~12]

Compound represented by the acridine pigment preferred formula (2-9).

[changing 26]

[in formula (2-9),

R¹⁶~R²³It is mutually indepedent to indicate hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

R^xIndicate the alkyl of carbon number 1~4 or the aryl of carbon number 6~12]

As the R in formula (2-7), formula (2-8) and formula (2-9)^xThe alkyl of represented carbon number 1~4, can enumerate: methyl, Ethyl, propyl, butyl, amyl and hexyl etc. can be enumerated as the aryl of carbon number 6~12: phenyl, toluyl groups, dimethylbenzene Base and naphthalene etc..

Compound represented by compound represented by the anthocyanidin preferred formula (2-10) and formula (2-11).

[changing 27]

[in formula (2-10),

D¹And D²Any represented base in mutually indepedent expression (2-10a)~formula (2-10d).

[changing 28]

N5 indicates 1~3 integer]

[changing 29]

[in formula (2-11),

D³And D⁴Any represented base in mutually indepedent expression (2-11a)~formula (2-11h).

[changing 30]

N6 indicates 1~3 integer]

In addition, the commercially available product as dichroism pigment as described above, such as can enumerate: G-207, G-241, G-470 (woods Former company's manufacture), Yellow-8, KRD-901, KRD-902 (manufacture of Showa chemical industry limited liability company), SI-486 (three Well chemistry limited liability company manufacture).

The content that the dichroism pigment as (B) ingredient in composition is formed about polarizing layer, just makes dichroism pigment Orientation become good viewpoint for, relative to high molecular 100 mass parts of side chain shape as (A) ingredient, preferably 0.1 matter Part or more and 30 below the mass is measured, more than more preferable 0.1 mass parts and 20 below the mass, further preferred 0.1 mass parts Above and 10 below the mass, more than particularly preferred 0.1 mass parts and 5 below the mass.

< (C) ingredient >

Polymer composition of the invention can also contain compound represented by following formula (c) and be used as (C) ingredient.

[changing 31]

[changing 32]

It as the halogen atom in this specification, can enumerate: fluorine atom, chlorine atom, bromine atom and iodine atom.Furthermore this The notation of " halogen " also illustrates that these halogen atoms in specification.

C in this specification_a~C_bThe notation of alkyl indicates the hydrocarbon for the straight-chain or branched that carbon atom number is a~b Base as concrete example, such as can be enumerated: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, N-pentyl, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1- ethyl propyl, 1,1- dimethyl propyl, 1,2- dimethyl Propyl, 2,2- dimethyl propyl, n-hexyl, 1- methyl amyl, 2- methyl amyl, 1,1- dimethylbutyl, 1,3- dimethyl butyrate Base, heptyl, octyl, nonyl, decyl, undecyl, dodecyl etc., can according to the range of respectively specified carbon atom number and It is selected.

C in this specification_a~C_bThe notation of alkylhalide group indicates that the hydrogen atom being bonded on carbon atom is arbitrarily substituted by The alkyl of straight-chain or branched that the carbon atom number of halogen atom is a~b, at this point, being taken by 2 or more halogen atoms In the case where generation, these halogen atoms can be identical each other, can also be different each other.It as concrete example, such as can enumerate: fluorine first Base, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, chlorine methyl fluoride, dichloromethyl, bromine methyl fluoride, trifluoromethyl, chlorine difluoro first Base, dichlorofluoromethyl, trichloromethyl, bromine difluoro methyl, bromine chlorine methyl fluoride, dibromo methyl fluoride, 2- fluoro ethyl, 2- chloroethyl, 2- The chloro- 2- fluoro ethyl of bromoethyl, 2,2- bis-fluoro ethyls, 2-, 2,2- Dichloroethyl, the bromo- 2- fluoro ethyl of 2-, 2,2,2- trifluoroethyl, The chloro- 2,2- bis-fluoro ethyls of 2-, the chloro- 2- fluoro ethyl of 2,2- bis-, 2,2,2- trichloroethyl, the bromo- 2,2- bis-fluoro ethyls of 2-, the bromo- 2- of 2- The bromo- 2,2- Dichloroethyl of chloro- 2- fluoro ethyl, 2-, tetra- fluoro ethyl of 1,1,2,2-, pentafluoroethyl group, the chloro- 1,2,2,2- tetrafluoro second of 1- Chloro- tetra- fluoro ethyl of 1,1,2,2- of base, 2-, the chloro- 1,2,2- trifluoroethyl of 1,2- bis-, bromo- tetra- fluoro ethyl of 1,1,2,2- of 2-, 2- fluorine third The chloro- 2- fluoropropyl of base, 2- chloropropyl, 2- bromopropyl, 2-, bis- chloropropyl of 2,3-, the bromo- 3- fluoropropyl of 2-, the bromo- 2- chloropropyl of 3-, Bromo- bis- fluoropropyl of 3,3- of 2,3- dibromopropyl, 3,3,3- trifluoro propyl, 3-, tetra- fluoropropyl of 2,2,3,3-, the chloro- 3,3,3- tri- of 2- Fluoropropyl, 2,2,3,3,3- pentafluoropropyl group, 1,1,2,3,3,3- hexafluoro propyl, heptafluoropropyl, the chloro- 1,1,2,3,3- five of 2,3- bis- The fluoro- 1- Methylethyl of fluoropropyl, 2-, the chloro- 1- Methylethyl of 2-, the bromo- 1- Methylethyl of 2-, the fluoro- 1- (fluoroform of 2,2,2- tri- Base) ethyl, 1,2,2,2- tetra- fluoro- 1- (trifluoromethyl) ethyl, 2,2,3,3,4,4- hexafluoro butyl, 2,2,3,4,4,4- hexafluoro fourth Base, seven fluorine butyl of 2,2,3,3,4,4,4-, 1,1,2,2,3,3,4,4- octafluoro butyl, nona-fluoro butyl group, 4- chloro- 1,1,2,2,3,3, The fluoro- 2- methyl-propyl of 4,4- octafluoro butyl, 2-, the chloro- 1,1- dimethyl ethyl of 2-, the bromo- 1,1- dimethyl ethyl of 2-, 5- chloro- 2, 2,3,4,4,5,5- seven fluorine amyl groups, ten trifluoro hexyls etc. can be selected according to the range of respectively specified carbon atom number.

C in this specification_a~C_bThe notation of naphthenic base indicates that carbon atom number is a~b cricoid alkyl, being capable of shape At 3 Yuans rings to the monocycle or composite ring structure of 6 Yuans rings.In addition, each ring can be in the range of specified carbon atom number through alkyl It is any to replace.It as concrete example, such as can enumerate: cyclopropyl, 1- methylcyclopropyl groups, 2- methylcyclopropyl groups, 2,2- diformazan basic ring Propyl, 2,2,3,3- tetramethyl-ring propyl, cyclobutyl, cyclopenta, 2- methylcyclopentyl, 3- methylcyclopentyl, cyclohexyl, 2- first Butylcyclohexyl, 3- methylcyclohexyl, 4- methylcyclohexyl, bicyclic [2.2.1] heptane -2- base etc., can be according to respectively specified The range of carbon atom number and selected.

