CN101636469B

CN101636469B - Comprise the liquid crystal polymer of the patternable of thio-ether units

Info

Publication number: CN101636469B
Application number: CN200780047888.2A
Authority: CN
Inventors: P·施图德; I·布里; T·巴舍尔斯; H·塞伯勒; G·马克; S·图古卢
Original assignee: Rolic AG
Current assignee: Rolic Technologies Ltd
Priority date: 2006-12-22
Filing date: 2007-12-11
Publication date: 2016-08-17
Anticipated expiration: 2027-12-11
Also published as: CN101636469A

Abstract

The present invention relates to photo polymerization, patterning or non-patterned liquid crystal polymer, particularly liquid crystalline polymer film or liquid crystal polymer network, it comprises the thio-ether units of formula (I): * covalent bond, the unit of formula (I) is connected on the remainder of polymer by it, wherein LC¹Selected from liquid crystal residue group, X¹Selected from aliphatic organic residue group, and n¹It is >=integer of 0 and m¹It it is >=the integer of 0；Premise is if n¹It is 0, then m¹＞ 0, and if m¹It is 0, then n¹＞ 0；It is preferably to contain aerobic with the amount of 0.1≤oxygen≤50%, more preferably containing with the amount of 1≤oxygen≤25% in the oxygen-containing atmosphere of aerobic, prepare the most in atmosphere；Premise is not include the scattered liquid crystal of polymer.Moreover, it relates to be used for preparing the compositions of the liquid crystal polymer of this photo polymerization of the present invention, the method preparing this liquid crystal polymer, and its purposes.

Description

Comprise the liquid crystal polymer of the patternable of thio-ether units

The present invention relates to photo polymerization, patterning or non-patterned liquid crystal polymer, particularly to liquid crystal polymer Film or liquid crystal polymer network, it comprises the thio-ether units of formula (I)

* covalent bond, the unit of formula (I) is connected on the remainder of polymer by it

Wherein

LC¹Selected from liquid crystal residue group,

X¹Selected from aliphatic organic residue group, and

n¹Be >=integer of 0 and

m¹It it is >=the integer of 0；

Premise is if n¹It is 0, then m¹＞ 0, and if m¹It is 0, then n¹＞ 0；With

It is preferably to contain aerobic with the amount of 0.1≤oxygen≤50%, more preferably containing aerobic with the amount of 1≤oxygen≤25% Oxygen-containing atmosphere in, prepare the most in atmosphere；

Premise is not include the scattered liquid crystal of polymer.

The invention still further relates to preparation patterning and non-patterned liquid crystal polymer, liquid crystalline polymer film or polymerizable mesogenic The method of thing network, and its application in optics or photoelectric cell.

Broer et al., at Molecular Crystal Liquid Crystal (1999), describes following in 332,259 The synthesis of the liquid crystal of the mercaptan-alkene functionalization of the formula be given

The shortcoming of this material is, the initial orientation of the liquid crystal of this mercaptan-alkene functionalization part in photo polymeric process is damaged Lose, cause opaque polymer liquid crystal polymeric film.Polymerization shrinkage, is separated and crystallization is the master that the orientation of described macroscopic view is disturbed Want reason.In order to overcome these problems, devise crosslinkable multiple functionalized mercaptan-alkene liquid crystal (seeing below):

But, as Wilderbeek (J.Phys.Chem.B (2002), 106,12874) points out, liquid crystal has low dissolving Property character.Low-solubility may cause serious problem in the preparation method of liquid crystal film, such as, be coated on base due to liquid crystal The suitability in method on material.And, there is no the easy way of this polyfunctional liquid crystal.Prepare their method bag Include several processing step and at last uneconomic purification.It addition, use the LCP compound of such functionalization, finely Regulate described mercaptan/alkene and still there is no motility than aspect.

GB2394718-A describes by controlling polymerizing condition such as radiant intensity, atmosphere and temperature, and/or uses properly Polymerisable liquid crystal compound obtain there is the liquid crystal film of polymerization postponing pattern.Need nonetheless remain for obtaining patterned optical character Simpler method to two or more different length of delays.This being readily available property all right and wrong for various application Chang Youyong's.

The present invention relates to liquid crystal polymer, it comprises the thio-ether units of formula given above (I).

Preferably, the present invention relates to liquid crystal polymer given above, it is in the feelings not using cation light initiator Preparation under condition.

Liquid crystal polymer the most given above, it is in the feelings not using the oxygen barrier layer getting rid of oxygen Preparation under condition.

Additionally preferably, the present invention relates to liquid crystal polymer given above, it is to use low UV lamp power and energy system Standby.

Wording " oxygen-containing atmosphere " has discharged inert gas atmosphere.

Preferably, the present invention relates to the liquid crystal polymer in above-mentioned prioritizing selection and restriction, the sulfur of its contained (Ia) Ether unit

* covalent bond, the unit of formula (Ia) is connected on the remainder of polymer by it

(Ia)

Wherein

LC¹, LC²And LCⁱIt is liquid crystal residue independently of one another,

Wherein

LCⁱSelected from lower group: LC³, LC⁴, LC⁵, LC⁶, LC⁷And LC⁸, they represent liquid crystal residue independently of one another,

X¹And X²Being aliphatic organic residue independently of one another, it is preferably without reactive carbon-to-carbon degree of unsaturation,

n¹And n²It is >=the integer of 0, the integer of preferably 1-10,

R is >=integer of 0, and the integer of preferably 0-1000,

m¹, m²And m³It is >=the integer of 0 independently of one another, the integer of preferably 0-10,

Q is 0 or 1；

Premise is, if q is 0, then LC²And LCⁱIt is connected directly to one another；If with n¹And n²It is 0, then at least one m¹, m²Or m³It is ＞ 0, and if m¹, m²And m³It is 0, then at least one n¹And n²It is ＞ 0.

It is highly preferred that the liquid crystal polymer that the present invention relates in above-mentioned prioritizing selection and restriction, its contained (Ib's) Thio-ether units

* covalent bond, the unit of formula (Ib) is connected on the remainder of polymer by it

(Ib)

Wherein

LC¹, LC²And LCⁱIt is liquid crystal residue independently of one another,

Wherein

T^bSelected from lower group: T¹, T², T³, T⁴, T⁵And T⁶, they are and the residue representing reactive additive independently of one another,

X¹, X²And X³Being independently from each other aliphatic organic residue, preferably bivalence or polyvalent organic residue, it is the most not Containing reactive carbon-to-carbon degree of unsaturation,

n¹, n²And n³It is >=the integer of 0 independently of one another, the integer of preferably 1-10,

m¹, m², m³And m⁴It is >=the integer of 0 independently of one another, the integer of the integer of preferably 0-10, more preferably 0-2,

Q and q1 is 0 or 1 independently of one another, and

R and s is the integer of the integer of the integer of 0-1000, preferably 0-500, more preferably 0-100 independently of one another；Most preferably " s " is the integer of 0-10, and particularly most preferably " s " is the integer of 0-5；" r " is in the range of 0-10；

Premise is, if q is 0, then LC²And LCⁱIt is connected directly to one another；If with n¹, n²And n³It is 0, then at least one Individual m¹, m², m³And m⁴More than 0, and if m¹, m², m³And m⁴It is 0, then at least one n¹, n²And n³More than 0.

The value of subscript r and s depends on described material, is particularly depending on the group of compound for preparing described liquid crystal film Become and prepare the process conditions of described liquid crystal polymer.

The preferably liquid crystal polymer of formula (Ib),

Wherein:

R and s is the integer of the integer of 0-500, more preferably 0-100 independently of one another；Most preferably " s " is in the scope of 0-10 In, particularly most preferably s represents that 0-5 and " r " are in the range of 0-10；And/or

n¹, n²And n³It is the integer of 0-4 independently of one another, the integer of more preferably 0,1-2, most preferably 1 or 2.

Liquid crystal polymer is preferably liquid crystal liquid crystal property (co) polymer, elastomer, polymer gel, film or polymer network, more Preferably liquid crystal polymer network or film.

Term " photo polymerization " describes below in the method for the invention.

Term " liquid crystal residue ", " reactive additive residue " and " compounds residues " is illustrated respectively in described polymerizable mesogenic The polymerized form of described liquid crystal, reactive additive or compound in thing.

In a further preferred embodiment, the present invention relates to formula (I), (Ia) or the liquid crystal polymer of (Ib), wherein It is connected to liquid crystal LC¹、LC²And/or LCⁱThioether bond "-S-" comprise connection unit, it is selected from compound group given below Compounds residues: norborene, vinyl ethers, vinyl esters, allyl ether, allyl ester, propenyl ether, pi-allyl triazine, Isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, acid imide, maleimide, methacrylate, propylene Nitrile, styrene, alkadienes, vinylamide and alkynes,

And it is most preferably selected from the compounds residues of given below group: alkynes, alkene, vinyl ethers, vinyl esters, alkene Propyl ether, allyl ester, acrylate and methacrylate,

And particularly most preferably selected from the compounds residues of given below group: acrylate and methacrylate.

The residue of liquid crystal and the residue of reactive additive have the polymerisable sense of at least two at its non-polymerized form Group, particularly two undersaturated carbon-carbon bonds.Described undersaturated carbon-carbon bond preferably comprises double bond and/or three keys, more preferably Comprise double bond.

Preferably, the polymerisable functional group of described liquid crystal comprises undersaturated carbon-carbon bond, and it is preferably selected from including as follows The compound group of compound: norborene, alkynes, vinyl ethers, vinyl esters, allyl ether, allyl ester, propenyl ether, Pi-allyl triazine, isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, acid imide, maleimide, methyl-prop Olefin(e) acid ester, acrylonitrile, styrene, alkadienes and vinylamide；There is described in it is highly preferred that gathering of unsaturated carbon-carbon bond The functional group closed is selected from the compound group including following compound: alkynes, alkene, vinyl ethers, vinyl esters, allyl ether, Allyl ester, acrylate and methacrylate；Be most preferably selected from acrylate and methacrylate.

The term liquid crystal used in the context of the present invention refer to have the ability of induction Mesomorphic behavior material or Compound, such as, comprise one or more rod, plate shape (board-shaped) or disc (disk-shaped) mesomorphic base Group.The liquid-crystal compounds with rod or plate shape group is also referred to as calamitic liquid crystal in the art.There is disc base The liquid-crystal compounds of group is also referred to as discotic liquid crystal in the art.The described compound comprising mesomorphic group or material are originally Body necessarily shows liquid crystalline phase.They only with the mixture of other compound in or when described mesomorphic compound or material or Their mixture shows when being polymerized that Mesomorphic behavior is also possible.

The example of the suitable polymerisable liquid crystal that can use in the present invention is disclosed in such as WO2005/105932, WO 2005/054406, WO 2004/085547, WO 2003/027056, US 2004/0164272, US 6746729, US 6733690, WO 2000/48985, WO2000/07975, WO 2000/04110, WO 2000/05189, WO 99/37735, In US6395351, US 5700393, US 5851424 and US 5650534.

The term " aliphatic organic residue " used in the context of the present invention relates to the organic residue of multi-thiol, In the range of the implication being provided below and prioritizing selection.

In the context of the present invention, term " aliphatic " includes straight chain and branched hydrocarbon and saturated and undersaturated Group, at least one of which carbon, hydrogen and/or hydrogen carbon can be by hetero atom such as N, S, O, OOC, COO, OCO, OCOO, OOCO, CO etc. Substitute.Possible substituent group includes alkyl, cycloalkyl aryl, and amino, cyano group, epoxy, halogen, hydroxyl, nitro, oxo Deng.The possible hetero atom that can substitute for carbon atom includes nitrogen, oxygen and sulfur.In the case of nitrogen, can be by group such as alkyl, virtue Base and cycloalkyl are further substituted with.Similarly, term used herein " alkyl " and " alkylidene " include straight chain or branched Group, and saturated and undersaturated group.

In the context of the present invention, during suitable multi-thiol can be those multi-thiols as known in the art Any.As multi-thiol, it is possible to use comprise per molecule and there is molecule any of two or more thiol groups Compound.Described multi-thiol has the molecular weight in the range of about 50-about 20,000.

Preferably, multi-thiol is monomeric fatty race multi-thiol, oligomer multi-thiol and polymer polyol mercaptan.

Preferably multi-thiol relate to two-, three-, four-or polyfunctional mercaptan.

Preferably polymer polyol mercaptan is that such as polytrimethylene ether glycol is double (β-mercaptopropionic acid ester), and it is anti-by esterification Should be by polytrimethylene ether glycol (such as Pluracol P201, Wyandotte Chemical Corp.) and β-mercaptopropionic acid system Standby.Poly-alpha mercaptoacetic acid ester or poly-β-mercaptopropionic acid ester, particularly trimethylolpropane triester or tetramethylolmethane four ester are excellent Choosing.

Preferably the compound of alkyl hydrosulfide functionalization is such as 1,2-dimercaptoethane, 1,6-dimercaptohexane, 1,10- Decanedithiol etc..The polythiaether resin that mercaptan blocks can also be used.

The most aliphatic two mercaptan include 1,2-dimercaptoethylsulfide, butanediethiol, 1,3-propanedithiol, 1,5- Pentanedithiol, 2,3-dimercapto-1-propanol, 1,4-Dithioerythritol, 3,6-dioxa-1,8-octanedithiol, 1,8-octane Two mercaptan, hexanedithiol, dithiodiglycol, pentanedithiol, decanedithiol, 2-methyl isophthalic acid, 4-butanediethiol, Two-mercaptoethyl phenylmethane, 1,9-nonane two mercaptan (1,9-dimercapto nonane), ethylene glycol dimercapto acetate.

Preferably oligomer two mercaptan includes the oligourethane of dual functional Mercaptofunctional, and it is derived from hydroxyl Ethanethio, hydroxypropyl mercaptan, dimercaptopropane, the end of dimercaptoethane, such as patent USP of Shustack Described in 5744514.

The compound of preferred three thiol-functionals includes trimethylolethane trimethacrylate mercaptopropionic acid ester, trimethylolpropane tris Mercaptopropionic acid ester (TMPTSH), trimethylolethane trimethacrylate mercaptoacetate, and trimethylolpropane tris mercaptoacetate, glycerol three (11-sulfydryl hendecoic acid ester), trimethylolpropane tris (11-sulfydryl hendecoic acid ester).

The mercaptan of preferred four senses includes tetramethylolmethane four mercaptopropionic acid ester, tetramethylolmethane four mercaptoacetate, and season Penta tetrol four (11-sulfydryl hendecoic acid ester).

The multi-functional thiol preferably with the degree of functionality more than 4 includes the 7th of the patent of Loctite (WO/8802902) Multi-thiol described by Ye.

Polyfunctional mercaptan can be by making mercaptoalkyl carboxylic acid such as TGA, mercaptopropionic acid and the alcohol of high official energy, amine Obtain with thiol reactant.And, polyfunctional mercaptan can react with silanol by making mercaptoalkyl trialkoxy silane And obtain, described silanol can be polymer or silicon-dioxide-substrate silanol.Other preferred multi-functional thiol uses mercaptan Carboxylic acid (HS-R-COOH, wherein R=alkyl or aryl group) such as sulfydryl hendecoic acid obtains, the COOH base of described thiol carboxylic acid Group reacts with polyfunctional reactive alkene, alcohol, mercaptan or amine.

Preferably, multi-thiol has-C₁-C₁₀Alkylidene-COOH and polyol such as glycol, triol, tetrol, five Alcohol or the organic residue of six alcohol.

It is highly preferred that organic residue is glycolic (-CH₂COOH), α-propionic acid (-CH (CH₃)-COOH and β-propanoic acid (- CH₂CH₂COOH) with polyol such as glycol, triol, tetrol, pentol or the ester of six alcohol.

Preferably-C₁-C₁₀Alkylidene-COOH, preferably-C₁-C₄Alkylidene-COOH, most preferably-C₂-C₃Alkylidene- The organic residue of the organic ester of COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

More preferably-CH₂COOH ,-CH (CH₃)-COOH ,-CH₂CH₂COOH and polyol such as glycol, triol, The organic residue of the ester of tetrol, pentol or six alcohol.