C in this specification_a~C_bThe notation of halogen naphthenic base indicates that the hydrogen atom being bonded on carbon atom is arbitrarily replaced The cricoid alkyl that carbon atom number for halogen atom is a~b, is capable of forming the monocycle or complex loop knot of 3 Yuans rings to 6 Yuans rings Structure.In addition, each ring can arbitrarily replace in the range of specified carbon atom number through alkyl, it can by the substitution that halogen atom carries out To be located at hoop sections, pendant moiety can also be located at, or the two parts can also be located at, in addition, by 2 or more In the case that halogen atom replaces, these halogen atoms can be identical each other, can also be different each other.As concrete example, such as It can enumerate: 2,2- difluorocyclopropyl, 2,2- dichloro cyclopropyl, 2,2- dibromo cyclopropyl, the fluoro- 1- methylcyclopropyl groups of 2,2- bis-, 2, The chloro- 1- methylcyclopropyl groups of 2- bis-, the bromo- 1- methylcyclopropyl groups of 2,2- bis-, 2,2,3,3- tetrafluoro cyclobutyl, 2- (trifluoromethyl) hexamethylene Base, 3- (trifluoromethyl) cyclohexyl, 4- (trifluoromethyl) cyclohexyl etc., can according to the range of respectively specified carbon atom number and It is selected.

C in this specification_a~C_bThe notation of alkenyl indicates the straight-chain that carbon atom number is a~b or branched and divides With the unsaturated alkyl of 1 or 2 or more double bond in sub, as concrete example, such as can enumerate: vinyl, 1- acrylic, 2- acrylic, 1- methyl ethylene, 2- cyclobutenyl, 1- methyl -2- acrylic, 2- methyl -2- acrylic, 2- pentenyl, 2- first Base -2- cyclobutenyl, 3- methyl-2-butene base, 2- ethyl -2- acrylic, 1,1- dimethyl -2- acrylic, 2- hexenyl, 2- first Base -2- pentenyl, 2,4- dimethyl -2,6- heptadiene base, 3,7- dimethyl -2,6- octadienyl etc., can be according to each referring to The range of fixed carbon atom number and selected.

C in this specification_a~C_bThe notation of haloalkenyl indicates that the hydrogen atom being bonded on carbon atom is arbitrarily substituted by The straight-chain or branched and intramolecular that the carbon atom number of halogen atom is a~b have 1 or 2 or more double bond not Saturated hydrocarbyl.At this point, these halogen atoms can be identical each other in the case where being replaced by 2 or more halogen atoms, it can also With different each other.As concrete example, such as can enumerate: the fluoro- 2- acrylic of 2,2- dichloroethylenes, 2-, 2- chloro-2-propene base, The bromo- 2- acrylic of 3- chloro-2-propene base, 2-, the bromo- 2- acrylic of 3-, the fluoro- 2- acrylic of 3,3- bis-, bis- chloro-2-propene of 2,3- Base, the chloro- 2- acrylic of 3,3- bis-, 2,3- dibromo-2-allyl, the fluoro- 2- acrylic of 2,3,3- tri-, tri- chloro-2-propene of 2,3,3- Base, 1- (trifluoromethyl) vinyl, the chloro- 2- cyclobutenyl of 3-, the bromo- 2- cyclobutenyl of 3-, the fluoro- 3- cyclobutenyl of 4,4- bis-, 3,4,4- tri- Fluoro- 3- cyclobutenyl, 3- chloro- 4, bromo- 2- methyl -2- acrylic of 4,4- tri- fluoro- 2- cyclobutenyls, 3- etc. can be according to respectively specified Carbon atom number range and selected.

C in this specification_a~C_bThe notation of cycloalkenyl indicates the ring-type that carbon atom number is a~b and has 1 or 2 The unsaturated alkyl of a above double bond, is capable of forming the monocycle or composite ring structure of 3 Yuans rings to 6 Yuans rings.In addition, each ring can be with Arbitrarily replace in the range of specified carbon atom number through alkyl, in addition, double bond can be appointing for endo- (interior) or exo- (outer) A kind of form.It as concrete example, such as can enumerate: 2- cyclopentene -1- base, 3- cyclopentene -1- base, 2- cyclohexene -1- base, 3- ring Hexene -1- base, bicyclic [2.2.1] -5- heptene -2- base etc. can be selected according to the range of respectively specified carbon atom number It selects.

C in this specification_a~C_bThe notation of halogen cycloalkenyl indicates that the hydrogen atom being bonded on carbon atom is arbitrarily replaced The unsaturated alkyl of ring-type and the double bond with 1 or 2 or more that carbon atom number for halogen atom is a~b, can Form the monocycle or composite ring structure of 3 Yuans rings to 6 Yuans rings.In addition, each ring can be in the range of specified carbon atom number through alkane Base arbitrarily replaces, in addition, double bond can be any form of endo- or exo-.In addition, can by the substitution that halogen atom carries out To be located at hoop sections, pendant moiety can also be located at, or the two parts can also be located at, by 2 or more halogens In the case that atom replaces, these halogen atoms can be identical each other, can also be different each other.As concrete example, such as can arrange Bicyclic [2.2.1] -5- heptene -2- base of 2- chlorine etc. is lifted, can be selected according to the range of respectively specified carbon atom number.

C in this specification_a~C_bThe notation of alkynyl indicates the straight-chain that carbon atom number is a~b or branched and divides With the unsaturated alkyl of 1 or 2 or more three key in sub, as concrete example, such as can enumerate: acetenyl, 1- propinyl, 2-propynyl, 2- butynyl, 1- methyl -2-propynyl, valerylene base, 1- methyl -2- butynyl, 1,1- dimethyl -2- propine Base, 2- hexin base etc. can be selected according to the range of respectively specified carbon atom number.

C in this specification_a~C_bThe notation of alkynyl halide indicates that the hydrogen atom being bonded on carbon atom is arbitrarily substituted by The straight-chain or branched and intramolecular that the carbon atom number of halogen atom is a~b have 1 or 2 or more three keys not Saturated hydrocarbyl.At this point, these halogen atoms can be identical each other in the case where being replaced by 2 or more halogen atoms, it can also With different each other.It as concrete example, such as can enumerate: 2- chloroethene alkynyl, 2- bromoacetylene base, 2- iodoacetylene base, the chloro- 2- propine of 3- The bromo- 2-propynyl of base, 3-, the iodo- 2-propynyl of 3- etc. can be selected according to the range of respectively specified carbon atom number.

C in this specification_a~C_bThe notation of alkoxy indicates that carbon atom number is the alkyl-O- of a~b definition Base as concrete example, such as can be enumerated: methoxyl group, ethyoxyl, n-propyl oxygroup, isopropyl oxygroup, normal-butyl oxygroup, isobutyl Base oxygroup, sec-butyl oxygroup, tert-butyl oxygroup, n-pentyloxy, n-hexyl oxygroup etc., can be according to respectively specified carbon atom number Range and selected.

C in this specification_a~C_bThe notation of alkyl groups in the halogenalkoxy indicates that carbon atom number is the alkyl halide of a~b definition Base-O- base as concrete example, such as can be enumerated: difluoro-methoxy, trifluoromethoxy, chlorine difluoro-methoxy, bromine difluoromethoxy Base, 2- fluorine ethyoxyl, 2- chloroethoxy, 2,2,2- trifluoro ethoxy, 1,1,2,2, the chloro- 1,1,2- trifluoro of-tetrafluoro ethyoxyl, 2- The bromo- 1,1,2- trifluoro ethoxy of ethyoxyl, 2-, five fluorine ethyoxyls, the chloro- 1,1,2- trifluoro ethoxy of 2,2- bis-, 2,2,2- tri- are chloro- The bromo- 1,1,2,2- tetrafluoro ethyoxyl of 1,1- difluoroethoxy, 2-, tetra- fluoropropyl oxygroup of 2,2,3,3-, 1,1,2,3,3,3- hexafluoro Propyl oxygroup, 2,2,2- tri- fluoro- 1- (trifluoromethyl) ethyoxyl, heptafluoropropyl oxygroup, the bromo- 1,1,2,3,3,3- hexafluoro propyl of 2- Oxygroup etc. can be selected according to the range of respectively specified carbon atom number.

(C in this specification_a~C_bAlkyl) notation of carbonyl indicates that carbon atom number is the alkane of the definition of a~b Base-C (O)-base as concrete example, such as can be enumerated: acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl Base, 2- methylbutyryl, pivaloyl group, caproyl, heptanoyl group etc., can according to the range of respectively specified carbon atom number and into Row selection.

(C in this specification_a~C_bAlkylhalide group) notation of carbonyl indicates that carbon atom number is the halogen of the definition of a~b Alkyl-C (O)-base as concrete example, such as can be enumerated: acetyl fluoride base, chloracetyl, difluoro acetyl group, dichloro-acetyl, three Acetyl fluoride base, chlorine difluoro acetyl group, bromine difluoro acetyl group, trichloroacetyl, five fluorine propionos, seven fluorine bytyries, the chloro- 2,2- of 3- Dimethylpropanoyl etc. can be selected according to the range of respectively specified carbon atom number.

(C in this specification_a~C_bAlkoxy) notation of carbonyl indicates that carbon atom number is the alkane of the definition of a~b Base-O-C (O)-base as concrete example, such as can be enumerated: methoxycarbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyl Base Epoxide carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, tert-butoxycarbonyl etc., can be according to respectively specified carbon atom Several ranges and selected.

(C in this specification_a~C_bAlkyl groups in the halogenalkoxy) notation of carbonyl indicates that carbon atom number is the definition of a~b Alkylhalide group-O-C (O)-base as concrete example, such as can be enumerated: 2- chloroethoxycarbonyl, 2,2- difluoroethoxy carbonyl, 2,2, 2- trifluoro ethoxy carbonyl, 2,2,2- tri-chloroethoxy base carbonyls etc., can according to the range of respectively specified carbon atom number and into Row selection.

(C in this specification_a~C_bAlkyl amino) notation of carbonyl indicates that one of hydrogen atom by carbon atom number is a The alkyl-substituted carbamyl of~b definition, as concrete example, such as can enumerate: methylcarbamoyl, ethyl ammonia Formoxyl, n-propyl carbamyl, isopropyl carbamyl, normal-butyl carbamyl, isobutyl group carbamyl, sec-butyl ammonia first Acyl group, tert-Butylcarbamoyl etc. can be selected according to the range of respectively specified carbon atom number.

(C in this specification_a~C_bAlkylhalide group amino) notation of carbonyl indicates that one of hydrogen atom is by carbon atom number The carbamyl that the alkylhalide group of a~b definition replaces, as concrete example, such as can enumerate: 2- fluoro ethyl carbamyl Base, 2- chloroethyl carbamyl, 2,2- bis-fluoro ethyls carbamyl, 2,2,2- trifluoroethyl carbamyls etc., can be according to each It is selected from the range of specified carbon atom number.

Two (C in this specification_a~C_bAlkyl) aminocarboxy notation indicates two hydrogen atoms by identical each other or mutual For the alkyl-substituted carbamyl for the definition that different carbon atom numbers is a~b, as concrete example, such as can enumerate: N, N- dimethylcarbamoyl, N- ethyl-N-methylcarbamoyl, N, N- diethylcarbamoyl, N, N- diη-propyl ammonia first Acyl group, N, N- di-n-butyl carbamyl etc. can be selected according to the range of respectively specified carbon atom number.

As the substituent R in the cinnamic acid or benzoic acid derivative of structure represented by formula (2)¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴ And R¹⁰⁵, wherein preferably it is each independently selected from hydrogen atom, halogen atom, C₁~C₆Alkyl, C₁~C₆Alkylhalide group, C₁~C₆Alcoxyl Base, C₁~C₆Substituent group in alkyl groups in the halogenalkoxy, cyano and nitro.

In addition, as R¹³, for the aspect of orientation sensitivity, the preferably described suitable R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵'s The substituent group other than hydrogen atom in definition, is more preferably selected from halogen atom, C₁~C₆Alkyl, C₁~C₆Alkylhalide group, C₁~C₆Alkane Oxygroup, C₁~C₆Substituent group in alkyl groups in the halogenalkoxy, cyano and nitro.

It is also preferable to R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In either one or two substituent group be the formula (3) institute table The base shown, wherein preferred R¹⁰³For base represented by formula (3).It can be arranged about this monomer as the monomer with cassia bark acidic group Lift the monomer in the formula M1-1~M1-7 and M1-17~M1-21.In addition, can be arranged as the monomer with benzoxy Lift the monomer in the formula M2-1~M2-9.

As this cinnamic acid and its derivative, can enumerate: cinnamic acid, 4- methoxyl group cinnamic acid, 4- ethyoxyl cinnamic acid, The cinnamic acid derivatives such as 4- propoxyl group cinnamic acid, 4- fluorine cinnamic acid；4- (6- Methacryloxyhexyl -1- oxygroup) cassia bark Acid, 4- (6- acryloxy hexyl -1- oxygroup) cinnamic acid, 4- (3- methacryloxypropyl -1- oxygroup) cinnamic acid, 4- (4- (6- Methacryloxyhexyl -1- oxygroup) benzoyloxy) cinnamic acid etc. has the monomer etc. of cassia bark acidic group.

In addition, can be enumerated as this benzoic acid and its derivative: benzoic acid, 4- methoxy benzoic acid, 4- ethoxybenzene The benzoic acid derivatives such as formic acid, 4- propoxy benzoic acid, 4- fluobenzoic acid；4- (6- Methacryloxyhexyl -1- oxygroup) Benzoic acid, 4- (6- acryloxy hexyl -1- oxygroup) benzoic acid, 4- (3- methacryloxypropyl -1- oxygroup) benzene first Acid, 4- (4- (6- Methacryloxyhexyl -1- oxygroup) benzoyloxy) benzoic acid etc. have the monomer etc. of benzoxy.

About the tree in polymer composition of the invention containing the content in the case where (C) ingredient, relative to (A) ingredient 100 mass parts of rouge, preferably 3 mass parts are to 100 mass parts.If the content of (C) ingredient below the mass, has no photograph for 3 The expansion of the amount of penetrating range.In addition, there are cured films obtained if the content of (C) ingredient is more than 100 mass parts and excessive Solvent tolerance reduce the case where.

< organic solvent >

As long as organic solvent used in polymer composition used in the present invention is that resin component can be made to dissolve Organic solvent is then not particularly limited.It is exemplified below the concrete example of organic solvent.

Can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl are in oneself Amide, 2-Pyrrolidone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, diformazan Base sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-imidazol pyridine ketone, ethylpentyl ketone, methyl nonyl ketone, methyl second Base ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- Hydroxy-4-methyl-2-pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, two Ethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, Acetic acid 3- methyl -3- methoxybutyl, tripropylene glycol methyl ether, isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl are molten Fine agent, butyl cellosolve, acetic acid methyl cellosolve, acetic cellosolve, butyl carbitol, ethyl carbitol, ethyl card must Alcohol acetic ester, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol list second Acid esters, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list second Acid esters list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, acetic acid 3- methyl -3- methoxybutyl, 3 third Glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, cream Sour methyl esters, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate monoethyl ether ester, methyl pyruvate, third Keto acid ethyl ester, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- third Alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- are single Methyl ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, lactic acid first Ester, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..These can be used alone, and can also mix makes With.