Especially, most preferably from the organic residue of following material: multi-thiol such as glycolate (glycolate) And propionic ester, such as ethylene glycol bis (mercaptoacetate), ethylene glycol bis (β-mercaptopropionic acid ester), trimethylolpropane tris (sulfydryl Acetas), trimethylolpropane tris (β-mercaptopropionic acid ester), tetramethylolmethane four (β-mercaptopropionic acid ester), ethylene glycol bisthioglycolate sulfydryl second Acid esters, 1,2,6-hexanetriol tri-thiol acetas, trimethylolethane trimethacrylate mercaptoacetate, tetramethylolmethane four (TGA Ester), trimethylolpropane tris mercaptoacetate and glyceryl thioglycolate；With propionic ester such as trimethylolethane trimethacrylate-(3- Mercaptopropionic acid ester), tetramethylolmethane four (3-thiopropionate), trimethylolpropane tris (3-thiopropionate) or ethylene glycol bisthioglycolate mercapto Base propionic ester, they are all available commercially, and maybe can be obtained by methods known in the art.

The term " reactive additive " used in the context of the present invention refers to polymerisable reactive additive, its There is at least one polymerisable group.Such as, reactive additive is cross-linking agent, reactive diluent, single reaction liquid crystal, The mercaptan of simple function, such as lauryl mercaptan.

It addition, reactive additive is selected from the additive with at least one polymerizable groups set forth below Group: antioxidant, accelerator, dyestuff, inhibitor, activator, filler, chain tra nsfer inhibitor, pigment, antistatic additive, fire retardant, increase Thick dose, thixotropic agent, surfactant, viscosity improver, extending oil, plasticizer, viscosifier, catalyst, sensitizer, stabilizer, Lubricant；Dispersant, water-repelling agent, binding agent, flow improving agent (flow improvers), defoamer, degasser, diluent, Auxiliary ingredient, coloring agent, dyestuff and pigment.

The term " single reaction liquid crystal " used in the context of the present invention refers to have a polymerisable functional group, The liquid crystal of preferably unsaturated carbon-carbon bond.Described unsaturated carbon-carbon bond preferably comprises double bond and/or three keys, and more preferably comprises double Key.

Preferably, described reactive additive has at least one, preferably greater than two polymerisable functional groups.Preferably It is such as unsaturated carbon-carbon bond, particularly acrylate and methacrylic acid ester group, more particularly acrylate group etc Polymerisable functional group.

Cross-linking agent is known to technical staff.Suitably compound is described in such as patent publications EP 0331233, WO 95/24454, US 5,567,349, US 5,650,534, WO00/04110, WO 00/07975, WO 00/48985, WO In 00/55110 and WO 00/63154.

Reactive additive can be selected from, but not limited to, with norborene, vinyl ethers, vinyl esters, allyl ether, Allyl ester, propenyl ether, pi-allyl triazine, isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, acyl is sub- Amine, maleimide, methacrylate, acrylonitrile, styrene, alkadienes, vinylamide and alkynes polymerizable groups Monomer.

It is most preferably selected from given below group: alkynes, alkene, vinyl ethers, vinyl esters, allyl ether, allyl ester, Acrylate and methacrylate.

Particularly most preferably, the polymerizable functional group of the reactive additive described in unsaturated carbon-carbon bond is propylene Acid esters or methacrylate, such as: trimethylolpropane trimethacrylate；Glycol diacrylate；TEG dipropyl Olefin(e) acid ester；1,6-hexanediyl ester；Pentaerythritol triacrylate；Diethylene glycol diacrylate；BDO Diacrylate；Tetramethylol methane tetraacrylate；1,3 butylene glycol diacrylate；Triethylene glycol diacrylate；New penta 2 Alcohol diacrylate；2-butylene-Isosorbide-5-Nitrae-diacrylate；1,3-bis-[(acryloyloxymethyl) phenethyl] tetramethyl two silica Alkane；Tripropylene glycol diacrylate；Trimethylolpropane b-oxide triacrylate；1,2-PD diacrylate；1, Ammediol diacrylate；2,2,3,3,4,4,5,5-octafluoro hexane-1,6-diacrylate；1,5-PD diacrylate Ester；Bis-phenol a diacrylate；Bis-phenol a propoxide diacrylate；Decamethylene-glycol diacrylate；2,2-dibromos new penta Omega-diol diacrylate；3,3 '-dimethyl bisphenol " a " diacrylate；Dipentaerythritol Pentaacrylate；Ethoxylation double Phenol a diacrylate；The tetrabromobisphenol a diacrylate of ethoxylation；Glyceryl propoxylate；4,4 '-(sub-six Fluorine isopropyl) diphenyl diacrylate；1,9-nonanediol diacrylate；Dimethyl pentaerythritol acrylate；Hydroquinone two Acrylate；Sorbitol diacrylate；Sorbitol five acrylate；2,2 ', 6,6 '-tetrabromobisphenol a diacrylate； 2,2 ', 6,6 '-tetrachlorobisphenol a diacrylate；Tetraethoxy bis-phenol a diacrylate；2,2,3,3-tetra-fluoro-Isosorbide-5-Nitrae-butane two Acrylate；Mercaptan diethylene glycol diacrylate；1,1,1-methylolethane triacrylate；Isocyanuric acid three (2-hydroxyl Base ethyl) ester triacrylate；5-ethyl-5-(hydroxymethyl)-β, beta-dimethyl-1,3-dioxane-2-ethanol diacrylate Ester；1,6-dihexyl two [oxygen (2-hydroxyl-3,1-glyceryl)] diacrylate；kayarad r-551； kayaradpeg400da；Isosorbide-5-Nitrae-cyclohexanedimethyl Isosorbide-5-Nitrae-diacrylate；Glycerol propoxylate triacrylate；Two seasons penta Tetrol five-and six-acrylate；Two (trimethylolpropane) tetraacrylate；Neopentyl glycol b-oxide diacrylate；Season Penta tetrol diacrylate monostearate；Trimethylolpropane b-oxide methyl ether diacrylate；(3- (allanoyloxy)-5-[4-(benzamido)-2-oxopyrimidin-1 (2h)-yl] oxolane-2-base；Diacrylate 1, 3-Asia phenyl ester；Fluorescein dimethylacrylate；3-hydroxyl-2,2-dimethyl propyl 3-hydroxyl-PA ester two Acrylate；2,2 ', 6,6 '-tetrabromobisphenol " a " diacrylate；Bis-phenol a glyceride (1 glycerol/phenol) diacrylate； Trimethylolpropane benzoate diacrylate；Propylene glycol glyceride diacrylate；Three (propylene glycol) glyceride two Acrylate；Glycerol 1,3-bis-glyceride diacrylate；Hydroxyl valeryl hydroxy new pentane acid ester two [6-(acryloyl-oxy Base) alkyl caproate]；1,6-hexanediol propoxide diacrylate；Tetramethylolmethane propoxide triacrylate；1,6-hexanediol B-oxide diacrylate；2,2,3,3,4,4-hexafluoro-1,5-amyl group diacrylate；2,2,3,3,4,4,5,5-octafluoros- 1,6-hexyl diacrylate；Three rings [5.2.1.02,6] decane Dimethanol Diacrylate.

It is highly preferred that described liquid crystal has at least two carbon-carbon bond polymerisable, undersaturated of formula (II)

Wherein:

A¹-A⁶It is hydrogen independently of one another, polar group, unsubstituted or substituted methyl group, or unsubstituted or replacement 2-40 carbon atom hydrocarbyl radical group, wherein one or more carbon atoms are substituted in the way of oxygen atom is not connected to each other by hetero atom Or do not substituted by hetero atom, or wherein one or more carbon atoms are replaced by unsubstituted or substituted aromatic carbocyclic or heterocyclic group Generation or do not substituted by unsubstituted or substituted aromatic carbocyclic or heterocyclic group；Include or do not include tool with wherein said hydrocarbyl group There is the polymerizable functional group of unsaturated carbon-carbon bond；Premise is A¹-A⁶At least one of, two preferably comprise have unsaturated carbon- The polymerizable functional group of carbon bond；

B¹And B²Represent singly-bound, oxygen atom or the hydrocarbyl group of optionally substituted 1-80 carbon atom independently of one another, one of them Or multiple carbon atom can be substituted in the way of oxygen atom is not connected to each other by hetero atom；

MG¹There is the implication of lower formula (III)

Wherein

C¹-C⁴It is substituted or unsubstituted, non-aromatic independently of one another or the carbocyclic ring of aromatics or heterocyclic group, the most logical Cross described bridge linkage group Z¹-Z³It is connected to each other in para-position,

Z1-Z3 is independently of one another

-CH(OH)-、-CO-、-CH2(CO)-、-SO-、-CH2(SO)-、-SO2-、-CH2(SO2)-、-COO-、-OCO-、- COCF₂-、-CF₂CO-、-S-CO-、-CO-S-、-SOO-、-OSO-、-SOS-、-CH₂-CH₂-、-OCH₂-、-CH₂O-,-CH= CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-,-CH=N-,-CH (CH₃)=N-,-N=N-or single covalent bond,

a₁, a₂And a₃It is the integer of 0-3 independently of one another so that 1≤a₁+a₂+a₃≤ 3,

A⁷And A⁸Have and A given above¹-A⁶Identical implication；

MG²And MG³There is the implication of lower formula (IV) independently of one another

Wherein

C¹’-C⁴', Z^1’-Z^3’, a_1’, a_2’And a_3’Have and corresponding " letter number ": C¹-C⁴, Z¹-Z³, a₁, a₂And a₃Identical Implication and prioritizing selection；

n₁And n₂It is 1 or 2 independently of one another, wherein " n₁=2 " (or " n₂=2 ") show at described group MG₁And MG₂(or MG₂And MG₃Two are had via described group B between)₁(or described group B₂) single connection；With

n₃It is the integer of the integer of 0-1000, preferably 0-5, more preferably 0 or 1；

n₄It is 0 or 1.

In the context of the present invention, term " hydrocarbon " includes straight chain or branched alkylidene, and saturated and unsaturated Group, and the carbocyclic ring of optionally substituted aromatics or heterocyclic group.

Term " aromatic monocyclic " includes the ring of 5 or 6 atoms, the monocycle of two adjacent 5 or 6 atoms, 8,9 or 10 The bicyclic ring system of atom, or three ring member ring systems of 13 or 14 atoms；Preferably, use in the context of the present invention Term " aromatics " preferably represents unsubstituted or substituted carbocyclic ring and heterocyclic group, is combined with 5,6,10 or 14 annular atomses, Such as furan, benzene or phenylene, pyridine, pyrimidine, naphthalene, it can form ring group, such as biphenylene or sub-terphenyl, its quilt Or be not interrupted by least one hetero atom and/or at least one bridge linkage group；Or the polycyclic system condensed, such as luxuriant and rich with fragrance, naphthane. Preferably, aromatic group is benzene, phenylene, biphenylene or sub-terphenyl.Preferred aromatic group is benzene, phenylene and Biphenylene.

Carbocyclic ring or heterocyclic aromatic group preferably have 5,6,10 or 14 annular atomses, such as such as furan, and benzene, pyridine, triazine, Pyrimidine, naphthalene, luxuriant and rich with fragrance, biphenylene or naphthane unit are such, preferably such as naphthalene, luxuriant and rich with fragrance, and biphenylene or phenylene are such, the most such as Naphthalene, biphenylene or phenylene are such, and most preferably as phenylene.

The carbocyclic ring of described aromatics or heterocyclic group are the most unsubstituted or single or multiple substituted.Carbocyclic ring or heterocyclic aromatic base The preferred substituent group of group is at least one halogen, hydroxyl, polar group, acryloxy, alkyl acyloxy, alcoxyl Base, alkyl carbonyl oxy, alkoxyl carbonyloxy group, alkoxo carbonyloxy group, methacryloxy, vinyl, vinyl epoxide and/ Or allyloxy group, wherein said alkyl residue preferably has 1-20 carbon atom, more preferably has 1-10 carbon atom.Preferably Polar group is nitro, cyano group or carboxylic group, and/or ring-type, straight chain or branched C₁-C₃₀Alkyl, it is unsubstituted, single Substituted or many.C₁-C₃₀The preferred substituent group of alkyl is methyl, fluorine and/or chlorine, wherein one or more, the most non-conterminous -CH₂-group can be connected group independently of one another and substitute.Preferably, described linking group is selected from-O-,-CO-,-COO- And/or-OCO-.

The monocycle of five or six atoms is such as furan, benzene, preferably phenylene, pyridine, pyrimidine.

Eight, the bicyclic ring system of nine or ten atoms is such as naphthalene, biphenylene or naphthane.

Three ring member ring systems of 13 or 14 atoms are such as luxuriant and rich with fragrance.

The term " phenylene " used in the context of the present invention preferably represents 1,2-, 1,3-or Isosorbide-5-Nitrae-phenylene base Group, it is optionally substituted.The most described phenylene group is 1,3-or Isosorbide-5-Nitrae-phenylene group.Isosorbide-5-Nitrae-phenylene group is special The most preferred.

Term " halogen " refers to chlorine, fluorine, bromine or iodine substituent group, preferably chlorine or fluoro substituents.

The term " polar group " used in the context of the present invention is primarily referred to as the base of such as nitro, cyano group or carboxyl Group.

The term " hetero atom " used in the context of the present invention is primarily referred to as oxygen, sulfur and nitrogen, preferably oxygen and nitrogen, rear Preferred form in-NH-in the case of one.At nitrogen as in the case of heteroatomic, it can be with group such as alkyl, aryl and cycloalkanes Base is further substituted with.

The term " substituted " used in the context of the present invention is primarily referred to as being replaced by following group: low alkyl group is such as C₁-C₆Alkyl, lower alkoxy such as C₁-C₆Alkoxyl, aryl and group of naphthene base, and amino, cyano group, carboxyl, epoxy, halogen Element, hydroxyl, nitro, oxo and hydroxyl.

Preferably, A¹And A⁸At least one of inclusion compound residue formula (V) independently of one another:

P-(Sp)_k-(X)_t- (V)

Wherein:

P is hydrogen or polar group, preferably nitro, cyano group, halogen；Or unsubstituted or substituted methyl group, or have The polymerizable functional group of unsaturated carbon-carbon bond, this polymerizable functional group is selected from and comprises norborene, vinyl ethers, vinyl esters, Allyl ether, allyl ester, propenyl ether, pi-allyl triazine, isocyanuric acid allyl ester, alkene, alkynes, acrylate, no Saturated ester, acid imide, maleimide, methacrylate, acrylonitrile, styrene, alkadienes, vinylamide and allyl The group of base amide；

Sp is unsubstituted or substituted straight chain or branched C_1-30Alkylidene group, wherein one or more-CH₂-group Can substitute by hetero atom and/or by polar group, and/or one or more carbon-to-carbon singly-bound is replaced by carbon-to-carbon double bond or three keys Generation, and/or be the most optionally possible by least one optionally substituted aromatic carbocyclic or heterocyclic group replacement,

K is integer, has the value of 0-4,

X is-O-,-S-,-NH-,-N (CH₃)-,-CH (OH)-,-CO-,-CH₂(CO)-,-SO-,-CH₂(SO)-,- SO₂-,-CH₂(SO₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-CH₂-CH₂-,- OCH₂-,-CH2O-,-CH=CH-,-C ≡ C-, or singly-bound,

T is the integer of the value with 0 or 1.

Described C_1-30Alkylidene or C_1-20Alkylidene group Sp can comprise branched or straight chain alkylen, and can Being unsubstituted, or by the single or multiple replacement of following groups: alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl Base, nitro, particularly F, Cl, Br, I or CN.Altematively or additionally, the one or more CH being present in described hydrocarbon chain₂ Group can be substituted by one or more groups selected from lower group independently :-O-,-S-,-NH-, N (CH₃)-,-CH (OH)-,- CO-,-CH₂(CO)-,-SO-,-CH₂(SO)-,-SO₂-,-CH₂(SO₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO- S-,-SOO-,-OSO-,-SOS-,-C ≡ C-,-(CF₂)_r1-,-(CH₂)_s1-or C (W₁)=C (W₂)-, premise is two oxygen atoms It is not connected directly to one another.W₁And W₂Represent H, H-(CH independently of one another₂)_q2-or Cl.Described integer r1, s2 and q2 are independently of one another Represent the number between 1 and 15.