< polymer composition >

Polymer composition of the invention contains the photosensitive side chain that (A) shows liquid crystal liquid crystal property in specific range of temperatures Type macromolecule, (B) dichroism pigment and organic solvent.In addition, as needed containing compound represented by (C) described formula (c).

[preparation of polymer composition]

Polymer composition used in the present invention is prepared preferably in the form of coating fluid to suitably form polarizing layer. That is, polymer composition used in the present invention preferably in organic solvent dissolved be used to form the resin of resin coating at Point and obtain solution form preparation.Herein, the resin component be comprising it is stated that can show the photosensitive of liquid crystal liquid crystal property The high molecular resin component of side chain type of property.At this point, the content of resin component preferably 1 mass of mass %~20 %, more preferable 3 matter Measure the mass of %~15 %, the particularly preferred 3 mass mass of %~10 %.

In the polymer composition of this implementation form, the resin component described can show liquid crystal liquid crystal property with all Photosensitive side chain type macromolecule, can also be mixed other than these in the range of lossless liquid crystal expressive ability and photosensitive property Other polymers.At this point, the content of the other polymers in resin component is the 0.5 mass % of mass %~80, preferably 1 matter Measure the mass of %~50 %.

As this other polymers, such as can enumerate comprising poly- (methyl) acrylate or polyamic acid or polyimides Deng can not show the high molecular polymer of photosensitive side chain type etc. of liquid crystal liquid crystal property.

Polymer composition used in the present invention can also contain the ingredient other than (A), (B) and organic solvent. As an example, the compound of the film thickness uniformity or surface smoothness when improving coated polymeric composition can be enumerated, improved partially The compound etc. of the adhesion of photosphere and substrate, but not limited to this.

As the compound for improving film thickness uniformity or surface smoothness, can enumerate: fluorine system surfactant, silicone-based table Face activating agent and nonionic surfactants etc..

More specifically, it such as can enumerate: Eftop (registered trademark) 301, EF303, EF352 (Tochem Products Company manufacture), MEGAFAC (registered trademark) F171, F173, R-30 (manufacture of DIC company), Fluorad FC430, FC431 (firmly The manufacture of friendly 3M company), AsahiGuard (registered trademark) AG710 (manufacture of Asahi Glass company), Surflon (registered trademark) S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC beautifies clearly company manufacture) etc..It is living about these surfaces The usage rate of property agent, relative to 100 mass parts of the resin component contained by polymer composition, preferably 0.01 mass parts~ 2 mass parts, more preferable 0.01 mass parts~1 mass parts.

The concrete example of compound as the adhesion for improving polarizing layer and substrate, can be listed below shown in contain function The compound etc. of property silane.

Such as it can enumerate: 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl three Methoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- Amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, three ethoxy of 3- ureido-propyl Base silane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3- aminopropyl triethoxysilicane Alkane, N- tri-ethoxy silylpropyl diethylenetriamine, N- trimethoxysilylpropyl diethylenetriamine, 10- front three Three azepine decane of oxysilane base -1,4,7-, three azepine decane of 10- triethoxysilicane alkyl -1,4,7-, acetic acid 9- trimethoxy Silylation -3,6- diaza nonyl ester, acetic acid 9- triethoxysilicane alkyl -3,6- diaza nonyl ester, N- benzyl -3- aminopropyl three Methoxy silane, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330, N- benzene Bis- (the ethylene oxide) -3- of bis- (the ethylene oxide) -3- TSL 8330s of base -3-aminopropyltriethoxysilane, N-, N- Aminopropyltriethoxywerene werene etc..

In addition, can also make in polymer composition to improve the adhesion of substrate and polarizing layer and assign heat resistance Additive containing phenolic resin (phenoplast) system such as below or the compound containing epoxy group.Specific phenol disclosed below Urea formaldehyde system additive, but it is not limited to these structures.

[changing 33]

As specifically containing the compound of epoxy group, can illustrate: ethylene glycol diglycidylether, polyethylene glycol diglycidyl are sweet Oily ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two Glycidol ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyl Ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N', N'- four glycidyl group m-xylene diamine, 1,3- it is bis- (N, N- diglycidyl amino methyl) hexamethylene, N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl-methane etc..

In the case where using improving with the compound of the adhesion of substrate, the usage amount of the compound is relative to polymer 100 mass parts of the resin component contained by composition, preferably 0.1 mass parts~30 mass parts, more preferable 1 mass parts~20 matter Measure part.If usage amount can not expect that the effect that adhesion improves is deposited if being more than 30 mass parts not up to 0.1 mass parts The case where the regiospecific of liquid crystal is deteriorated.

As additive, light sensitizer also can be used.It is preferred that colourless sensitizer and triplet sensitizer.

As light sensitizer, there are aromatic nitro compounds, cumarin (7- diethylamino -4- methylcoumarin, 7- Hydroxyl 4- methylcoumarin), ketone cumarin, carbonyl bicoumarin, aromatic series 2- hydroxy-ketone and through amino replace aromatic series 2- Hydroxy-ketone (2- dihydroxy benaophenonel, single or two to (dimethylamino) -2- dihydroxy benaophenonel), acetophenone, anthraquinone, xanthene Ketone, thioxanthones, benzanthrone, thiazoline (2- benzoyl methylene -3- methyl-β-aphthothiazoles quinoline, 2- (β-naphthoyl Methylene) -3- methylbenzothiazole quinoline, 2- (α-naphthoyl methylene) -3- methylbenzothiazole quinoline, 2- (4- dibenzoyl Methylene) -3- methylbenzothiazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthothiazoles quinoline, 2- (4- biphenyl Formyl methylene) -3- methyl-β-aphthothiazoles quinoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-aphthothiazoles Quinoline), oxazoline (2- benzoyl methylene -3- methyl-β-aphthoxazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzene And oxazoline, 2- (α-naphthoyl methylene) -3- methylbenzoxazole quinoline, 2- (4- dibenzoyl methylene) -3- methyl Benzoxazoles quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthoxazoles quinoline, 2- (4- dibenzoyl methylene) -3- Methyl-β-aphthoxazoles quinoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-aphthoxazoles quinoline), benzothiazole, nitrobenzene Amine (or paranitroanilinum, 2,4,6- trinitroaniline) or nitro acenaphthene (5- nitro acenaphthene), (2- [(hydroxyl is to methoxyl group) benzene Vinyl] benzothiazole, styrax alkyl ether, N- alkylation phthalein ketone, acetophenone ketal (2,2- Dimethoxyphenyl ethyl ketone), Naphthalene, anthracene (2- naphthalene methanol, 2- naphthalene-carboxylic acid, 9- anthryl carbinol and 9- anthracene carboxylic acid), chromene, azo indolizine, merocoumarin Deng.

Optimization aromatic 2- hydroxy-ketone (benzophenone), cumarin, ketone cumarin, carbonyl bicoumarin, acetophenone, anthracene Quinone, xanthone, thioxanthones and acetophenone ketal.

The manufacturing method of substrate with polarizing layer of the invention includes:

Step [I], coating shows the photosensitive side of liquid crystal liquid crystal property containing (A) in specific range of temperatures on substrate Chain macromolecule, (B) dichroism pigment and organic solvent polymer composition and form film；

Step [II] irradiates the ultraviolet light through polarisation to the film obtained in [I]；And

Step [III] heats the film obtained in [II].

By the step, the polarizing layer for being endowed polarizing properties can be obtained, can be obtained with the polarizing layer Substrate.

Each step for [I]~[III] for using polymer composition of the invention to obtain polarizing layer is illustrated below.

< step [I] >

In step [I], coating shows the photosensitive side of liquid crystal liquid crystal property containing (A) in specific range of temperatures on substrate Chain macromolecule, (B) dichroism pigment and organic solvent polymer composition and form film.

< substrate >

The generally transparent substrate of substrate.Furthermore not by polarizer (hereinafter sometimes referred to this polarizer) of the invention When substrate is set to the display surface of display element, for example, from this polarizer will remove substrate and the light polarizing film that obtains be set to it is aobvious In the case where the display surface for showing element, substrate can and it is nontransparent.So-called transparent substrate is to refer to make light, especially visible light What is penetrated has the substrate of the transparency, and the so-called transparency refers to that the transmissivity to the light in the range of 380~780nm of wavelength is 80% or more characteristic.As specific transparent substrate, translucent resin substrate can be enumerated.As composition translucent resin substrate Resin, can enumerate: the polyolefin such as polyethylene, polypropylene；The annular ethylene series resins such as norbornene-based polymer；Polyethylene Alcohol；Polyethylene terephthalate；Polymethacrylates；Polyacrylate；Triacetyl cellulose, diacetyl cellulose, second The cellulose esters such as sour cellulose propionate；Polyethylene naphthalate；Polycarbonate；Polysulfones；Polyether sulfone；Polyether-ketone；Polyphenylene sulfide And polyphenylene oxide.With regard to accessibility or the transparency viewpoint for, preferably polyethylene terephthalate, polymethacrylates, Cellulose esters, annular ethylene series resin or polycarbonate.

Cellulose esters be hydroxyl contained by cellulose part or all through being esterified, it is convenient to purchase from the market It buys.In addition, cellulose esters substrate is also convenient to commercially.As commercially available cellulose esters substrate, such as can enumerate: " Fujitac film " (film limited liability company of Fuji)；" KC8UX2M ", " KC8UY " and " KC4UY " (Konica Minolta Opto limited liability company) etc..

Annular ethylene series resin is convenient to commercially.As commercially available annular ethylene series resin, can enumerate: [the auspicious father-in-law's share of Japan is limited by " Topas " [Ticona company (Germany)], " ARTON " [JSR Corp.], " ZEONOR " Company], " ZEONEX " [Nippon Zeon Co., Ltd.] and " APEL " [Mitsui Chemicals Inc.'s manufacture].It can lead to The known method such as solvent casting method, extrusion by melting is crossed this annular ethylene series resin is filmed and makes substrate. Alternatively, it is also possible to use commercially available annular ethylene series resin substrate.As commercially available annular ethylene series resin substrate, can enumerate: " S-SINA " [ponding chemical industry limited liability company], " SCA40 " [ponding chemical industry limited liability company], " Zeonor Film " [Optronics limited liability company] and " ARTON film " [JSR Corp.].

In the copolymerization that annular ethylene series resin is cyclic olefin and chain olefin or the aromatic compound with vinyl In the case where object, lead to about the containing ratio for the structural unit for being originated from cyclic olefin relative to the entire infrastructure unit of copolymer It is often 50 moles of % hereinafter, it is preferred that the range of 15~50 moles of %.As chain olefin, ethylene and propylene can be enumerated, as tool There is the aromatic compound of vinyl, can enumerate: styrene, α-methylstyrene and alkyl-substituted styrene.In cyclic olefin In the case where being the terpolymer that resin is cyclic olefin, chain olefin and the aromatic compound with vinyl, about The containing ratio of structural unit from chain olefin usually 5~80 is rubbed relative to the entire infrastructure unit of copolymer You are %, the whole about the containing ratio for the structural unit for being originated from the aromatic compound with vinyl, relative to copolymer Structural unit, usually 5~80 moles of %.This terpolymer is high with that opposite can reduce price when manufacturing the copolymer The advantages of usage amount of expensive cyclic olefin.

Requirement characteristic to substrate is different according to the composition of polarizer, it is usually preferred to phase difference substrate as small as possible. It as phase difference substrate as small as possible, can enumerate: ZEROTAC (Konica Minolta Opto limited liability company), Z- TAC (film limited liability company of Fuji) etc. does not have the cellulose ester membrane of phase difference.In addition, it is also preferred that the cyclic annular alkene not extended Hydrocarbon system resin base material.

It, can be to not formed polarizing layer in the case where being formed with the polarizer of polarizing layer on substrate across alignment film Implement hard coating, anti-reflex treated, antistatic treatment etc. in the face of substrate.In addition, hard conating can be in the range for not influencing performance It is interior to include the additives such as ultraviolet absorbing agent.

About the thickness of substrate, if excessively thin, there are the tendencies that strength reduction, processability are deteriorated, therefore usually 5~ 300 μm, preferably 20~200 μm.

The method that the polymer composition is coated on substrate is not particularly limited.

Industrially generally it is coated by coating methods such as screen painting, hectographic printing, soft version printing or ink-jet methods.Make For other coating methods, there are infusion process, print roll coating method, slit coating method, method of spin coating (spinner method) or it is sprayed Method etc. can select these methods according to purpose.

On substrate after coated polymeric composition, heating plate, thermal cycle type baking oven or IR (infrared ray) type can use The heating equipments such as baking oven evaporate solvent 0.4 minute~60 minutes, preferably 0.5 minute at 50~230 DEG C, preferably 50~200 DEG C ~10 minutes and obtain film.Drying temperature at this time is preferably shorter than the high molecular liquid crystalline phase performance temperature of side chain type.

About the thickness of film, if blocked up, it is unfavorable for anisotropic performance, if excessively thin, polarized light property is deposited In problem, therefore thickness is usually 10 μm or less.It is preferred that 0.5 μm or more and 9.5 μm hereinafter, more preferable 0.8 μm or more and 5 μm with Under.Thickness can usually be found out and being measured using interference film thickness gauge, laser microscope or contact pin type film thickness gauge.

Furthermore it can also be arranged afterwards and before next step [II] substrate for being formed with film is cooled to room in step [I] The step of temperature.

< step [II] >

In step [II], the ultraviolet light through polarisation is irradiated to the film obtained in step [I].In the film surface irradiation to film In the case where ultraviolet light through polarisation, the ultraviolet light that polarisation is realized via polarizer is irradiated to substrate from certain orientation.As The ultraviolet light of the range of wavelength 100nm~400nm can be used in used ultraviolet light.It is preferred that according to the kind of used film Class selects optimal wavelength via optical filter etc..In addition, for example in order to selectively inducing photo-crosslinking, Ke Yixuan Select the ultraviolet light of the range using wavelength 290nm~400nm.As ultraviolet light, such as high-pressure mercury-vapor lamp can be used and radiated Light out.

Ultraviolet irradiation amount through polarisation depends on used film.Exposure is preferably set to realize the maximum of Δ A It is worth in the range of the 1%~70% of the amount of the polarisation ultraviolet light of (hereinafter also referred to Δ Amax), is more preferably set as 1%~50% In range, the maximum value of Δ A is the ultraviolet light on the parallel direction of the polarization direction of ultraviolet light of the sum through polarisation in the film Absorbance with and the vertical direction of the polarization direction on ultraviolet absorbance difference.

< step [III] >

In step [III], the film that the ultraviolet light through polarisation is irradiated in step [II] is heated.By heating, Polarizing properties can be assigned to film.