Preferably, Sp represents C_1-20Alkylidene group, more preferably C_1-13Alkylidene group, it is unsubstituted or with alkyl, Aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro is substituted, and wherein one or more-CH₂-group can To be substituted by hetero atom；And/or substituted by carbocyclic ring or the heterocyclic group of at least one optionally substituted aromatics, given above In the range of implication and prioritizing selection.

Preferably, P is hydrogen, nitro, cyano group, halogen, unsubstituted or substituted methyl group, or have unsaturated carbon- The polymerizable functional group of carbon bond, this polymerizable functional group is selected from and comprises vinyl ethers, vinyl esters, allyl ether, allyl ester, Propenyl ether, alkene, alkynes, acrylate, undersaturated ester and the group of methacrylate, be preferably selected from comprising acrylic acid Ester and the group of methacrylate.

Preferably, X represents-O-,-CO-,-COO-,-OCO-,-C=C-, and it is highly preferred that X be-O-,-COO-or- OCO-。

It is further preferred that

Sp represents C_1-20Straight chain alkylen, more preferably C_1-13Alkylidene group, it is unsubstituted or with alkyl, fragrant Base, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl or nitro are substituted, and wherein one or more carbon atoms can be by miscellaneous former Son substitutes and/or is substituted by carbocyclic ring or the heterocyclic group of at least one optionally substituted aromatics；

X represents-O-,-CO-,-COO-,-OCO-,-C=C-, and preferably, X is-O-,-COO-,-OCO-, and

P is hydrogen or the polymerizable functional group with unsaturated carbon-carbon bond, and this polymerizable functional group is selected from comprising vinyl Ether, vinyl esters, allyl ether, allyl ester, acrylate, the group of methacrylate, and preferably-O-,-COO-,- OCO-。

Preferably, B¹And/or B²Comprise the group of formula (VI) independently of one another:

(X⁴)_t2-(Sp²)_k2-(X⁵)_t3 (VI)

Wherein:

Sp²Represent C_1-20Alkylidene group；

X⁴And X⁵Expression-O-independently of one another ,-S-,-NH-, N (CH₃)-,-CH (OH)-,-CO-,-CH₂(CO)-,- SO-,-CH₂(SO)-,-SO₂-,-CH₂(SO₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,- SOS-,-CH₂-CH₂-,-OCH₂-,-CH₂O-,-CH=CH-,-C ≡ C-or singly-bound；

K2 is integer, has the value of 0 or 1；

T2 and t3 is integer, has the value of 0 or 1 independently of one another；

Premise is that oxygen atom is not connected to each other.

Preferably, B¹And B²Represent the group of formula (VI) independently of one another, wherein:

X⁴And X⁵Expression-O-,-CO-,-COO-,-OCO-,-C ≡ C-, or singly-bound independently of one another, particularly-O-,- COO-,-OCO-or singly-bound；With

Sp₂Represent C_1-20Straight chain alkylen, particularly ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub- Heptyl, octylene, nonamethylene, decylene, alkylene undecyl or sub-dodecyl.

A kind of particularly preferred polymer is wherein B¹And B²Represent group and the A of formula (VI) independently of one another¹-A⁸Each Represent the polymer of the group of formula V independently.

Preferably, C¹-C⁴It is selected from:

Wherein:

L is-CH₃,-COCH₃,-NO₂,-CN or halogen,

U1 is 0,1,2,3, or 4,

U2 is 0,1,2, or 3,

U3 is 0,1, or 2.

It is highly preferred that C¹-C⁴It is selected from: cyclohexylidene, phenylene, naphthylene or phenanthrylene.

Most preferably, C¹-C⁴It is selected from: phenylene

Preferably, Z¹-Z³Expression-COO-,-OCO-,-CH independently of one another₂-CH₂-,-OCH₂-,-CH₂O-,-CH= CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-or single covalent bond.

It is highly preferred that Z¹-Z³Expression-COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or list independently of one another Covalent bond.

The most preferably liquid crystal of the present invention of formula (VII)

Wherein:

A¹, A², A⁷, C¹, C², C³, Z¹And Z²And a1 with a2 has identical implication given above and prioritizing selection.

The most particularly most preferably be the compound of formula (VII), wherein:

-A₁And A₂It is compound formula V independently of one another:

P-(Sp)_k-(X)_t- (V)

Wherein

P is the polymerizable functional group with unsaturated carbon-carbon bond, and it is selected from comprising vinyl ethers, vinyl esters, pi-allyl Ether, allyl ester, propenyl ether, alkene, alkynes, acrylate, undersaturated ester and the group of methacrylate, preferably select Self-contained acrylate and the group of methacrylate；

Preferably, at A¹And A²Middle P is identical；

Sp represents C_1-20Alkylidene group, more preferably C_1-13Alkylidene group, it is unsubstituted or with alkyl, aryl, ring Alkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro is substituted, and wherein one or more-CH₂-group can be by miscellaneous former Son substitutes；And/or substituted by least one optionally substituted aromatic carbocyclic or heterocyclic group, implication given above is with preferential In the range of choice；

X represents-O-,-CO-,-COO-,-OCO-,-C=C-, and more preferably X is-O-,-COO-,-OCO-；

K is the integer of the value with 0-4,

T is the integer of the value with 0 or 1；And/or

-A⁷There is identical implication given above and prioritizing selection；Preferably, A⁷It is hydrogen or polar group, preferably nitre Tool in the range of base, cyano group, halogen, unsubstituted or substituted methyl group, or implication given above and prioritizing selection There is the polymerizable functional group of unsaturated carbon-carbon bond；Preferably, A⁷It is hydrogen or polar group, preferably nitro, cyano group, halogen, do not take Generation or substituted methyl group and/or

-C¹, C²And C³It is identical identical meanings given above and prioritizing selection；Especially, C¹, C²And C³It is sub-benzene Base；And/or

-Z¹And Z²It is identical, and there is identical implication given above and prioritizing selection；Preferably, Z¹And Z²Be- COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound；If Z¹And Z²One of be singly-bound, then another Z is excellent Choosing is-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH-.

It addition, most preferably A¹And A²It is identical.

It addition, the liquid crystal polymer of the most preferably present invention of formula (VIII)

Wherein:

A¹, A², A⁵, A⁶, C¹, C², C³, B¹, Z¹And Z², C¹', C²', C³', Z¹' and Z²' and a1, a2, a1 ' and a2 ' have Identical implication given above and prioritizing selection.

The most particularly most preferably be the compound of formula (VIII), wherein

-A¹, A², A⁵, A⁶It is compounds residues formula (V) independently of one another:

P-(Sp)_k-(X)_t- (V)

Wherein

P is the polymerizable functional group with unsaturated carbon-carbon bond, and it is selected from comprising vinyl ethers, vinyl esters, pi-allyl Ether, allyl ester, propenyl ether, alkene, alkynes, acrylate, undersaturated ester and the group of methacrylate, and preferably Selected from the group comprising acrylate and methacrylate；Preferably at A¹, A², A⁵, A⁶In P be identical；

Sp represents C_1-20Alkylidene group, more preferably C_1-13Alkylidene group, it is unsubstituted or with alkyl, aryl, ring Alkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro are substituted, and wherein one or more-CH₂-group can be miscellaneous Atom substitutes；And/or substituted by least one optionally substituted aromatic carbocyclic or heterocyclic group, implication given above and excellent In the first range of choice；

X represents-O-,-CO-,-COO-,-OCO-,-C=C-, it is highly preferred that X is-O-,-COO-,-OCO-；

K is the integer of the value with 0-4,

T is the integer of the value with 0 or 1；

Preferably A¹, A², A⁵, A⁶It is identical；

And/or

-B¹Comprise the group of formula (VI):

(X⁴)_t2-(Sp²)_k2-(X⁵)_t3 (VI)

Wherein:

Sp²Represent C_1-20Alkylidene group；

K2 is integer, has the value of 0 or 1；

T2 and t3 is integer, has the value of 0 or 1 independently of one another；

Premise is that oxygen atom is not connected to each other；

Preferably, B¹Represent the group of formula (VI), wherein:

Sp²Represent C_1-20Straight chain alkylen, particularly ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub- Heptyl, octylene, nonamethylene, decylene, alkylene undecyl or sub-dodecyl；And/or

-C₁', C₂' and C₃' and C₁, C₂And C₃It is identical and there is identical implication given above and prioritizing selection；Special Not, C₁', C₂' and C₃' and C₁, C₂And C₃It it is phenylene；And/or

-Z¹And Z²And Z¹' and Z²' it is identical, and there is identical implication given above and prioritizing selection；Preferably, Z¹And Z²And Z¹' and Z²' it is-COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound；If Z¹And Z²One of be Singly-bound, then another Z preferably-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH-, and if Z¹' and Z²’ One of be singly-bound, then another Z preferably-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH.

The invention still further relates to compositions (XX), it comprises:

A) multi-thiol of at least one formula (IX)

Wherein

X^aIt is aliphatic organic residue,

n^tIt is >=the integer of 2, the integer of preferably 2-10, more preferably 3 or 4, and

B) at least one has the liquid crystal of at least two polymerizable functional group, and

C) a kind of reactive and/or non-reacted additive, and

D) optionally at least a kind of initiator, and

E) optionally at least a kind of solvent.

The preferably compositions of the present invention, does not the most include tetramethylolmethane four (β-dodecy) propionic ester.

The more preferably compositions of the present invention, wherein said liquid-crystal compounds is with more than 50 weight % to described compositions The amount of gross weight exists.

Furthermore it is preferred that the present invention relates to liquid crystal polymer given above, it does not contains cation light initiator.

In another preferred embodiment, described solvent account for described compound less than 50 weight %, preferably comprise institute State compound less than 30 weight %, more preferably account for described compound less than 10 weight %.

In a preferred embodiment in accordance with this invention, described compositions comprises initiator.

Described liquid crystal, multi-thiol, aliphatic organic residue, polymerisable functional group and non-reacted additive have Identical implication given above and prioritizing selection.

It is particularly preferred that X^aIt is-C₁-C₁₀Alkylidene-COOH and polyol such as glycol, triol, tetrol, pentol or The multivalence aliphatic organic residue of the organic ester of six alcohol.

It is highly preferred that X^aIt is glycolic (-CH₂COOH), α-propionic acid (-CH (CH₃)-COOH and β-propanoic acid (-CH₂CH₂COOH) With polyol such as glycol, triol, tetrol, pentol or the ester of six alcohol.

Preferably HS-C₁-C₁₀Alkylidene-COOH, preferably HS-C₁-C₄Alkylidene-COOH, most preferably HS-C₂-C₃Alkylene The multi-thiol of the organic ester of base-COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

More preferably TGA (HS-CH₂COOH), alpha-mercapto propanoic acid (HS-CH (CH₃)-COOH and β-mercaptopropionic acid (HS-CH₂CH₂COOH) with polyol such as glycol, triol, tetrol, the multi-thiol of ester of pentol or six alcohol.

Especially, most preferred multi-thiol is ethyl glycolate and propionic ester, such as ethylene glycol bis (mercaptoacetate), second Glycol is double (β-mercaptopropionic acid ester), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (β-mercaptopropionic acid ester), Tetramethylolmethane four (β-mercaptopropionic acid ester), ethylene glycol dimercapto acetate, 1,2,6-hexanetriol tri-thiol acetas, trihydroxy methyl Ethane tri-thiol acetas, tetramethylolmethane four (mercaptoacetate), trimethylolpropane tris mercaptoacetate and glyceryl sulfydryl Acetas；And propionic ester, such as trimethylolethane trimethacrylate-(3-thiopropionate), tetramethylolmethane four (3-thiopropionate), three Hydroxymethyl-propane three (3-thiopropionate) or glycol dimercaptopropionate, all these be all available commercially, or Can be obtained by methods known in the art.

Polymerization can be carried out with or without initiator, initiator is preferably used and carries out.Initiator whether is used to depend on The kind of beginning material and technological parameter.Any kind of initiator in addition to cation light initiator can be selected.Preferably Radical initiator.Described initiator can be heat or light trigger or a combination thereof.More preferably free radical photo-initiation.

Generally, light trigger has absorption at the wavelength of actinic radiation.When polymerization utilizes UV light to carry out, it is possible to use UV irradiates the lower free radical decomposed to produce starting polyreaction or the light trigger of ion.UV light trigger is preferred, special It it not free radical UV light trigger.The example of free radical photo-initiation or maleimide light trigger is by Dias et al. (SurfaceCoatings International, JOCCA 2000,10,502-506 and WO-01/27040) describes.

Light trigger as the standard for radical polymerization, it is possible to use be such as available commercially907,651,369,184, 1173 or4205 (all deriving from Ciba SpecialtyChemicals).

Non-reacted additive such as relates to antioxidant, accelerator, dyestuff, inhibitor, activator, filler, pigment, resists quiet Electricity agent, fire retardant, thickening agent, thixotropic agent, surfactant, viscosity improver, extending oil, plasticizer, viscosifier, catalyst, Sensitizer, stabilizer, such as phenol derivatives, such as 4-thanatol or 2,6-di-tert-butyl-4-methy phenol (BHT), Lubricant；Dispersant, water-repelling agent, binding agent, flow improving agent, defoamer, degasser, diluent, curing inhibitors, auxiliary is joined Photo-orientable monomer described in mixture, coloring agent, dyestuff, pigment or EP1 090 325 B or oligomer or polymer；

Especially, if requiring colored filter, can add dye in the compositions of the present invention.

The conventional solidification that can be used to stable component or curable compositions thus prevent premature solidification from starting presses down Preparation or polymerization inhibitor can include hydroquinone；P-tert-butyl catechol；2,6-di-t-butyls-p-methyl phenol；Phenothiazine；N-benzene Base-2-naphthylamine.

Described compositions is solid, or dilutes in a solvent with the form of solution, gel, dispersion or emulsion, described molten Agent is organic solvent and/or water.

Preferably, described compositions is transparent solution.The described solvent used in this application or solvent mixture can To be any compound of the liquid-crystal composition that can dissolve the present invention.At least one solvent, the most common pole can be used Property solvent or non-polar solven.Particularly preferred solvent is the solution causing described material good coating on applied base material Those of property or printing.

Non-polar solven is to have low dielectric constant and water-immiscible compound, such as hexane, benzene, toluene, Ether, chloroform, ethyl acetate, dichloromethane.

Polar solvent is non-proton or proton.

Polar non-solute is to have the ion-solubility ability of proton solvent but does not have the solvent of acidic hydrogen.These are molten Agent is generally of high dielectric constant and high polarity.Example is Isosorbide-5-Nitrae-dioxane, oxolane (THF), acetone, acetonitrile (MeCN), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), ethyl pyrrolidone, N-second Vinyl pyrrolidone, butoxy ethanol (BC), gamma-butyrolacton (BL), N-methylmorpholine, gamma-butyrolacton, acetonitrile, diethylene glycol One ether, DEGMBE, diethylene glycol monoethyl ether acetate, ethylene glycol, Propylene glycol monoacetate, propylene-glycol diacetate, Dipropylene glycol, and DPGME, chlorobenzene, oxolane, butyl cellosolve, Ketocyclopentane (CP), methyl ethyl ketone (MEK), ethyl acetate (EA), methyl phenyl ethers anisole (AN), Ketohexamethylene (CHN), methyl iso-butyl ketone (MIBK) (MIBK), 1-methoxy-2-propanol Acetas (MPA), N, N-dimethyl-formamidine (DMF), dichloromethane, gamma-butyrolacton (BL), and their mixture.

Polar aprotic solvent is the solvent containing dissociable H+, such as fluohydric acid gas.The molecule of such solvent can be given Go out H+ (proton).On the contrary, aprotic solvent can not give hydrogen bond.The total characteristic of proton solvent is display hydrogen bonding, has acid Property hydrogen (although they are probably very weak acid), it is possible to stabilizing ion is (by not sharing free electron to stable cationic, logical Cross hydrogen bond and stablize anion).Example is acetic acid, n-butyl alcohol, isopropanol, normal propyl alcohol, ethanol, methanol, formic acid and water.

Preferably, the organic solvent used in this application is proton or non-proton polarity or non-polar solven.

Preferably solvent is but not limited to:

-one, such as acetone, Ketocyclopentane (CP), Ketohexamethylene (CH), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone (MEK),

-amide, such as DMF (DMF), N-Methyl pyrrolidone (NMP), N-ethyl pyrrolidone, N- Vinyl pyrrolidone, N,N-dimethylacetamide,

-carbamate,

-ether, such as methyl phenyl ethers anisole (AN), oxolane (THF), ethylene glycol, dipropylene glycol, DEGMBE, diethylene glycol Monoethyl ether acetate, DPGME,

-ester, such as ethyl acetate (EA), 1-methoxy-2-propanol acetas (MPA), gamma-butyrolacton (BL), propylene glycol Monoacetate, propylene-glycol diacetate, DPGME,

-ol, such as butoxy ethanol (BC), ethyl cellosolve, butyl cellosolve,

-dimethyl sulfoxide (DMSO),

-halogenated hydrocarbons, such as dichloromethane, chlorobenzene,

-non-polar solven, such as but not limited to hydrocarbon, such as hexane, heptane, toluene, petroleum ether,

Mixture with them.

Preferred solvent is acetone, Ketocyclopentane (CP), Ketohexamethylene (CH), methyl iso-butyl ketone (MIBK) (MIBK), Methylethyl Ketone (MEK), DMF (DMF), N-Methyl pyrrolidone (NMP), N-ethyl pyrrolidone, N-vinyl pyrrole Alkanone, N,N-dimethylacetamide, (AN), and oxolane (THF), ethylene glycol, dipropylene glycol, DEGMBE, diethylene glycol Monoethyl ether acetate, DPGME, ethyl acetate (EA), 1-methoxy-2-propanol acetas (MPA), γ-Ding Nei Ester (BL), Propylene glycol monoacetate, propylene-glycol diacetate, DPGME, dimethyl sulfoxide (DMSO).

Most preferably Ketocyclopentane (CP), Ketohexamethylene (CH), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone (MEK), second Acetoacetic ester (EA), 1-methoxy-2-propanol acetas (MPA), dimethyl sulfoxide (DMSO).

The amount of described reactive or non-reacted additive in the composition is prepared by by described compositions (XX) Film liquid crystalline phase limit, described liquid crystalline phase must be kept.Generally, the amount of described reactive or non-reacted additive is institute State 0.1-50 weight % of compositions, 1-30 weight % of the most described compositions, the most described compositions 1-10 weight %.

In the case of the compositions of the present invention comprises stabilizer, stabilizer is generally with 0.01-5 weight %, preferably 0.1-1 The amount of weight % exists, based on described compositions meter.

Initiator is effectively to measure use for causing the solidification of described compound.Described effective dose depends on technique Parameter and the character of initiation material.Typically, described amount is in the range of 0.1-10 weight %, preferably in 0.5-8 weight % In the range of, more preferably in the range of 1-5 weight %, based on the gross weight of described compositions.Can also use two kinds or The combination of more kinds of initiators (light trigger or thermal initiator).

Preferably liquid crystal polymer of the present invention (I), (Ia) or (Ib) is prepared by compositions, multi-thiol in said composition Thiol group is less than 2, preferably in the range of about 0.005-1, more preferably at 0.001-with the mol ratio of unsaturated carbon-carbon bond In the range of 0.5, most preferably in the range of 0.002-0.5.

Depend on intended purposes, add solvent and be probably favourable.The typical case of the described compositions being placed in solvent is dense Degree between 2 and 50%, preferably between 10 and 40%, with active component such as multi-thiol, liquid crystal and optional polymerization agent, Initiator and the additive weight concentration meter in described solvent.

In another embodiment, the compositions (XX) that the present invention relates to the present invention is used for preparing elastomer, and liquid crystal gathers The application of compound gel, liquid crystal polymer, liquid crystal polymer network or liquid crystalline polymer film.

The compound of the present invention can use method well known to those skilled in the art (such as at Houben-Weyl, Methoden der Organischen Chemie, Thieme-Verlag, Stuttgart or at U.S. Patent number 6630076 Or those methods described in WO 2005/054406) easily prepare.

Different methods can be used for being initially formed liquid crystal film or the liquid of needs by described polymerisable composition (XX) Crystal mesh network.Can use base material such as glass or plastic basis material, described base material can optionally be coated with tin indium oxide (ITO).For Prepare liquid crystal film or network, particularly importantly avoid the formation of defect or inhomogeneities.Accordingly, it is preferred that base material includes glass Glass or plastics, (polyimides such as rubbed or the layer of polyamic acid or the photic of Photoinduced alignment are gathered particularly to include both alignment layers The layer of compound (LPP)) those.Use described layer to allow the homogeneous orientation of liquid crystal compound.Homogeneous orientation can also be passed through Other method known in the art realizes.Described polymerisable composition (XX) is coated on base material and is polymerized.Preferably, institute State the compositions (XXI) of polymerisable coating by photo polymerization, it means that making to use up, preferably UV light makes it solidify, to provide Liquid crystal polymer (LCP) film of crosslinking.Hardening time depends on the reactivity of described polymerizable material among others, the layer of coating Thickness, the type of polymerization initiator and the power of UV lamp.According to the present invention, it is preferably no longer than described hardening time 10 minutes, Particularly preferably it is no longer than 5 minutes, is very particularly preferably shorter than 2 minutes.For producing in enormous quantities, 1 minute or less, very preferably 1 minute or less, particularly 10 seconds or less short hardening time were preferred.After being exposed to light and temperature, described film It it is mechanical resistance.

In the context of the present invention, term " radiation curing " and " photo polymerization " synonymously use.

The method that the invention still further relates to prepare liquid crystal polymer, particularly liquid crystal film or liquid crystal network, the method includes:

Preferably containing aerobic with the amount of 0.1≤oxygen≤50%, more preferably with amount the containing containing aerobic of 1≤oxygen≤25% In oxygen atmosphere, the most in atmosphere,

A) coating composition (XX), wherein said compositions has identical meanings given above and prioritizing selection；So After

B) optionally it is dried, and then

The compositions (XXI) of the described coating obtained after c) being aggregated in step a) or step b), it is preferably film.

Preferably, the present invention relates to method presented above, the most do not use the oxygen barrier layer getting rid of oxygen.

Additionally, it is preferred that the present invention relate to liquid crystal polymer given above, it is to use low UV lamp power and energy system Standby.

Moreover, it relates to the compositions (XXI) of coating, it can be according to processing step a) described above with optional Ground b) obtains.

Usual described compositions is coated with by general coating known in the art and printing process.Coating process is such as to revolve Being coated with, air doctor blade, scratch (blade coating), blade coating (knifecoating), reverse roll coating, transferring roller is coated with, recessed Print roller coat cloth, kiss roll is coated with, and casting is coated with, spraying, slotted opening coating (slot-orifice coating), calendering coating, electricity Deposition (electrodepositing coating), dip-coating or die orifice coating (diecoating).

Printing process is such as: letterpress, such as aniline printing, ink jet printing；Intaglio printing, such as directly intaglio process Brush or offset gravure (offset gravure printing)；Lithographic printing, such as hectographic printing；Or silk screen printing, example Such as screen printing.

Whether it is dried step and depends on the denseness of described compositions.

If described compositions comprises solvent, generally it is dried described compositions after the coating step.

Generally, " being dried " is to extract described solvent, such as, by applying heated air, use and such as pass through Convection current applies described heat and takes away the air stream (convective drying or convection drying) of solvent vapour.It is dried at a higher temperature Comparatively fast；But, the liquid crystalline phase of the compositions (XXI) of described coating must be kept, and which has limited the temperature that can apply, preferably less than Clear point in the compositions (XXI) of described coating.It addition, when determining to be dried applied temperature, it is necessary to Consider product or the quality of film.Other probability is: vacuum drying, is wherein conducted by contact or radiates (or microwave) supply heat Amount, the steam simultaneously produced is removed by vacuum system；Indirectly or contact drying (being heated by hot wall), such as drum dried, Vacuum drying；Dielectric drying (radio frequency or microwave are absorbed in described material)；Lyophilization or lyophilizing；The machinery of solvent carries Take.

The initiator of described reactive and/or non-reacted additive and described compositions is generally before described method With described polymerizable liquid-crvstalline or multi-thiol premixing during or.

In a preferred embodiment in accordance with this invention, described method includes the compositions of coating described in photo polymerization (XXI)。

Described photo polymerization is carried out by radiation.

In the context of the present invention, radiation is polarization or unpolarized light.

The most unpolarized light, but in the embodied case, it is also possible to that applying polarizes or partial polarization, line Property, circle or the light of elliptical polarization.

Generally, lamp is used for photo polymerization.Intensity for the lamp of described irradiation should be preferably above 0.2mW/cm², more preferably Higher than 10mW/cm², most preferably higher than 20mW/cm², particularly most preferably higher than 50mW/cm².Most probable ground, described polyreaction can To be caused by any photochemical light source.Generally, it is aggregated under common room temperature condition and completes.The class that can be used for the present invention is photochemical Just ultraviolet light and by the sun or by artificial light source such as RS type daylight lamp, carbon lamp, xenon arc lamp, mercury vapor lamp, tungsten halogenation The actinic radiation of other form being generally found in the ray that thing lamp etc. sends.If described photo curable polyenoid/polynary sulfur Alcohol composition contains suitable photo polymerization accelerator, and ultraviolet radiation can use most effectively.By suitably selecting ultraviolet light Source, photo polymerization accelerator and its concentration, temperature and molecular weight, and described polymerizable liquid-crvstalline and the reactive base of multi-thiol Group's degree of functionality, can be adjusted to the shortest, and be the most commercially economical hardening time.

Described liquid crystal polymer can also be passed through electron beam (EB) and obtain.This curing is without requiring initiator.

Optionally, described photo polymerization can be in the situation not using light trigger in the way of being similar to Bowman description Under carry out, wherein use have strong transmitting specific UV light source (Bowman et al., Macromolecules 2002,35, 5361-5365), and maleimide can be used as described in EP0618237 to carry out.

The invention still further relates to liquid crystal polymer, preferably formula (I), (Ia) or the liquid crystal polymer of (Ib), it can be by above The inventive method described obtains, and the polymerization especially by the present composition obtains.

Preferably, the present invention relates to liquid crystal polymer, preferably formula (I), (Ia) or the liquid crystal polymer of (Ib), it can pass through Present invention as described above method obtains, and the polymerization especially by the present composition obtains, and premise is not include polymer Scattered liquid crystal.

The invention still further relates to described liquid crystal polymer (I), the liquid crystal film of the compositions (XXI) of described coating or network are in system Application in the standby non-patterned or optics of patterning or photoelectric cell and system (particularly multilayer system) or device.

Optical element, system or device produce, handle or measure electromagnetic radiation.

Photoelectric cell, system or device are run by the optical property being changed material by electric field.Therefore, it relates to electromagnetism Interaction between electricity (electronics) state of (light) and material.

Non-patterned or that pattern optics or photoelectric cell can be used for (but not limited to): waveguide, safety or business Mark protection element, bar code, grating, light filter, delayer (retarder), compensation film, reflective polarizer films, absorbability polarizes Film, anisotropic scattering film, compensate and phase shift films, the phase shift films (twisted retarder film) of torsion, cholesteric liquid Epitaxial, guest of honour's type liquid crystal film, monomer ripple film, smectic liquid crystal film, polariser, piezoelectric battery (piezoelectric cell), aobvious Showing the thin film of nonlinear optical property, ornamental optical element, brightness improves film, the element compensated for wavelength band selectivity, The element compensated for multizone, the element of multi-view angle LCD, achromatic retarder (achromaticretarder), partially Polarization state correction/regulation film, optics or the element of photoelectric sensor, brightness improves the element of film, for the unit of light base telecommunications devices Part, has the G/H-polariser of the patterning of anisotropic absorption device, the reflexive circuit polarizer of patterning, the reflection of patterning Property linear polarization, the MC (monomer ripple film) of patterning.

Preferably safety element, compensator and phase shift films.

Another aspect of the present invention provides optics or photoelectric cell and multilayer system, and its liquid crystal comprising the present invention gathers Compound, liquid crystalline polymer film or network.

Preferably, patterning refers to birefringence patterning and/or the thickness patterning and/or patterning of optic axis orientation, And/or the patterning of the degree of polymerization.Birefringence refers to the difference between the extra-ordinary index of refraction and ordinary refractive index.

The invention still further relates to the liquid crystal polymer of preparation patterning, the particularly method of birefringent film, the method includes figure The compositions (XXI) of polymerisable coating described in case, the most birefringence patterning and/or thickness patterning and/or optic axis The patterning of orientation, and/or the patterning of the degree of polymerization, and further preferably include photo polymerization.

Moreover, it relates to the liquid crystal polymer (I) of patterning, particularly birefringent film, or include such pattern The network of the liquid crystal polymer changed and optical element.

In the context of the present invention, the thin film of the liquid crystal polymer (I) of patterning preferably patterning.

It is highly preferred that the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, the method includes planar Two-dimensional patterned or three dimensional patterned in space, the most described pattern is periodic or acyclic.Three dimensional form is Such as specific surface relief structure (relief structure), that such as tilt or the liquid crystal polymer structures of bending, example Such as lenticule or micro-prism structure.

The method of the liquid crystal polymer (I) of described preparation patterning provides preparation and has specific surface relief structure such as The convenient means of the birefringent film of lenticule or micro-prism structure.

It is highly preferred that patterning refers to the method for the compositions (XXI) of coating described in radiation curing.Most preferably, The present invention relates to the degree of polymerization that patterned by generation and then optionally by rinsing the remaining of described liquid-crystal composition Unpolymerized liquid crystal or component prepare the method for the liquid crystal polymer of patterning, the step bag of the degree of polymerization of described generation patterning Include and make the present composition (XXI) the one or many ground of coating be exposed to radiation by one or more masks, the most parallel Radiation, and/or be exposed to the radiation of scanning beam form.

The degree of polymerization of local can be by the local ratio of unreacted polymerizable groups in liquid-crystal composition after polymerisation The measurement of example quantifies.

Being it desired to realize the high-resolution of described patterning, it is favourable for using parallel radiation.

By radiation-induced polymerization, preferably radical polymerization feasible region selective polymerisation, be wherein coated with by not gathering Close the compositions (XXI) (i.e. wet film) of liquid crystal composition by by planar mask (shadow mask) or gray masks (gray Mask) radiant exposure, and/or utilize flying spot bundle radiant exposure.

In the context of the present invention, polymerization refers to obtain any reaction of polymer according to it.Polymerization is such as Any polyreaction, solidification and cross-linking reaction.Term solidification refers to polymerization.

Especially, most preferably, the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, the method includes In single step of exposure or in multiple step of exposure,

A) by black/white ash or spectral selection mask, or by can reappose between step of exposure black/ White or ash or spectral selection mask, or by the black/white can being replaced between step of exposure or ash or spectral selection Mask；

And/or

B) by the radiation of scanning beam form

It is polymerized the present composition (XXI) of described polymerisable coating.

In the context of the present invention, black/white mask refers to that described mask is by district wholly transmissive for each radiation Territory and the region composition blocked completely.Lycoperdon polymorphum Vitt mask refers to there is also the region of the absorbance with by-level.

It is highly preferred that the method that the present invention relates to the liquid crystal polymer (I) by birefringent patterning preparation patterning.

Birefringent impact can be utilized by process conditions, the compositions (XXI) of described coating to be patterned.Institute State the birefringence in the compositions (XXI) of polymerisable coating or liquid crystal polymer (I) and depend on the order parameter of liquid crystal molecule (order parameter).Described order parameter such as can be gathered by the compositions (XXI) of described polymerisable coating or liquid crystal The temperature impact of compound (I).Therefore temperature on the impact of described order parameter and depends on polymerization to described birefringent impact Degree.Complete unpolymerized liquid-crystal composition shows the birefringence strong dependency to temperature.Along with the degree of polymerization improves, described dependence Property dies down.Therefore, the patterning of the above-mentioned degree of polymerization can be used by making described liquid-crystal composition be exposed to a certain temperature Carry out the patterning of induced birefringence.The birefringent pattern so produced can fix by applying the second polymerization procedure.