The heating equipments such as heating plate, thermal cycle type baking oven or IR (infrared ray) type baking oven can be used in heating.Heating temperature It is considered that used film shows the temperature of liquid crystal liquid crystal property and determines.

The preferred side chain type high molecular form of heating temperature reveals the temperature of the temperature (hereinafter referred to as liquid crystal performance temperature) of liquid crystal liquid crystal property It spends in range.In the case where the film surface of such as film, predict that the liquid crystal performance temperature of film coated surface is lower than and can show Liquid crystal when the photosensitive side chain type macromolecule of liquid crystal liquid crystal property is observed under block state shows temperature.Therefore, heating temperature is more It is preferred that within the temperature range of the liquid crystal performance temperature of film coated surface.That is, the temperature model of the heating temperature after irradiation polarisation ultraviolet light It encloses preferably to compare low 10 DEG C of temperature with the lower limit of the temperature range of the high molecular liquid crystal performance temperature of used side chain type The temperature of range of low 10 DEG C of the temperature as the upper limit is compared as lower limit, using the upper limit with the liquid crystal temperature range.If plus Hot temperature is lower than the temperature range, then the anisotropic amplification effect realized using heat existed in film becomes not fill Point tendency, in addition, if heating temperature compared with the temperature range it is excessively high, there are the state of film become close to it is each to The tendency of the liquid condition (isotropic phase) of the same sex exists in this case and is difficult to carry out by self assembly along a direction Again the case where orientation.

Furthermore liquid crystal performance temperature refers to that from solid opposite liquid crystalline phase phase transfer occurs for side chain type macromolecule or film coated surface Glass transition temperature (Tg) more than, and the isotropism of phase transfer mutually occurs from the opposite isotropism of liquid crystal (isotropic) Phase inversion temperature (Tiso) temperature below.

About the thickness for being formed by film after heating, in view of the reason identical with the description in step [I], preferably 0.5 μ M or more and 9.5 μm hereinafter, more preferable 0.8 μm or more and 5 μm or less.

By the way that with above step, the manufacturing method of the present invention, which can be realized, expeditiously imports anisotropy to film. In addition, the substrate of the attached polarizing layer for being endowed polarizing properties can be manufactured expeditiously.

The manufacturing method of the substrate of attached film of the invention be on substrate coated polymeric composition and after forming film, Irradiate the ultraviolet light through polarisation.Then, it is heated, is achieved in expeditiously each to different to the importing of side chain type polymeric membrane Property, manufacture incidentally has the substrate of the polarizing layer of polarizing properties.

About film used in the present invention, induced using the light reaction of side chain and by the self assembly based on liquid crystal liquid crystal property The principle of molecule orientation again, and realize and anisotropy expeditiously is imported to film.About the manufacturing method of the present invention, in side chain In the case that type macromolecule has structure of the photocrosslinking reaction base as photoreactivity base, using side chain type macromolecule on substrate After forming film, the ultraviolet light through polarisation is irradiated, after then being heated, polarization element is made.

Therefore, film used in method of the invention passes through the ultraviolet light for sequentially carrying out being irradiated to film through polarisation and adds Heat treatment can expeditiously be imported anisotropy, and become the excellent polarizing layer of polarizing properties.

In addition, the film used in method of the invention, makes the ultraviolet irradiation through polarisation irradiated to film Heating temperature in amount and heat treatment becomes best.Anisotropy expeditiously is imported to film thereby, it is possible to realize.

The optimal polarisation ultraviolet irradiation for expeditiously importing anisotropy to film used in the present invention Amount corresponds to the photonasty for making to carry out scholar's rearrangement reaction in photo-crosslinking or photoisomerization reaction or light husband in the film The amount of base becomes optimal polarisation ultraviolet irradiation amount.Ultraviolet light through polarisation, knot are irradiated to film used in the present invention If fruit carries out the photonasty base of the side chain of scholar's rearrangement reaction in photo-crosslinking or photoisomerization reaction or light husband too Few, then light reaction amount is insufficient.In the case, even if hereafter heating, the progress of self assembly is also insufficient.On the other hand, exist In film used in the present invention, ultraviolet light to the structured illumination with photocrosslinking reaction base through polarisation, as a result if handed over The photonasty base for joining the side chain of reaction is too many, then the cross-linking reaction between side chain can be carried out excessively.In the case, film obtained Become rigidity, exists to hereafter because self assembly caused by heating is the case where carrying out generation obstruction.In addition, used herein Film in, to light Fu Lishi reset base structured illumination through the ultraviolet light of polarisation, as a result in case of light Fu Lishi weight The photonasty base for arranging the side chain of reaction is too many, then the liquid crystal liquid crystal property of film becomes excessively low.In the case, film obtained Liquid crystal liquid crystal property can also reduce, and exist to hereafter because self assembly caused by heating is the case where carrying out generation obstruction.In addition, to having In the case that the structured illumination of light Fu Lishi rearrangement base is through the ultraviolet light of polarisation, if ultraviolet irradiation amount is excessive, side chain Photodegradation occurs for type macromolecule, exists to hereafter because self assembly caused by heating is the case where carrying out generation obstruction.

Therefore, in film used in the present invention, photo-crosslinking or photic is carried out by irradiating polarisation ultraviolet light The optimised quantity of the photonasty base of the side chain of scholar's rearrangement reaction is preferably set to the side chain type macromolecule in isomerization reaction or light husband 0.1 mole of %~40 mole % of photonasty base possessed by film, is more preferably set as 0.1 mole of %~20 mole %.Passing through will The amount that the photonasty base of the side chain of light reaction occurs is set as this range, hereafter utilizes the carry out efficiency of the self assembly of heat treatment Well, anisotropy can be expeditiously formed in film.

In the film used in method of the invention, by the optimization of the ultraviolet irradiation amount through polarisation, and make The sense for carrying out scholar's rearrangement reaction in photo-crosslinking or photoisomerization reaction or light husband in the side chain of side chain type polymeric membrane The amount of photosensitiveness base becomes best.In addition, acting synergistically with heat treatment hereafter, and realize expeditiously to used herein Film import anisotropy.In the case, the amount about suitable polarisation ultraviolet light can be based on painting used in the present invention The evaluation of the UV absorption of film and carry out.

That is, be directed to film used in the present invention, after irradiate polarisation ultraviolet light, respectively measure and the ultraviolet light through polarisation The parallel direction of polarization direction on ultraviolet radiation absorption and the ultraviolet radiation absorption on the direction vertical with the polarization direction.Root According to the measurement result of UV absorption, the purple on the parallel direction of polarization direction of ultraviolet light of the sum through polarisation in the film is evaluated Outside line absorbance with and the vertical direction of the polarization direction on ultraviolet absorbance difference, i.e. Δ A.In addition, finding out this hair The maximum value (Δ Amax) for the Δ A that film used in bright may be implemented and the polarisation ultraviolet irradiation for realizing the maximum value Amount.In the manufacturing method of the present invention, it can will realize that the polarisation ultraviolet irradiation amount of Δ Amax as benchmark, and determines manufacture The preferred exposure of ultraviolet light when polarizing layer through polarisation.

In the manufacturing method of the present invention, preferably by the ultraviolet irradiation amount through polarisation to film used in the present invention It is set as in the range of realize the amount of the polarisation ultraviolet light of Δ Amax 1%~70%, is more preferably set as 1%~50% range It is interior.In film used in the present invention, realize that the polarisation in the range of the 1%~50% of the amount of the polarisation ultraviolet light of Δ Amax is purple The exposure of outside line, which is equivalent to, makes 0.1 mole of %~20 in photonasty base whole possessed by the side chain type polymeric membrane rub Your % carries out the amount of the polarisation ultraviolet light of photo-crosslinking.