Most preferably, the method that the present invention relates to the liquid crystal polymer (I) patterned by birefringent patterning preparation, The method includes

A) compositions (XXI) or the liquid crystal polymer (I) that make described polymerisable coating pass through one or more masks one Secondary or be repeatedly exposed to radiation, and/or one or many is exposed to the radiation of scanning beam form,

With

B) the most at elevated temperatures, preferably at a temperature of the clear point higher than described compositions second gather Close.Hot or photoinduced polymerization is all possible, preferably the combination of the polymerization of photo polymerization or light and heat induction.

Or, birefringent pattern can be produced by being polymerized described film the most under different conditions.Can be The birefringent condition affecting liquid crystal film in patterning polymerization procedure is the temperature of described film, for causing the radiation of described polymerization Intensity, dosage, spectrum, store the atmosphere of described film in the course of the polymerization process.The combination of these conditions is also possible.Described Partial polymerization under different condition can by realizing through the repeatedly radiant exposure of mask that is different or that reappose, or Utilize for causing the flying spot bundle of described polymerization to realize.

Birefringence additionally can utilize the induced reaction art pattern CAD of locally variable.Described radiation is preferably by electromagnetic radiation Composition, is preferably made up of visible ray and/or UV light and/or X-ray and/or electron beam.Described radiation can pass through black/white, ash Or wavelength selectivity mask applies, or applied by beam scanning on birefringent film region.Optionally, described reaction By subsequently or simultaneously applying the temperature of rising and/or can carry out in atmosphere reactive.

Most preferably, the method that the present invention relates to the liquid crystal polymer (I) patterned by birefringent patterning preparation, The method includes by under different process conditions, the most at different temperature；And/or in the radiation for exposure not Same energy (preferably above 1mJ/cm², more preferably at 1mJ/cm²-5J/cm²In the range of), under intensity or spectrum；And/or Under different atmosphere, described polymerizable liquid-crvstalline or polymerizable liquid-crvstalline compositions one or many is made to be covered by one or more Film is exposed to radiation and/or one or many is exposed to the radiation of scanning beam form and produces pattern in terms of the degree of polymerization.

Most preferably, the present invention relates to the use of radiation, compositions (XXI) or liquid crystal by described polymerisable coating are gathered The method of the liquid crystal polymer (I) of the birefringent patterning preparation patterning of compound (I).

Preferably, the radiation for described method represents in the visible and/or electromagnetic radiation of UV and/or x-radiation range And/or particle radiation, such as electronics and/or atom and/or ion and/or molecular radiation, most preferably UV radiates, and thus causes local Variable radiation-induced physically or chemically reaction.Described radiation-induced reaction changes local birefringence.In the present invention one In individual preferred embodiment, described radiation-induced reaction is realized by the change of the degree of polymerization.

In another embodiment of the invention, the one in the described polymerizable liquid-crvstalline compositions (XX) of the present invention Or the component of multiple radiation activatable allows to rely on partial radiation to process the birefringence regulating described liquid-crystal composition.Can spoke Penetrating the component of activation can be that such as can be transformed into a kind of different isomeric forms from a kind of isomeric forms (the most suitable Isomerization) component, depend on by the Local treatment that carries out of radiation.Preferably, the radioactivation process of described patterning is in institute Carry out before stating the polymerization of liquid-crystal composition.For between different isomers switching activation described radiation can by black/ In vain, ash or wavelength selectivity mask are applied or are applied by beam scanning on described liquid crystal combination object area.Optionally, The effect of described radiation can be by heat treatment subsequently or simultaneously or by the storage in particular atmosphere of the described liquid-crystal composition Deposit and improve.Process, according to described partial radiation, the described different isomer produced and affect having in liquid crystal film by different way Sequence, and therefore can realize birefringent local modulation.Preferably, the process of described photoisomerization and described polymerization Initiation separate.Described birefringent pattern can be fixed by causing the polymerization of described liquid-crystal composition subsequently.

The combination of the method for above-mentioned patterned birefringent is also possible.

Most preferably, the present invention relates to the use of the photoisomerization of the present composition (XXI) that radiation is coated with by use The method of liquid crystal polymer (I) of means preparation patterning, the present composition (XXI) of described coating is containing can light isomery The component changed.

Preferably the compound of photoisomerization can comprise N=N, C=C or C=N unit.

Most preferably, the present invention relates to by birefringent patterning or the patterning of the thickness of polymerizable liquid-crvstalline (I) Or the side of the liquid crystal polymer (I) of the patterning preparation patterning of the thickness of the present composition (XXI) of polymerisable coating Method.

This can be come by the part of the original uniform membrane material of regioselectivity removing (preferably rinse or dissolve) Realize.

Generally, such as by sample leaching is removed unpolymerized part in a solvent, or it is aggregated in the temperature of rising Under carry out, polymerization the most subsequently can by photochemistry or/and thermal initiation, preferably exceed described unpolymerized liquid crystal material Clarifying temp at a temperature of cause.In both cases, create and have or the region of high or low optical delay value Digital pattern.In the former case, thickness profile is defined due to the removal of unpolymerized material；In the later case, real Having showed more or less uniform film, its local is birefringent or non-birefringent, or local has or high or low two-fold Penetrate.

Such as, in one embodiment, the degree of polymerization of patterning is produced the most in the first step.? In second step, utilize the liquid-crystal composition of the degree of polymerization described in suitable solvent development with patterning, i.e. use described solvent Rinse described film, or described film is immersed in described solvent.Due to the dissolubility of described material and the material that therefore removes Amount can depend on the degree of polymerization, the pattern therefore pattern of the degree of polymerization translating into film thickness is possible.Use solvent Described developing method can be carried out at elevated temperatures.

For the suitable solvent of described developing method according to the component of the compositions (XXI) of described polymerisable coating and institute State the Comparative dissolution Sexual behavior mode of the liquid crystal film (I) of solidification, and be such as acetone, methyl phenyl ethers anisole, butyl acetate, methacrylic acid fourth Ester, butyl glycol (butyl cellosolve), gamma-butyrolacton, Ketohexamethylene, Ketocyclopentane, diethylene glycol-Anaesthetie Ether, diethylene glycol, Diethylene glycol dimethyl ether (Diglyme), DMF, dipropylene glycol dimethyl ether, DPGME, Dioxane, ethyl acetate, ethyl lactate, ethylene acetate, acetic acid 2-ethoxyethyl group ester, ethyl-3-ethyoxyl-the third Acid-ethyl ester, ethylene glycol, ethanol, 4-hydroxy-4-methyl-2-pentanone, isopropanol, 2-propanol, dichloromethane, methyl ethyl ketone, 4-methyl-2 pentanone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetas, methyl propyl ketone, 1-methyl-2-pyrroles Alkanone, propyl acetate, 2-Pyrrolidone, propylene glycol propyl ether, oxolane, toluene, dimethylbenzene.

Most preferably, the present invention relates to remove polymerizable liquid-crvstalline or polymerizable liquid-crvstalline compositions by regioselectivity Or the method for the liquid crystal polymer (I) of the component of described liquid-crystal composition and/or liquid crystal polymer preparation patterning.

Particularly most preferably, the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, the method includes

The described polymerizable liquid-crvstalline film one prepared by the compositions (XXI) of described coating is made under different process conditions It is secondary or be exposed to radiation by one or more masks in multiple times and/or be exposed to the radiation of scanning beam form,

With

Followed by solvent development, and/or by the temperature polymerizations raised.

The liquid crystal polymer (I) of the degree of polymerization with patterning produced by said method is it can in addition contain by pattern Change, wherein by utilizing the uniform material ablation of particle and/or electromagnetic radiation to realize the layer thickness of patterning.Described particle spoke Penetrating can be by ion, atom, and molecule and/or electronics composition, described electromagnetic radiation can be by IR, it is seen then that UV light or x-ray groups Become.

In another embodiment, for the liquid crystal polymer (I) of homogeneous polymerization, described material ablation is with patterning Mode is carried out.The ablation of described patterning is realized by uneven applying particle and/or electromagnetic radiation.Described uneven applying is led to Cross described birefringence liquid crystal compositions to be exposed by the single or multi-step of one or more black/whites or ash or wavelength selectivity mask Light and/or the beam scanned by applying are realized on described liquid-crystal composition.Described particle radiation can be divided by atom Son, ion and/or electronics composition, described electromagnetic radiation can be by IR, it is seen then that UV light or x-ray composition.

Another method of the film thickness producing patterning is to be selectively deposited on base material by described material area.Institute State and be preferably deposited by printing process and complete.The printing process of typical types is ink jet printing, spin coating, hectographic printing, intaglio process Brush, aniline printing etc..

Another the inventive method for film thickness patterning is the use of regioselectivity manufacturing process, such as impressing, Punching press or method of moulding.Described manufacturing process can be applied in birefringence that is unpolymerized, partially polymerized or that be polymerized completely Film.

The another kind of method of the film thickness of patterned birefringent film is to use lithographic plate printing method.Described lithographic plate printing method May include steps of: coating photoresist, expose by radiation patternization, development step, etching step and strip step.Described Lithographic plate printing method is preferably applied in the birefringent film being partially or completely polymerized.

In order to obtain the patterning of optical delay, birefringence patterning and thickness patterning combination is also possible.

Particularly most preferably, the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, pass through

A) with making the described polymerizable liquid-crvstalline film one or many prepared by the compositions (XXI) of described coating by one Individual or multiple masks are exposed to radiation and/or are exposed to the radiation of scanning beam form,

With

B) followed by uniform particle radiation and/or uniform electromagnetic radiation, preferably with the radiation ablation of patterning by The liquid crystal film of non-homogeneous solidification prepared by the compositions (XXI) of described coating.

It addition, particularly most preferably, the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, pass through

A) regioselectivity ground prints described material area selectivity, and/or

B) regioselectivity ground impressing, punching press or mould described material, and/or

C) material described in offset printing.

Another embodiment of the invention is the method including patterning the optic axis of described liquid crystal polymer (I).

In the case of alignment, by seen from partial polarization and/or UV light, preferably partial linear, circle or ellipse The inclination of the light of polarization or vertical exposure, or the exposure by the inclination of non-polarized light, introduce described orientation function Both alignment layers.

The patterning of described optic axis can realize by means of the both alignment layers of the patterning below liquid crystal film.Described orientation Layer allows to introduce the azimutal orientation of the patterning of optic axis liquid crystal film, or the inclination angle that will be patterned into introduces in institute State both alignment layers and the liquid crystal molecule of the intermembranous interface of described liquid crystal.Depending on the type of both alignment layers, described orientation function is permissible Producing by being exposed to radiation, wherein said radiation can be electromagnetic radiation, particularly visible and/or UV light, or particle spoke Penetrate, particularly atom, molecule, ion and/or electronics.It addition, described orientation such as can be rubbed by the mechanical treatment of both alignment layers Wipe described layer, stretch described layer and/or introduce the groove of submicron in said layer and induce.The function of base material and both alignment layers is permissible It is combined, i.e. depends on that the type of base material, described base material can functionalised itself, with to the liquid being coated on described base material top Epitaxial introduces orientation.The method of all above-mentioned induction orientation functions can also be applied directly to such suitable base material.

In liquid crystal film (I), the another way of patterned optical axle orientation is to use additive, and preferred reactive is added Agent, described additive depends on that their characteristic affects described slant characteristic (tilt profile) and/or azimuth orientation is special Levy (azimuthal alignmentprofile).Such additive be such as convert activation after change they polarity, Their pKa constant, their additive of screw twisted merit (helical twisting power) etc..

The conversion activation of described additive can be exposed to radiation, preferred electromagnetic radiation, more preferably UV and/or visible ray Rear generation.

By be exposed to radiation combined also change environmental condition such as temperature and/or surrounding atmosphere carry out activating also be Possible.

Patterning can by described compound under different reactive additive activation conditions regioselectivity Ground is polymerized each district, or is realized by the patterning activation of the conversion of the most described additive.

The combination of the method for above-mentioned patterned birefringent, film thickness and optic axis orientation is also possible.

Most preferably, the method that the present invention relates to be prepared the birefringent film of the polymerization of patterning by both alignment layers.

Particularly most preferably, the present invention relates to the liquid crystal polymer by preparing patterning with both alignment layers pattern liquid-crystalline (I) method, the display of described both alignment layers tilts and/or azimutal orientation.

Particularly most preferably, the method that the present invention relates to the liquid crystal polymer (I) of preparation patterning, described liquid crystal polymer (I) liquid crystal and additive, preferred reactive additive are comprised；And/or chiral dopant.

In a preferred embodiment in accordance with this invention, additive represents that impact tilts and/or the adding of azimutal orientation Add agent, and chiral dopant represents the chiral dopant preferably with variable torsional work.

Particularly most preferably, the present invention relates to prepare patterning by the combination of method presented above and/or additive The method of liquid crystal polymer (I) of polymerization.

In the context of the present invention, the radiation of patterning refers to the incident illumination that the local being radiated on object changes.

In the context of the present invention, both alignment layers refers to have induce in the liquid crystal layer being coated in described both alignment layers and joins To the layer of function.

In the context of the present invention, chiral dopant is used as additive, is preferably used as reactive additive, its Making described polymerizable liquid-crvstalline film is thermochromism, and thermochromism mode makes the pitch that reflected by said composition and therefore Wavestrip can be selected by variations in temperature, and the color i.e. reflected by described film is partially dependent on temperature when described film is cured Degree (as described in such as US6117920).Described chiral dopant such as can be selected from the n-nonanoic acid cholesteric being available commercially Alcohol ester (CN), CB15, R/S-811, R/S-1011, R/S-2011, R/S-3011 or R/S-4011 (Merck KGaA, Or derive from BASF's Darmstadt)LC756.Be particularly suitable to comprise chirality glycosyl group, have The adulterant of high torsional work, the most double anhydrous hexitol (dianhydrohexitol) derivants, such as Sorbitol, sweet Dew sugar alcohol or the derivant of iditol, the sorbitol derivatives disclosed in highly preferred WO98/00428.Further preferably: GB 2,348, the adulterant comprising benzyleneglycol group disclosed in 207, the chiral binaphthyl base disclosed in WO 02/94805 Derivant, the chirality bis-phenol acetal derivant disclosed in WO 02/34739, chirality TADDOL disclosed in WO 02/06265 is spread out Disclosed in biology, and WO 02/06196 and WO 02/06195, there is at least one fluorination linking group and end or center hands The chiral dopant of property group, and U.S. Patent number 5,250,222, U.S. Patent number 5,411,676, U.S. Patent number 5, 093,027, U.S. Patent number 5,637,255, U.S. Patent number 5,230,828, U.S. Patent number 5,356,559, United States Patent (USP) Chiral dopant disclosed in numbers 5,360,577.

In the context of the present invention, optical delay is by the long-pending definition of the thickness of birefringence and birefringent film.Birefringence quilt The difference being defined as between the extra-ordinary index of refraction and ordinary refractive index.

In the context of the present invention, azimuth alignment direction refers to that the azimuth of abnormal axle takes in the plane of described layer To.It addition, alignment features (profile) refers to azimuth and/or the polarity alignment direction thickness direction along described birefringent film Change, as such as in twisted retarder (retarder).

In the context of the present invention, tilt to refer to the angle between the orientation of membrane plane and liquid crystal molecule, and tilt Feature indicates that described inclination angle changes along the depth direction of described film, and the most in some cases, described slant characteristic can lead to Cross and illustrate average slope angle and approximate.

In the context of the present invention, ' A plate ' refers to utilize the optical delay of the layer of uniaxial birefringent material, described list The abnormal axle of axle birefringent material is parallel to the planar orientation of described layer.

In the context of the present invention, ' C plate ' refers to utilize the optical delay of the layer of uniaxial birefringent material, described list The abnormal axle of axle birefringent material is perpendicular to the planar orientation of described layer.

In the context of the present invention, ' O plate ' refers to utilize the optical delay of the layer of uniaxial birefringent material, described list The abnormal axle of axle birefringent material relative to described layer plane with tilt angular orientation.

Comprise A-, C-and O-plate also referred to as "+A/C/O with positive birefringent, optically uniaxial birefringent material Plate " or " positive A/C/O plate ".Comprise and there is A-, C-and O-plate of negative birefringent, optically uniaxial birefringent material film also It is referred to as "-A/C/O plate " or " negative A/C/O plate ".

In the context of the present invention, term " radiation curing " refers to by radiation-induced polymerization or crosslinking or process.