Accordingly, in the manufacturing method of the present invention, anisotropy expeditiously is imported to film in order to realize, preferably by the side The high molecular liquid crystal temperature range of chain determines heating temperature suitable as described above as benchmark.Thus, for example in this hair In the case that the high molecular liquid crystal temperature range of side chain type used in bright is 60 DEG C~200 DEG C, it is generally desirable to polarisation will be irradiated The temperature of heating after ultraviolet light is set as 50 DEG C~190 DEG C.Film used in the present invention is endowed bigger each to different as a result, Property.

Polarization element provided by the present invention shows high reliability to external stresses such as light or heat as a result,.

Polarizing layer in this polarization element with a thickness of 10 μm hereinafter, more preferable 1 μm or more and 9 μm or less.Both alignment layers and The thickness of polarizing layer can usually be asked and being measured using interference film thickness gauge, laser microscope or contact pin type film thickness gauge Out.

The polarization element obtained by such as upper type can be widely used in needing the various of polarisation using known method Display element, such as can be used for liquid crystal display element, organic EL (Electroluminescence, electroluminescent cell) etc. Anti-reflective film (circular polarizer), photoswitch and optical light filter and using these as the various optical detecting machines of constituent element Device etc..

Hereinafter, being based on embodiment and illustrating the present invention, but the present invention is not limited by the embodiment.

[embodiment]

It is exemplified below the embodiment of the present invention and specifically describes the present invention, but the present invention is not limited by these examples Property explain.

< solvent >

Each resin combination of Examples and Comparative Examples contains solvent, as the solvent, uses Isosorbide-5-Nitrae-dioxanes (DO), first Base isobutyl ketone (MIBK).

The measurement > of the molecular weight of < polymer

The molecular weight of acrylic acid series copolymer in polymerization example is that the room temperature manufactured using Shodex limited liability company is coagulated The tubing string (KD-803, KD-805) that glue penetration chromatography (GPC) device (GPC-101), Shodex company manufacture, in the following way Measurement.

Furthermore following number average molecular weights (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are with poly- The form of styrene scaled value indicates.

Tubing string temperature: 50 DEG C

Eluent: n,N-Dimethylformamide is (as additive, lithium bromide hydrate (LiBrH₂Be O) 30mmol/L, Phosphoric acid anhydrous crystal (adjacent phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10mL/L)

Flow velocity: 1.0mL/min

Make the standard sample of calibration curve: (molecular weight is about the TSK standard polyethylene oxide of Tosoh company manufacture 900,000,150,000,100,000,30,000) and the polyethylene glycol (molecule of Polymer Laboratories company manufacture Amount about 12,000,4,000,1,000).

1 > of < synthesis example

4- (6- hydroxyl hexyl oxygen is synthesized and heating 4-Hydroxycinnamic Acid and 1- bromo- 6- hexanol under alkaline condition Base) cinnamic acid.It reacts the product and methacrylic chloride under alkaline condition, and obtains change represented by following formula (1) Close object.

2 > of < synthesis example

4- (6- hydroxyl hexyl oxygen is synthesized and heating 4-HBA and 1- bromo- 6- hexanol under alkaline condition Base) benzoic acid.It reacts the product and methacrylic chloride under alkaline condition, and obtains change represented by compound (A) Close object.

[changing 34]

3 > of < synthesis example

Make methacrylate represented by methacrylate 5.0g represented by the formula (1), the formula (A) 18.4g, as the α of polymerization catalyst, α '-azodiisobutyronitrile 0.6g be dissolved in Isosorbide-5-Nitrae-dioxanes 216.0g, it is anti-at 80 DEG C It answers 20 hours, thus to obtain acrylic acid series copolymer solution.Acrylic acid series copolymer solution is slowly dropped into diethyl ether Solid is precipitated in 2000.0g, is filtered and is dried under reduced pressure, thus removes residual monomer, and obtains acrylic polymeric Object (P1).The Mn of acrylic acid series copolymer obtained is 10,000, Mw 21,000.

4 > of < synthesis example

Make methacrylate 16.0g represented by the formula (1), the α as polymerization catalyst, two isobutyl of α '-azo Nitrile 0.4g is dissolved in Isosorbide-5-Nitrae-dioxanes 180.0g, reacts 20 hours at 80 DEG C, thus to obtain acrylic acid series copolymer solution.It will Acrylic acid series copolymer solution slowly drops in diethyl ether 1000.0g and solid is precipitated, and is filtered and is dried under reduced pressure, by This removal residual monomer, and obtain acrylic acid series polymeric compounds (P2).The Mn of acrylic acid series copolymer obtained is 9,300, Mw It is 16,000.

1 to 2 > of < embodiment

Composition is formed according to each polarizing layer for forming shown in table 1 and preparing embodiment 1 to 2.To using each polarizing layer It forms composition each polarization element obtained and carries out degree of polarization measurement, dichroic ratio measurement.

[table 1]

1 > of < embodiment

[formation of polarizing layer]

Polarizing layer shown in rotary coating table 1 forms composition on a quartz substrate, dry 60 in 55 DEG C of heating plate After second, the film of film thickness 1200nm is formed.Then, to coated surface across polarizer with 20mJ/cm²Light exposure vertical irradiation The linear polarization of 313nm.Then, it is heated 5 minutes at 150 DEG C using heating plate and forms polarizing layer.

[degree of polarization measurement]

The degree of polarization of polarization element obtained is to measure in the following way.Using to spectrophotometer, (Shimadzu is made The UV-3600 of limited liability company of institute manufacture) fixture (folder) with polaroid is installed and the device of acquisition, measurement transmission The transmissivity (T1) of axis direction and the transmissivity (T2) for absorbing axis direction.According to the transmissivity (T1) of measured transmission axis direction And the value of the transmissivity (T2) of axis direction is absorbed, degree of polarization is calculated using following formula.Measurement result is shown in table 2.

Degree of polarization (%)={ (T1-T2)/(T1+T2) }^1/2×100

[dichroic ratio measurement]

The dichroic ratio of polarization element obtained is to measure in the following way.Using to spectrophotometer (Shimadzu system The UV-3600 of Zuo Suo limited liability company manufacture) fixture for having polaroid is installed and the device obtained, measurement transmission axis direction Absorbance (A1) and absorb axis direction absorbance (A2).According to the absorbance (A1) of measured transmission axis direction and absorb The value of the absorbance (A2) of axis direction, dichroic ratio is calculated using following formula.Show the results of the evaluation table 2.

Dichroic ratio=(A2)/(A1)

2 > of < embodiment

By making polarization element with the identical mode of embodiment 1.Evaluation result is shown in table 2 together.

1 > of < comparative example

[formation of both alignment layers]

Acrylic acid series polymeric compounds (P2) 5.0g obtained in synthesis example 4 is set to be dissolved in 1,4- dioxanes 95.0g and prepare and match Composition is formed to layer.The rotary coating both alignment layers form composition on a quartz substrate, dry 60 in 55 DEG C of heating plate After second, the film of film thickness 200nm is formed.Then, to coated surface across polarizer with 5mJ/cm²Light exposure vertical irradiation The linear polarization of 313nm, and form both alignment layers.