In a preferred embodiment in accordance with this invention, the liquid crystal polymer (I) of patterning is three-dimensional or two-dimensional pattern The liquid crystal polymer changed.

Additionally, it is preferable that the liquid crystal polymer of patterning, the preferably liquid crystal polymer of formula (I), it can pass through the present invention Method obtain, particularly its can by polymerization, preferably obtained by photo polymerization.

Preferably, the present invention relates to the liquid crystal polymer (I) of the patterning prepared by the compositions (XXI) of described coating.

Preferably, the present invention relates to liquid crystal polymer (I), it has the performance that at least one is lateral patterning, Qi Zhongsuo It can be periodic or acyclic for stating pattern.

" lateral patterning " in above-mentioned definition refers to that the character of described birefringent film becomes in the plane of described film Change.

Described liquid crystal polymer (I) also can be passed through electron beam (EB) and obtain.This curing is without requiring initiator.

Preferably, the present invention relates to optics or photoelectric cell, it comprises the torsion of the liquid crystal polymer (I) containing patterning Delayer film and/or cholesteric liquid crystal film and/or guest of honour's type liquid crystal film and/or smectic liquid crystal film.

Described birefringent film is toleration (resistant) when being exposed to light and temperature, and can be used for system Make device, such as safety element, compensate film, phase shift films, light filter, polariser, grating, waveguide, light cell, piezoelectric battery or display The thin film of nonlinear optical property.Preferably compensate and phase shift films.

Furthermore it is preferred that the present invention relates to the delayer film reversed, it comprises the liquid crystal polymer of the present invention of patterning (I)。

Furthermore it is preferred that the present invention relates to cholesteric liquid crystal film, it comprises the liquid crystal polymer of the present invention of patterning (I).Preferably, described cholesteric liquid crystal film is the A-plate reversed, and display wavelength and polarization selectivity luminous reflectance wherein reflect The wavelength band of light depend on pitch or the pitch gradient of through-thickness, and depend on the two-fold of described liquid crystal polymer (I) Penetrate character.

Furthermore it is preferred that the present invention relates to guest of honour's type liquid crystal film, it comprises the liquid crystal polymer of the present invention (I) of patterning. Preferably, described guest of honour's type liquid crystal film includes the molecule of the anisotropic absorption added, and described molecule is preferably about parallel to Indicator (director) orientation of described liquid crystal.

Preferably, the molecule of anisotropic absorption is for the typically different polarization in about 150-2000nm wave-length coverage The light of state shows different absorbent properties.

The molecule of normally used described anisotropic absorption has carbon-to-carbon, carbon-to-nitrogen or nitrogen-nitrogen double bond.

The molecule of described anisotropic absorption is such as azo dye, anthraquinone, mericyanine, methane, 2-phenylazo Thiazole (2-phenylazothiazole), 2-phenylazobenzthiazole (2-phenylazobenzthiazole), 1,2-bis- Styrene, Isosorbide-5-Nitrae-bis-(2-phenyl vinyl) benzene, 4,4 '-bis-(arylazo) stilbene classes, 4,8-diaminourea- 1,5-naphthoquinone dyestuff, has the ketone part with two aromatic ring conjugation or the diaryl ketone of ketone derivatives, the most substituted hexichol Ketone, benzophenone imines, phenyl hydrazones, and semicarbazone class or cinnamate.

The preparation of the material of anisotropic absorption listed above is it is well known that such as such as Hoffman et al. is in U.S. State's patent No. 4,565,424, Jones et al. at U.S. Patent number 4,401,369, Cole, Jr. et al. at U.S. Patent number 4, 122,027, Etzbach et al. at U.S. Patent number 4, and 667,020, and Shannon et al. is at U.S. Patent number 5, in 389,285 Disclosed.

Preferably the molecule of anisotropic absorption is arylazo, anthraquinone, poly-(arylazo), stilbene and two Aryl ketones derivant and cinnamate.

More preferably arylazo, stilbene, diaryl ketone and cinnamate.

The molecule of described anisotropic absorption can be by covalent bonding in trunk polymer, and they can be as side chain radical Roll into a ball by covalent bonding on main chain, or they can exist in the polymer as the solute of nonbonding.

Polymer such as represents polyacrylate, polymethacrylates, polyimides, polyamic acid, poly-maleimide Amine, poly-2-chloropropene acid esters, poly-2-phenyl acrylate；Unsubstituted or use C₁-C₆The substituted polyacrylamide of alkyl, poly- Methacrylamide, poly-2-chloroacrylamide, poly-2-Phenyl Acrylamide, polyvingl ether, polyvinylesters, polystyrene The straight chain of derivant, polysiloxanes, polyacrylic acid or polymethylacrylic acid or branched alkyl ester；Polyacrylic acid phenoxyalkyl Ester, polymethylacrylic acid phenoxyalkyl ester, there is the polymethylacrylic acid phenylalkyl ester of the alkyl residue of 1-20 carbon atom； Polyacrylonitrile, polymethacrylonitrile, polystyrene, poly-4-methyl styrene or their mixture.

Preferably, the invention still further relates to the non-patterned of the present invention or the optics patterned or photoelectric cell as delay Film and/or compensate film and/or reflective polarizer films and/or absorb polarizing coating and/or the application of anisotropic scattering film, is used for

(a) stable twisted nematic (TN) liquid crystal display, nematic (HAN) liquid crystal display of hydridization orientation, electric control Birefringence (ECB) liquid crystal display, super-twisted nematic (STN) liquid crystal display, birefringence (OCB) liquid crystal of optical compensation Showing device, π-pond liquid crystal display, copline switching (IPS) liquid crystal display, fringing field switches (FFS) liquid crystal display, vertically (VA) liquid crystal display of orientation；All aforementioned display device types are with transmission or reflection or transflector (transflective) mould Formula is applied；

B () produces 3-D view or the display of the image with visual angle change；

(c) safety or trademark protection device；

(d) ornamental optics；

E () brightness improves film；

(f) optical pickocff；

(e) light base telecommunications devices.

Furthermore it is preferred that the present invention relates to monomer ripple film (monomer corrugatedfilm).

Furthermore it is preferred that the present invention relates to comprise the smectic liquid crystal film of described liquid crystal polymer (I).

Smectic liquid crystal film refers to the liquid crystal film of the polymerization in smectic phase, and wherein the liquid crystal molecule in smectic phase removes and has orientation Outer have certain position degree of order the most in one direction.

Furthermore it is preferred that the present invention relates to the stacked body of device given above.

Another embodiment of the invention relates to comprising optics or photoelectric cell, preferred compensation and phase shift films (visual angle, color Displacement (color shift), contrast, grey level's stability (graylevel stability), brightness) device, it is used In:

Safety element,

Wavelength band selectivity compensates: birefringence-compensated film, and it is sub-by the RGB (i.e. red, green and blue) according to liquid crystal display Pixel (subpixels) patterns, and most preferably adapts to the compensatory of respective wavelength band by described sub-pix transmission to provide Matter,

Multizone (such as permeable reflective liquid crystal display device) compensates: have according to the cross directional variations character pattern being compensated device The birefringence-compensated film of the character changed,

The element of multi-view angle LCD: as compensation or the phase shift films of display device, described display is not for Same visual angle provides different images,

The element of three-dimensional liquid crystal display: be used as the compensation of the element of the liquid crystal display of three-dimensional image information is provided or prolongs Film late,

Achromatic delayer: delayer film, different from simple colored delayer, this delayer film is for wider Wavelength band (the most whole visible wavelength range) provides the similar change of polarization state,

Polarization state correction/regulation film: birefringent film, it is used for revising or regulation polarization state, it is therefore an objective to make function energy Enough performances played or improve optics,

Optics or the element of photoelectric sensor, the particularly element of polarization sensitivity/selective sensor,

Brightness improves the element of film,

Safety device or ornamental optics,

For light base telecommunications devices, it is based particularly on the element of the device of polarized light.

Another embodiment of the invention relates to the G/H-polariser with anisotropic absorption agent comprising patterning Device.

Preferably, the G/H-polariser with anisotropic absorption agent of described patterning is thin film polarizer, liquid crystal cell Built-in (in-cell) polariser, safety device or ornamental optics.

Another embodiment of the invention relates to the device of the reflexive circuit polarizer comprising patterning.

Preferably, the reflexive circuit polarizer of described patterning is that brightness improves film, safety device or ornamental optics device Part.

Another embodiment of the invention relates to the device of the reflective linear polarizer comprising patterning.

Preferably, the reflective linear polarizer of described patterning is that brightness improves film, safety device or ornamental optics device Part.

Another embodiment of the invention relates to beam steering optics, and it comprises optics or photoelectric cell, is preferred for The compensation of wavefront modification device and phase shift films.

Another embodiment of the invention relates to the device of MC (the i.e. monomer ripple) film comprising patterning.

Preferably, the monomer ripple film of described patterning is anisotropic scattering film, anisotropic emission body, antireflection Film, has the birefringent film of raising, safety device or ornamental optics.

In the present invention, the most following device: nematic (TN) liquid crystal display of torsion, hydridization Nematic (HAN) liquid crystal display of orientation, birefringence (ECB) liquid crystal display of electric control, super-twisted nematic (STN) liquid Crystal display, birefringence (OCB) liquid crystal display of optical compensation, π-pond liquid crystal display, copline switching (IPS) liquid crystal Show device, fringing field switching (FFS) liquid crystal display, (VA) liquid crystal display of vertical orientation；All aforementioned display device types with Transmission or reflection or transflector model application, they can be used to 3-D view or the display of the image with visual angle change Device；Beam steering optics；Light base telecommunications devices；Optical pickocff；The stacked body of device.

In the present invention, it was discovered that the liquid crystal compound of novel patternable, it is given by simple method and obtains Patterned optical character to two or more different length of delays by way of.This being readily available property is for various application It is all highly useful.

As a result, due to use standard acrylate LCP time for exposure dose and temperature very limited amount of process window Mouthful, described delay patterning method with use described in include having the mercaptan described in the present invention or thio-ether units component, Can the method for LCP material of air curing to compare be extremely difficult.Only have dissolubility contrast (developing method) or postpone right Than trading off and can be conditioned between degree (method with the more than clear point second polymerization) and the resolution of described pattern.Can The LCP mixture of air curing major advantage in terms of patterning is that the exposure dose regulation using and causing the reasonable degree of polymerization exists Polymerization in LCP film and the probability of the transition of non-polymeric interregional good restriction.

Embodiment

Wt% % weight

The photopolymerizable polymer that LPP is linear

LCP liquid crystal polymer

LC liquid crystal

Min minute

Rpm rev/min

FTIR fourier-transform infrared

IR is infrared

T_ANAnnealing temperature

T_cClarifying temp

CP Ketocyclopentane

MIBK methyl iso-butyl ketone (MIBK)

CHN Ketohexamethylene

AN methyl phenyl ethers anisole

LCP (1) 2,5-pair [4-6-acryloxy hexyloxy) benzoyloxy] benzoic acid amyl group ester, it is available commercially Derive from ROLIC Technologies, Switzerland or be similar to U.S. Patent number 5, the route 1,2,3,4 of 593,617 Preparation

LCP (2) has the implication of the liquid-crystal compounds of following formula

LCP (2) can be known by those skilled in the art

Preparation method obtain.Preferably, LCP (2) is obtained by the method described in the embodiment of WO 95/24454.

LCP (3) has the implication of the liquid-crystal compounds of following formula

LCP (3) can be known by those skilled in the art

Preparation method obtain.Preferably, LCP (3) is by described in the route of WO 00,/55,110 1 and 2 and embodiment Method obtain.

LPP has the implication of the polymer of photo polymerization " can linearly ".

In order to prepare LPP both alignment layers, suitable LPP material is such as described in patent publications EP 0611786, WO In 96/10049 and EP 0763552, and include cinnamic acid derivative and ferulic acid derivative.Such as, following LPP material ROP-103 is chosen.

ROP-103 is commercially available alignment material

(ROLIC Technologies, Switzerland).This alignment polymer is based on as photoreactive group Cinnamate.The polymer backbone of described alignment material is acrylic ester type.

Embodiment 1 (compositions M1):

Polymerisable composition M1 preparation is as follows:

It is stirred at room temperature described compositions M1 30wt% solution in Ketocyclopentane 30 minutes.

The preparation of both alignment layers

In order to both alignment layers is spun on base material, ROP-103 is dissolved in Ketocyclopentane with the solid concentration of 2 weight %. It is stirred at room temperature described LPP solution 30 minutes.

Base material (glass baseplate) is with described LPP solution spin coating (1 minute under 2000rpm).It is dried 10 minutes at 180 DEG C After, by sample with from there is optical filter to select the polarized light of the high pressure Hg arc light of 300-330nm spectral region (such as 100mJ/cm², use Schott UG11 and WG 295) irradiate.

Then by the solution of mixture M 1 by spin-on deposition on the base material that this LPP is coated with, and at 39 DEG C anneal 2 points Clock.The clarifying temp of M1 is 44 DEG C.Unpolarized UVA light is used to make described thin film the most photic subsequently Polymerization (500mJ/cm², lamp intensity=50mW/cm², time=10s), to provide tack-free LC film (thickness=2.44 of polymerization μm).Refer to that viscosity (finger tack) is test for sample by touching with forefinger and records the most described sample glues (i.e. viscosity) tests.Described film can be referred to as tack-free (touching dry), although may not be completely crued.

In order to characterize the orientation performance of described liquid crystal material, the polarizing microscope with crossed polarizers is used to measure described The contrast of the liquid crystal layer of crosslinking, described polarizing microscope is further configured with the photodiode for luminous intensity measurement.Described Contrast be calculated as along relative to one of described polariser in 45 ° and 0 ° orientation described crosslinked fluid crystal layers optic axis mensuration The ratio of light intensity.The high-contrast of 4000: 1 confirms the excellent orientation performance of M1.

Use FTIR (ATI Mattson Genesis Series FTIR Spectrometer) for described alkene part Determine chemistry conversion ratio.The layer of 2.65 μ m-thick of described reactive composition is spin-coated on silicon chip.The thickness of described film is last Measure with Tencor alpha-stepper 500.The infrared spectrum of described film is measured before curing with after solidification.At 810cm^-1 Bands of a spectrum (corresponding to C=C-H deformation peak) less affected by overlapping with other bands of a spectrum, be therefore selected for described conversion ratio Measurement.The formula calculating described unsaturated carbon-carbon bond conversion ratio is as follows: conversion ratio (%)=(A₀-A_t)/A₀, wherein A₀And A_t Represent before UV exposes and (500mJ/cm after UV exposure²) at 810cm^-1IR bands of a spectrum.

Described 810cm^-1Bands of a spectrum are relative to as interior target 1510cm^-1Bands of a spectrum (v (Isosorbide-5-Nitrae-C₆H₄) bands of a spectrum of aromatics) normalizing Change.

The conversion ratio of described unsaturated carbon-carbon bond is 68%.

Comparative example 1 (compositions C1)

The preparation of polymerizable liquid-crvstalline compositions C1 is as follows:

Coating is carried out in the way of similar with described in embodiment 1.LC annealing is carried out 2 minutes at 50 DEG C.Ca-M1's is clear Clear temperature is 55 DEG C.Subsequently by described thin film isotropism UVA light photo polymerization (500mJ/ the most in air atmosphere cm², lamp intensity=50mW/cm², time=10s), obtain the film of viscosity.The conversion ratio of described alkene part is the lowest (42%).

Comparative example 2 (compositions C2)

The preparation of polymerizable liquid-crvstalline compositions C2 is as follows:

Coating is carried out in the way of similar with described in embodiment 1.LC annealing is carried out 2 minutes at 43 DEG C.Ca-M1's is clear Clear temperature is 47 DEG C.Subsequently by described thin film isotropism UVA light photo polymerization (500mJ/ the most in air atmosphere cm², lamp intensity=50mW/cm², time=10s), obtain the film of viscosity.The conversion ratio of described alkene part is the lowest (41%).

This embodiment highlights the photoinitiator concentration material impact at air curing aspect of performance.