[formation of polarizing layer]

Make polymerizable liquid crystal (manufacture of RMM141C, Merck company) 14.4g, dichroism pigment (G-241, woods original corporation Making) 0.58g is dissolved in MIBK 35.0g, and the polarizing layer for preparing 30 mass % of solid content constituent concentration forms composition.Matching Composition is formed with 2000rpm30sec rotary coating polarizing layer obtained on layer, dry 60 in 65 DEG C of heating plate Second and form film.Then, to the film with 500mJ/cm²It is exposed, thus to obtain polarization element.

[evaluation of regiospecific]

The regiospecific of polarization element obtained is confirmed by polarized light microscope observing.In the orthogonal Buddhist nun of petrographic microscope Sample is inserted into direction between Cole's prism along 0 ° and 45 °, implements the observation of light leakage state.In the case where having realized orientation, Light leakage will not occur at 0 ° and observe the state of dark field, 45 ° of whens can occur light leakage and observe the state of bright-field.Compare The polarization element obtained in example 1 obtains dark field at 0 °, and bright-field is obtained at 45 °, and good orientation is realized in confirmation.

[degree of polarization, dichroic ratio measurement]

By the degree of polarization and dichroic ratio that measure polarization element obtained with the identical mode of embodiment 1.It will evaluation As a result it is shown in table 2 together.

2 > of < comparative example

[formation of both alignment layers]

By forming both alignment layers with the identical mode of comparative example 1.

[formation of polarizing layer]

The dichroism pigment that polarizing layer forms composition is changed to G-207 (manufacture of Lin Yuan company), in addition to this, is passed through Polarization element is made with the identical mode of comparative example 1.

[evaluation of regiospecific]

By the evaluation for carrying out regiospecific with the identical mode of comparative example 1.The polarization element obtained in comparative example 2 is at 0 ° Dark field is obtained, bright-field is obtained at 45 °, good orientation is realized in confirmation.

[degree of polarization, dichroic ratio measurement]

[table 2]

Table 2

It is the high-caliber inclined of equal extent that the embodiment 1 to 2 that both alignment layers are not used, which also can be realized with comparative example 1 to 2, Luminosity, dichroic ratio.

[industrial availability]

Composition polarization element obtained is formed due to being not necessarily to alignment film, so being expected to reality using polarizing layer of the invention Now manufacture the simplification of processing procedure and the reduction of component cost.

Claims

1. a kind of polymer composition, contains (A) and have and show the structure of photoreactivity and show the structure of liquid crystal liquid crystal property Side chain type macromolecule, (B) dichroism pigment and organic solvent.

2. polymer composition according to claim 1, wherein (A) ingredient, which has, can cause photo-crosslinking, photoisomerization Or the photonasty side chain that light Fu Lishi is reset is as the structure for showing photoreactivity.

3. polymer composition according to claim 2, wherein (A) ingredient has selected from by following formula (1)~(6) institute group At group in any photonasty side chain,

[changing 1]

In formula, A, B, D separately indicate singly-bound ,-O- ,-CH₂,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；

Y₁Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or It is identical or different 2~6 ring in these substituent groups via base made of bonding base B bonding, institute's key on these bases The hydrogen atom of conjunction can separately be substituted by-COOR₀(in formula, R₀Indicate the alkyl of hydrogen atom or carbon number 1~5) ,- NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

Y₂For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the ester ring type hydrocarbon of carbon number 5~8 and these rings The base in composed group is combined, the hydrogen atom being bonded on these bases can separately be substituted by-NO₂、-CN、-CH =C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= CH-, when the quantity of X is 2, X can be the same or different each other；

Cou indicates that Coumarin-6-base or coumarin-7-base, the hydrogen atom being bonded on these bases can separately be taken On behalf of-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

Q1 and q2 mono- for 1 and another is 0；

Q3 is 0 or 1；

P and Q respectively stand alone as selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type Base in group composed by the combination of hydrocarbon and these rings；Wherein, the case where X is-CH=CH-CO-O- ,-O-CO-CH=CH- Under, the P or Q for the side that-CH=CH- is bonded are aromatic rings；

L1 is 0 or 1；

The integer that l2 is 0~2；

When l1 is 1, B also illustrates that singly-bound when T is singly-bound；

4. polymer composition according to any one of claim 1 to 3, wherein (A) ingredient has selected from by following formula (21) any liquid crystal liquid crystal property side chain in group composed by~(31),

[changing 2]

In formula, A, B, q1 and q2 have and the identical definition；

Y₃For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon and this Base in group composed by the combination of a little rings, the hydrogen atom being bonded on these bases can separately be substituted by-NO₂、- CN, halogen, the alkyl of carbon number 1~5 or carbon number 1~5 alkyl oxy；

R₃Indicate hydrogen atom ,-NO₂,-CN ,-CH=C (CN)₂,-CH=CH-CN, halogen, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan It mutters the alkoxy of ring, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12；

L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (25)~(26), all m's adds up to 2 or more, In formula (27)~(28), all m's adds up to 1 or more, and m1, m2 and m3 separately indicate 1~3 integer；

Z₁、Z₂Indicate singly-bound ,-CO- ,-CH₂O- ,-CH=N- ,-CF₂-。

5. polymer composition according to any one of claim 1 to 4 contains chemical combination represented by following formula (c) Object is used as (C) ingredient,

[changing 3]

In formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In wantonly three to five separately indicate former selected from hydrogen atom, halogen Son, C₁~C₆Alkyl, C₁~C₆Alkylhalide group, C₁~C₆Alkoxy, C₁~C₆Alkyl groups in the halogenalkoxy, C₃~C₈Naphthenic base, C₃~C₈Halogen cycloalkanes Base, C₂~C₆Alkenyl, C₂~C₆Haloalkenyl, C₃~C₈Cycloalkenyl, C₃~C₈Halogen cycloalkenyl, C₂~C₆Alkynyl, C₂~C₆Alkynyl halide, C₁ ~C₆Alkoxy, C₁~C₆Alkyl groups in the halogenalkoxy, (C₁~C₆Alkyl) carbonyl, (C₁~C₆Alkylhalide group) carbonyl, (C₁~C₆Alkoxy) carbonyl Base, (C₁~C₆Alkyl groups in the halogenalkoxy) carbonyl, (C₁~C₆Alkyl amino) carbonyl, (C₁~C₆Alkylhalide group) amino carbonyl, two (C₁~C₆Alkane Base) substituent group in amino carbonyl, cyano and nitro, in R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In wantonly three to four be described In the case where definition, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In it is remaining one or two indicate following formula (c-2)

[changing 4]

(in formula (c-2), dotted line indicates bonding key, R¹⁰⁶For the carbocyclic ring of the alkylidene of carbon number 1~30, phenylene or divalent or miscellaneous Ring, the alkylidene, the carbocyclic ring of phenylene or divalent or one or more hydrogen atoms in heterocycle can be substituted by fluorine atom or Organic group；In addition, R¹⁰⁶In-CH₂CH₂- CH=CH-, R can be substituted by¹⁰⁶In-CH₂Phenylene can be substituted by Or the carbocyclic ring or heterocycle of divalent, it is substituted in the case where alternatively, it is also possible to not adjoin each other in any one base being exemplified below For these bases :-O- ,-NHCO- ,-CONH- ,-COO- ,-OCO- ,-NH- ,-NHCONH- ,-CO-；R¹⁰⁷For hydrogen atom or methyl) Represented base, n indicate 0 or 1.

6. a kind of polarizing layer forms composition, contain polymer composition according to any one of claim 1 to 5.