Comparative example 3 (compositions C1)

The coating of C1 is carried out in the way of similar with described in embodiment 1.LC annealing is carried out 2 minutes at 50 DEG C.M1's Clarifying temp is 55 DEG C.Subsequently by described thin film isotropism UVA light photo polymerization (500mJ/cm in a nitrogen atmosphere², lamp Intensity=50mW/cm², time=10s), obtain the tack-free LC film (thickness=2.57 μm) of polymerization.Turning of described alkene part Rate is 70%.

Comparative example 4 (compositions M1)

The coating of M1 is carried out in the way of similar with described in embodiment 1.LC annealing is carried out 2 minutes at 39 DEG C.Subsequently By described thin film isotropism UVA light photo polymerization (500mJ/cm in a nitrogen atmosphere², lamp intensity=50mW/cm², the time =10s), obtain the tack-free LC film (thickness=2.44 μm) of polymerization.The conversion ratio of described alkene part is 79%.

Embodiment 5 (compositions M2)

Polymerizable liquid-crvstalline mixture M 2 is prepared as follows:

Coating is carried out in the way of similar with described in embodiment M1.LC annealing is carried out 2 minutes at 30 DEG C.The clarification of M3 Temperature is 33 DEG C.Subsequently by described thin film isotropism UVA light at room temperature photo polymerization (500mJ/cm in air atmosphere², Lamp intensity=50mW/cm², time=10s), obtain tack-free LC film (thickness=2.45 μm).The conversion ratio of described alkene part It is 62%.

This example illustrates the reactive additive participating in network and being formed (here for dipentaerythritol five propylene Acid esters) use.

Embodiment 6

Mercaptan structure and the impact of concentration

The preparation of film

Unless otherwise mentioned, following application conditions is used.

In order to both alignment layers be spin-coated on base material, described ROP-103 is dissolved in Ketocyclopentane with the solid concentration of 2 weight % In.Described LPP solution is stirred at room temperature 30 minutes.

Base material (glass baseplate) is with described LPP solution spin coating (1 minute under 2000rpm).It is dried 10 minutes at 180 DEG C After, by sample polarized light (the such as 100mJ/cm from the high pressure Hg arc light with optical filter², spectral region is 300- 330nm) irradiate.

For result below, described LCP compound is as follows, except as otherwise noted.

Described solution is stirred at room temperature 30 minutes, by spin coating (2500rpm-3000rpm, 1min；Average thickness is about 1.20 μm) it is deposited on the base material of this LPP coating, and at T_AN(annealing temperature) anneals 2 minutes.The clarifying temp of described mixture It is T_c(being given in table).Unpolarized UVA light is used to make the photo polymerization the most in air atmosphere of described thin film subsequently (500 or 1000mJ/cm², lamp intensity=60mW/cm²), to provide the LC film of polymerization.Refer to that viscosity is by touching tested with forefinger Sample and record described sample and the most how to glue (i.e. viscosity) and test.Orientation performance and chemical conversion rate the most above institute State mensuration.

Table (I)

Embodiment 7

The additive impact on curing performance

The preparation of film

With described LPP solution spin coating (1 minute under 2000rpm) base material (glass baseplate).It is dried 10 minutes at 180 DEG C After, by sample polarized light (the such as 100mJ/cm from the high pressure Hg arc light with optical filter², spectral region is 300- 330nm) irradiate.

Except as otherwise noted, described LCP compound is as follows:

Described solution is stirred at room temperature 30 minutes, by spin coating (2000rpm-3000rpm, 1min；Average thickness is about 1.20 μm) it is deposited on the base material of this LPP coating, and at T_AN(annealing temperature) anneals 2 minutes.The clarifying temp of described mixture It is T_c(being given in table).Unpolarized UVA light is used to make the photo polymerization the most in air atmosphere of described thin film subsequently (500 or 1000mJ/cm², lamp intensity=60mW/cm²), to provide the LC film of polymerization.Refer to that viscosity is by touching tested with forefinger Sample and record described sample and the most how to glue (i.e. viscosity) and test.Orientation performance and chemical conversion rate the most above institute State mensuration.

Embodiment 8

LCP " alkene " part and the degree of functionality impact on curing performance

The preparation of film

Explanation

A Al.p. P √ 0 ++ + 0

Can air curing Orientation performance Multi-thiol (weight %) Can air curing Can not air curing Extraordinary contrast (＞ 500) Good contrast (＜ 500) Without contrast

Embodiment 9

Have studied the art methods (Journal of SID 12/3,2004) described by Philips, with the present invention Method compare.In order to reappear the result of described prior art, employ the acrylate polymerizable LC mixture of standard (composition as listed is in Table A), and being aggregated in nitrogen atmosphere of patterning carry out.In order to prevent region wide (area-wide) Polymerization, the least exposure energy must be used according to the description of described prior art.

It is prepared for 4 samples according to the process conditions listed in table B.Washed D263 glass plate is used as base material. By ROP-103 (the alignment material of ROLICTechnologies) that spin coating solid content is 2 weight % in Ketocyclopentane Solution, is prepared for dry thickness and is of about the both alignment layers of 60nm.Described both alignment layers subsequently by hot plate at a temperature of 180 DEG C heat Process 10 minutes.Then, make described alignment layer be vertically exposed to linear polymerization UVB light (wavelength 280 and 320nm it Between).With 3mW/cm²Intensity apply 150mJ/cm²Dosage.In the next step, will according to Table A (a), standard based on The polymerisable liquid crystal compound of acrylate is spin-coated on above the alignment layer of described functionalization.Use in methyl phenyl ethers anisole for this 25 weight % solution.Realize the build of about 800nm by this way.Then carry out on hot plate at a temperature of 40 DEG C Heat treatment 10 minutes.Then, the radiation curing patterned is carried out.To this end, make described film by having 100 microns of bar patens Black and white mask be exposed to collimated light.Described mask is maintained at the distance on about 15 microns of the surface away from described liquid crystal layer.Logical Mask described in transmission from one meridian to another with 1,5,10 and 500mJ/cm²UV dose exposure carry out polymer sample.Then, carry out developing process, will Described sample is immersed in ethyl acetate 10 seconds, to remove unpolymerized material.Fig. 1 shows employing 1mJ/cm in blanket of nitrogen² The thickness profile (Alpha-stepper 500, KLA-TencorCorporation) of measurement of sample of dosage polymerization, Fig. 2 Show employing 10mJ/cm in blanket of nitrogen²The thickness profile of sample of dosage polymerization, and Fig. 3 shows in blanket of nitrogen Use 500mJ/cm²The thickness profile of sample of dosage polymerization.

The most described patterning also works according to art methods.But, two basic shortcomings are apparent :

(1) if polymerization dosage increase, lateral resolution reduces (1mJ/cm²: with and without the mistake between the district of LCP Crossing district is 7 microns；5mJ/cm²: 30 microns of transition regions；10mJ/cm²: 45 microns of transition regions), for 500mJ/cm², unexposed area In the degree of polymerization of material be too high and in developing process to completely remove described material, and

(2) if polymerization decrease in dose, then dissolubility contrast is at a fairly low, the non-event of material of the most considerable fraction of polymerization It is dissolved (1mJ/cm to meaning²: residual thickness 600nm；10mJ/cm²: residual thickness: 800nm).

Therefore, the method only allows regulation compromise between the lateral resolution of dissolubility contrast and pattern.

Another sample is prepared according to the present invention.Use previously described identical method.But, use containing mercaptan list The liquid crystal compound of unit replaces the acrylic ester compound thing of described standard.The component of described mixture indicates in Table A (b).For Carry out the exposure patterned, use 500mJ/cm²UV dosage.In this case, developing process is in the exposure of described sample Region only results in the least material unaccounted-for (MUF) (＜ 5%), and at the quilt in developing process of material described in unexposed area Completely remove, i.e. dissolubility contrast is the highest.And, lateral resolution is the highest (transition region is 5 microns), and And the much lower dependency that display is to actual processing conditions.The thickness profile of described sample shows in the diagram.Technological parameter exists Table C indicates.

Table A: the component of polymerizable liquid-crvstalline mixture

The acrylate mixture of (a) standard:

(b) acrylate/mercaptan mixture:

Table B: for the technological parameter of the acrylate mixture of standard

Base material:	Washed D263 glass (Schott AG)
		Both alignment layers:
Material:	ROP-103 (alignment material derives from ROLIC Technologies)
		Solution:	2%, in Ketocyclopentane
Spin coating:	The 2000rpm60 second
		Heat treatment:	180 DEG C 10 minutes, on hot plate
LPUV exposes:	150mJ/cm²(UVB), 3mW/cm²
		Polymerizable liquid-crvstalline material:
Material:	The acrylate mixture (Table A (a)) of standard, T_c≈55℃
		Solution:	25%, in methyl phenyl ethers anisole
Spin coating:	The 800rpm60 second
		Heat treatment:	40 DEG C 10 minutes, on hot plate
The radiation curing of patterning:	1,5,10 and 500mJ/cm²(UVA and UVB), 8mW/cm², collimated light
		(a) developing method:	Sample be immersed in ethyl acetate bath in about 10 seconds
(b) second spoke at elevated temperatures Penetrate solidification:	500mJ/cm²(UVA and UVB), 50mW/cm², non-collimated light Without the second radiation curing exposure of mask, in atmosphere Temperature: ≈ 60 DEG C, is applied through hot plate

Table C: for the technological parameter of acrylate/mercaptan mixture.

Base material:
		Both alignment layers:	Identical with table B
Polymerizable liquid-crvstalline material:
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	500mJ/cm²(UVA and UVB), 8mW/cm², collimated light, In air atmosphere
(a) developing method:	Identical with table B
		(b) second spoke at elevated temperatures Penetrate solidification:	Identical with table B

Embodiment 10

Method is according to embodiment 9, and premise is not carry out developing method, but in the clarification higher than unexposed LCP region The second polymerization (parameter indicates in table B) is applied at a temperature of Dian.

Using the acrylate material of described standard, the restriction to low exposure dose causes such problem, is i.e. only capable of reality The least between exposure area with the degree of polymerization of the unexposed area existing difference the least difference of clear point (and therefore).Cause This, it is very difficult on the described region of described sample, control temperature with enough degree of accuracy so that unexposed region Temperature is still below described clear point just above described clear point and described partially polymerized region.

If described first exposure, the patterned exposure of the acrylate LCP film of the most described standard uses 10mJ/cm²'s Dosage is carried out, and resolution has significantly reduced compared with the situation using lower dosage.But on the other hand, exposing and do not exposing The contrast of the interregional clear point of light has been sizable.However it has been found that between the unexposed striped reduced and exposure striped Contrast.In the case of being aggregated in carry out at a temperature of 50 DEG C described second, find residual in described unexposed striped Remaining birefringence, it is isotropic by inference.If applying lower exposure dose such as 5 or 1mJ/cm²To improve described horizontal stroke To resolution, this shortcoming becomes even more to highlight.

For the described polymerizable liquid-crvstalline mixture containing mercaptan, it is possible to achieve the highest exposure and unexposed area Between the contrast of clear point.The 2nd UV exposure the most at elevated temperatures easily provides has birefringent region The region of exposure (in the patterning polymerization process of the described first step) and not there is the region of any residual birefringence (described The region not exposed in the patterning polymerization process of the first step).

As a result, due to use standard acrylate LCP time for exposure dose and temperature very limited amount of process window Mouthful, use that include there is the component of mercaptan or thio-ether units, can the delay patterning method of LCP material of air curing be phase When readily, and cause the most preferably resolution.Only have dissolubility contrast (developing method) or delay contrast (has The method of the second more than clear point polymerization) and the resolution of described pattern between compromise can be conditioned.Can air curing LCP mixture major advantage in terms of patterning is that the exposure dose using and causing the reasonable degree of polymerization regulates in LCP film The probability of the transition of polymerization and non-polymeric interregional good restriction.

Embodiment 11: contain the polymerizable liquid of thiol component at the upper patterning of plastic basis material i.e. cellulose triacetate (TAC) The method of brilliant compound

Processing conditions is listed in table D.

The thickness profile measured after development confirms that described patterning method works in a preferred manner.

Table D: processing conditions: the patterning on plastic basis material TAC

Base material:	There is the TAC (cellulose triacetate) of solvent barrier
		Both alignment layers:
Material:	ROP-103 (alignment material derives from ROLIC Technologies)
		Solution, spin coating:	2%, in MEK, the 2000rpm60 second
Heat treatment:	60 DEG C 10 minutes, on hot plate
		LPUV exposes:	150mJ/cm²(UVB), 3mW/cm²
Polymerizable liquid-crvstalline material:
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	500mJ/cm²(UVA and UVB), 8mW/cm², collimated light In air atmosphere
(a) developing method:	Sample is rinsed about 10 seconds by ethyl acetate

Embodiment 12: as the patterning polymerisable liquid crystal compound containing thiol component on the silicon wafer of base material.

Processing conditions is listed in table E.

Table E: processing conditions: patterning on silicon

Base material:	Si wafer
		Both alignment layers:
Material:	ROP-103 (alignment material derives from ROLIC Technologies)
		Solution, spin coating:	2%, in Ketocyclopentane, the 2000rpm60 second
Heat treatment:	180 DEG C 10 minutes
		LPUV exposes:	150mJ/cm²(UVB), at 3mW/cm²Under
Polymerizable liquid-crvstalline material:
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	500mJ/cm²(UVA and UVB), 8mW/cm², collimated light In air atmosphere
(a) developing method:	Sample is rinsed about 10 seconds by ethyl acetate

Embodiment 13: the polyimide layer rubbed by use makes the polymerisable liquid crystal compound containing thiol component join To patterning

First, by polymerizable liquid-crvstalline compound orientation, and carry out patterning method subsequently.Processing conditions is listed in table F In.Perfect orientation can be realized by the method.The thickness profile measured after development confirms that described patterning method is with excellent The mode of choosing works.

Table F: processing conditions: there is rubbed polyimides as the patterning on the glass of both alignment layers

Base material:	Washed D263 glass
		Both alignment layers:
Material:	Nissan SE-150
		Spin coating:	The 2000rpm60 second
Heat treatment:	80 DEG C 15 minutes, 250 DEG C 50 minutes
		Friction treatment
Polymerizable liquid-crvstalline material:
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	500mJ/cm²(UVA and UVB), 8mW/cm², collimated light In air atmosphere
(a) developing method:	Sample is immersed in ethyl acetate bath in about 10 seconds

Embodiment 14: the TAC base material rubbed by use come that orientation is coated directly onto on TAC base material containing thiol component The patterning of polymerisable liquid crystal compound

First, by polymerizable liquid-crvstalline compound orientation, and carry out patterning method subsequently.Processing conditions is listed in table G In.Perfect orientation can be realized by the method.The thickness profile measured after development confirms that described patterning method is with excellent The mode of choosing works.

Table G: processing conditions: the patterning on rubbed TAC base material

Base material:	TAC (cellulose triacetate)
		Both alignment layers:
Material:	Without extra play
		Friction treatment
Polymerizable liquid-crvstalline material:
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	500mJ/cm²(UVA and UVB), 8mW/cm², collimated light In air atmosphere
(a) developing method:	Sample is immersed in ethyl acetate bath in about 10 seconds

The method of the pattern of the length of delay (isotropism or certain Δ nd) that embodiment 15: two or three is different

The stacked body of the liquid crystal layer (is to be patterning uniformly with) of two polymerizations is applied according to reality The binary executing example 15 postpones patterning method, and two kinds of different length of delays can be conditioned (delay of ground floor and ground floor Postpone to add the delay of the second layer).In this embodiment, it is not required that additional alignment layer, because described additional LCP can pass through The following direct orientation of the LCP layer being uniformly directed.

But, the additional alignment layer for described second liquid crystalline polymer layer brings additional degree of freedom, its example As allowed to regulate three kinds of different length of delays, if described alignment layer is LPUV exposure in a patterned manner, with choosing Shift to selecting property 0 ° and 90 ° orientation of optic axis to liquid crystal molecule atop.Described three kinds of different length of delays are by such as Lower means are given: the delay of a LCP, and the delay of a LCP adds the delay of the second layer, and the delay of a LCP subtracts the second layer Delay.The method represents digital delay patterning and the combination of azimutal orientation patterning in double LCP layer methods.

The digital delay patterning diagram of combination is patterned in Figure 5 with the azimutal orientation of the second LCP layer.With in Fig. 5 Description contrast, patterned the azimutal orientation and then of the first LCP layer by the alignment of the patterning of LPP1 The delay of the second LCP layer patterning uniform orientation is also possible.In this way, it is also possible to regulate three kinds of different prolonging Value late.It addition, described first LCP layer can have the variable azimutal orientation having identical optical delay level.If it is described The value of the azimutal orientation of patterning is not restricted to 0 ° and 90 °, can regulate the different local more than three kinds or four kinds double Refractive properties.The additional delay of the Photoinduced alignment of patterning and the second layer by allowing two LCP layer patterns, described from It is further augmented by degree.In the case of described film the most developed (i.e. part remove), if or described film developed but Covering with planarization (planarization) layer subsequently, the patterning of the delay of two LCP layer is also possible.

Use the method for development in ethyl acetate and be described in unexposed area according to the processing method in table 8 and 9 Clear point more than polymerization method be prepared for sample.

Table H: processing conditions: there is the delay patterning of two LCP layer: the orientation of the second LCP layer is perpendicular to ground floor Orientation

Base material:	Washed D263 glass
		Both alignment layers: ground floor
Material:	ROP103 (alignment material, derive from ROLIC)
		Solution, spin coating:	2%, in Ketocyclopentane, the 2000rpm60 second
Heat treatment:	180 DEG C 10 minutes
		LPUV exposes:	150mJ/cm²(UVB), 3mW/cm²
Polymerizable liquid-crvstalline material: ground floor
		Material:	The acrylate mixture (Table A (a)) of standard, T_c≈55℃
Solution, spin coating:	40%, in methyl phenyl ethers anisole, the 1000rpm60 second

Heat treatment:	40 DEG C 10 minutes, on hot plate
		Radiation curing:	5J/cm²(UVA and UVB), 50mW/cm², non-collimated light, without covering Film, in nitrogen atmosphere
Both alignment layers: the second layer
		Material:	ROP103 (alignment material derives from ROLIC)
Solution, spin coating:	2%, in Ketocyclopentane, the 2000rpm60 second
		Heat treatment:	180 DEG C 10 minutes
LPUV exposes:	150mJ/cm²(UVB), 3mW/cm², it is perpendicular to the first both alignment layers and joins To
		Polymerizable liquid-crvstalline material: the second layer
Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
		Solution, spin coating:	25%, in methyl phenyl ethers anisole, the 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	1J/cm²(UVA and UVB), 8mW/cm², collimated light, at air gas In atmosphere
(a) developing method:
			Sample is immersed in ethyl acetate bath in about 10 seconds
(b) second spoke at elevated temperatures Penetrate solidification:
		Radiation curing:	500mJ/cm²(UVA and UVB), 50mW/cm², non-collimated light Second radiation curing exposes without mask, in atmosphere
Temperature:	≈ 60 DEG C, utilizes hot plate to apply

In one example, use the second alignment layer, prepare this second alignment layer to induce first and second The vertical optic axis (table H) of liquid crystalline polymer layer.In this embodiment, the observed result of the sample between crossed polarizers shows Corresponding to the darker area by the delay given by the difference between the delay level of said two LCP film, with corresponding to only described The brighter areas of the delay of (the most non-patterned) liquid crystalline polymer film uniformly.

In second example, between said two liquid crystalline polymer film, do not use additional alignment layer (Table I). Therefore, the liquid crystalline polymer film of described second patterning is parallel to described first polymeric film orientation.Orthogonal polariser it Between observed result show, create the relatively Gao Yan with two length of delay sums corresponding to said two liquid crystalline polymer film The region of slow value and the relatively low length of delay of the length of delay having corresponding to only following non-patterned liquid crystalline polymer film Region.

Additionally determine if the alignment direction of the second layer utilizes the LPUV of the patterning of alignment layer to expose (0 ° or 90 °) Justice, it is possible to achieve there is the film of the arbitrary graphic pattern of three kinds of different optical delay values.

Table I: processing conditions: there is the delay patterning of two LCP layer: the orientation of the second LCP layer is perpendicular to ground floor Orientation.

Base material:	Washed D263 glass
		Both alignment layers:
Material:	ROP103 (alignment material, derive from ROLIC)
		Solution, spin coating:	2%, in Ketocyclopentane, the 2000rpm60 second
Heat treatment:	180 DEG C 10 minutes
		LPUV exposes:	150mJ/cm²(UVB), 3mW/cm²
Polymerizable liquid-crvstalline material: ground floor
		Material:	The acrylate mixture (Table A (a)) of standard, T_c≈55℃
Solution:	40%, in methyl phenyl ethers anisole
		Spin coating:	The 1000rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		Radiation curing:	5J/cm²(UVA and UVB), 50mW/cm², non-collimated light, without mask, In nitrogen atmosphere
Polymerizable liquid-crvstalline material: the second layer
		Material:	Acrylate/mercaptan mixture (Table A (b)), T_c≈44℃
Solution:	30%, in methyl phenyl ethers anisole
		Spin coating:	The 1000rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	1J/cm²(UVA and UVB), 8mW/cm², collimated light, in air atmosphere
(a) developing method:	Sample is immersed in ethyl acetate bath in about 10 seconds
		(b) second spoke at elevated temperatures Penetrate solidification:	500mJ/cm²(UVA and UVB), 50mW/cm², non-collimated light Temperature: ≈ 60 DEG C, utilizes hot plate to apply

Embodiment 16: use the delay patterning of Lycoperdon polymorphum Vitt mask radiation curing

Allow patterned retardation to the straightforward procedure of two or more different length of delays for various application all It is highly useful.Due to the benefit mentioned above of described acrylate/mercaptan patterning method, there is variable delay value The several methods of such patterning is feasible.

A kind of probability is to use gray level mask, and the local pattern of its transmitted radiation intensity is to the liquid crystal being polymerized Monomer film.The intensity pattern so produced causes the pattern of the degree of polymerization in described sample area.For shifting the described degree of polymerization The first method of the pattern pattern that becomes optical delay be to carry out the second radiation curing at elevated temperatures.Depend on polymerization Degree, the optical delay in each part (partition) of described film will reduce a certain amount.The region of strong polymerization will be aobvious Show the least reduction, and the region of weak polymerization will experience sizable reduction or lose optical delay completely.In order to allow Regulating described desired optical delay value, the method requires precise control of temperature and accurately regulates institute in described sample area State the probability of temperature.

Further possibility is that the film utilizing gray level mask to be polymerized that the leaching of described film developed in a suitable solvent.? In this example, LCP material will be removed according to partial polymerization degree, and therefore shows the pattern of optical delay.

The present embodiment includes described second method.The technological parameter of application is listed in table J and K.Each sample is by four Region forms, and described region uses different exposure dose polymerization specified in table J.It is aggregated in nitrogen atmosphere described In the case of row, described patterning method is invalid.But using acrylate/thiol material, described patterning method is imitated Fruit is very well.Four kinds of different delay levels can be conditioned.Value including the exposure dose of described acrylate/mercaptan mixture Shown in figure 6 at interior described sample with the value of optical delay.Described result shows, with it, described delay can With by the intermittent pattern with non-constant width.Depending on application, the post polymerization method after described developing method is probably needs, To improve Bulk polymerization degree.

Table J: processing conditions: use the delay patterning of Lycoperdon polymorphum Vitt mask radiation curing: the acrylate liquid crystal of standard is polymerized Thing material

Base material:	Washed D263 glass
		Both alignment layers: ground floor
Material:	ROP103 (alignment material, derive from ROLIC)
		Solution, spin coating:	2%, in Ketocyclopentane, the 2000rpm60 second
Heat treatment:	180 DEG C 10 minutes
		LPUV exposes:	150mJ/cm²(UVB), mW/cm²
Polymerizable liquid-crvstalline material: the second layer
		Material:	The acrylate mixture (Table A (a)) of standard, T_c≈55℃
Solution:	25%, in methyl phenyl ethers anisole
		Spin coating:	The 800rpm60 second
Heat treatment:	40 DEG C 10 minutes, on hot plate
		The radiation curing of patterning:	1J/cm², 6,1 and 0mJ/cm²(UVA and UVB), 8mW/cm², Collimated light, in atmosphere
(a) developing method:	Sample is immersed in ethyl acetate bath in about 10 seconds

Table K: processing conditions: use the delay of Lycoperdon polymorphum Vitt mask radiation curing to pattern: acrylate/mercaptan mixture

The same process conditions be given in table J, premise is to use described acrylate/mercaptan mixing Thing (Table A (b)), and in order to carry out the radiation curing patterned, use air atmosphere generation For nitrogen atmosphere

Claims

1. photo polymerization, patterning or non-patterned liquid crystal polymer, the thio-ether units of its contained (Ia)

(Ia)

Wherein

LC¹, LC²And LCⁱIt is liquid crystal residue independently of one another,

Wherein

Wherein said liquid crystal residue is the polymerized form of liquid crystal, and this liquid crystal has a lower formula (VII):

Wherein:

-A¹And A²It is compound formula V independently of one another:

P-(Sp)_k-(X)_t- (V)

Wherein

P is selected from lower group: vinyl ethers, allyl ether, propenyl ether, alkene, alkynes, and undersaturated ester；

Sp represents C_1-13Alkylidene group, it is unsubstituted or with alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, Hydroxyl, nitro is substituted, and wherein one or more-CH₂-group is optionally selected from the hetero atom of oxygen, sulfur and nitrogen and substitutes；

X represents-O-,-CO-,-COO-,-OCO-or-C=C-；

K is the integer of the value with 0-4,

T is the integer of the value with 0 or 1；And/or

-A⁷It is hydrogen, nitro, cyano group, halogen, methyl group, or above-mentioned group P；

-C¹, C²And C³It is unsubstituted benzene, phenylene, biphenylene or sub-terphenyl independently of one another, or by halogen, hydroxyl Base, nitro, cyano group, carboxyl, acryloxy, alkyl acyloxy, alkoxyl, alkane carbonyloxy group, alkyl oxy carbonyl oxygen, methyl-prop Alkene acyloxy, vinyl, vinyl epoxide and/or the substituted benzene of allyloxy, biphenylene, phenylene, sub-terphenyl, on State the alkyl residue in the group containing alkyl and there is 1-10 carbon atom；

-Z¹And Z²It is-COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound；If Z¹And Z²One of be singly-bound, So another Z is-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH-；

Or described liquid crystal has a lower formula (VIII):

Wherein:

-A¹, A², A⁵, A⁶It is compounds residues formula (V) defined above independently of one another；

-C¹, C^1′, C², C^2′, C³And C^3′It is unsubstituted benzene, phenylene, biphenylene or sub-terphenyl independently of one another, or Person is by halogen, hydroxyl, nitro, cyano group, carboxyl, acryloxy, alkyl acyloxy, alkoxyl, alkane carbonyloxy group, alcoxyl carbonyl Epoxide, methacryloxy, vinyl, vinyl epoxide and/or the substituted benzene of allyloxy, biphenylene, phenylene, Asia Terphenyl, the alkyl residue in the above-mentioned group containing alkyl has 1-10 carbon atom；

-Z¹, Z^1′, Z²And Z^2′It is-COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound；

-a1, a2, a1 ' and a2 ' are the integer of 0 to 3 independently of one another so that 1≤a1+a2≤a3 and 1≤a1 '+a2 '≤3；

-B¹Comprise the group of formula (VI):

(X⁴)_t2-(Sp²)_k2-(X⁵)_t3 (VI)

Wherein:

Sp²Represent C_1-20Alkylidene group；

X⁴And X⁵Expression-O-,-S-,-NH-,-N (CH independently of one another₃)-,-CH (OH)-,-CO-,-CH₂-CO-,-SO-,-CH₂- SO-,-SO₂-,-CH₂-SO₂-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-CH₂- CH₂-,-OCH₂-,-CH₂O-,-CH=CH-,-C ≡ C-or singly-bound；

K2 is integer, has the value of 0 or 1；

T2 and t3 is integer, has the value of 0 or 1 independently of one another；

Premise is that oxygen atom is not connected to each other；

X¹And X²It is aliphatic organic residue independently of one another,

n¹And n²It is >=the integer of 0,

R is >=integer of 0,

m¹, m²And m³It is >=the integer of 0 independently of one another,

Q is 0 or 1；

Premise is, if q is 0, then LC²And LCⁱIt is connected directly to one another；If with n¹And n²It is 0, then at least one m¹, m² Or m³It is ＞ 0, and if m¹, m²And m³It is 0, then at least one n¹And n²It is ＞ 0；With

It is prepared in oxygen-containing atmosphere in the case of not using cation light initiator；

Premise is not include the scattered liquid crystal of polymer and cholesteric crystal.

2. the liquid crystal polymer described in claim 1, wherein P is selected from lower group: vinyl esters, allyl ester, acrylate and first Base acrylate.

3. the liquid crystal polymer described in claim 1, the residue of wherein said liquid crystal is the polymerized form of liquid crystal, its unpolymerized shape Formula has at least two and has the polymerizable functional group of undersaturated carbon-to-carbon or carbon-nitrogen bond.

4. compositions (XX), it comprises:

A) multi-thiol of at least one formula (IX)

Wherein

X^aIt is aliphatic organic residue,

Nt is >=integer of 2, and

B) formula (VII) described at least one claim 1 or the liquid crystal of formula (VIII),

C) a kind of reactive and/or non-reacted additive,

D) optionally at least a kind of initiator, and

E) optionally at least a kind of solvent.

5. the method for preparation liquid crystal polymer described in claim 1, the method includes

A) coating compositions (XX) described in claim 4, and then

B) optionally it is dried, and then

C) in oxygen-containing atmosphere, it is aggregated in the compositions (XXI) of the described coating obtained after step a) or step b).

6. the compositions (XXI) of coating, it according to the processing step a) described in claim 5 and b) can obtain.

7. liquid crystal polymer, it can obtain in accordance with the method for claim 5.

8. the method for liquid crystal polymer of preparation patterning, the method includes described in claim 6 and according to claim 5 Compositions (XXI) patterning of the coating of described preparation.

9. the method described in claim 8, including birefringence patterning and/or the thickness patterning and/or figure of optic axis orientation Case and/or the patterning of the degree of polymerization.

10. the method described in claim 8 or 9, including photo polymerization.

The liquid crystal polymer of 11. patternings, it can be obtained by the method described in claim 8-10.

Described in 12. claim 1 or 7 or according to the liquid crystal polymer of preparation described in claim 5, or described in claim 4 Compositions (XX), or the compositions (XXI) of the coating described in claim 6, or the liquid crystal of the patterning described in claim 11 Polymer purposes in preparation patterning and non-patterned optics or photoelectric cell, system or device.

The 13. non-patterned or optics of patterning or photoelectric cell, system or devices, its comprise described in claim 1 or 7 or by According to the liquid crystal polymer of preparation described in claim 5, or the liquid crystal polymer of the patterning described in claim 11, or right will Seek the liquid crystal polymer of patterning described in 8-10.

Non-patterned or the optics of patterning or photoelectric cell described in 14. claim 13 are protected for waveguide, safety or trade mark Protection element, bar code, grating, light filter, delayer, compensate film, reflective polarizer films, absorb polarizing coating, anisotropic scattering film Compensate and phase shift films, the delayer film of torsion, cholesteric liquid crystal film, guest of honour's type liquid crystal film, monomer ripple film, smectic liquid crystal Film, polariser, piezoelectric battery, brightness improves film, the element compensated for wavelength band selectivity, the element compensated for multizone, The element of multi-view angle LCD, achromatic retarder, polarization state correction/regulation film, optics or the element of photoelectric sensor, bright Degree improves the element of film, for the element purposes of light base telecommunications devices.

Non-patterned or the optics of patterning or photoelectric cell described in 15. claim 13 are used for showing nonlinear optical property The purposes of thin film.

Non-patterned or the optics of patterning or photoelectric cell described in 16. claim 13 are used for having anisotropic absorption agent The G/H-polariser of patterning, the reflecting circular polariser of patterning, the reflective linear polarizer of patterning, the monomer of patterning The purposes of ripple film.

Non-patterned described in 17. claim 13 or the optics of patterning or photoelectric cell are for the use of ornamental optical element On the way.

18. comprise the non-patterned or optics of patterning described in claim 13 or the device of photoelectric cell.