CN101636469A

CN101636469A - Patternable liquid crystal polymer comprising thio-ether units

Info

Publication number: CN101636469A
Application number: CN200780047888A
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: 2010-01-27
Anticipated expiration: 2027-12-11
Also published as: CN101636469B

Abstract

The present invention relates to a photo-polymerized, patterned or unpatterned liquid crystal polymer, especially a liquid crystal polymer film or a liquid crystal polymer network, comprising thio-ether units of formula (I): * covalent bond, which links the unit of formula (I) to the residue of the polymer wherein LC<1> is selected from the group of liquid crystal residues, X<1> is selected from the group of aliphatic organic residues, and n<1> is an integer = 0 and m<1> is an integer =O; with the proviso that if n<1> is 0, then m<1> is >0, and if m<1> is 0, then n<1> >0; which is prepared in an atmosphere containing oxygen, preferably with an amount of 0.1 = oxygen = 50%, more preferably 1 = oxygen = 25%, most preferably in air; with the proviso that polymer dispersed liquid crystals are excluded. Further, this inventiorr relates to a composition used for the preparation of that photo- polymerized liquid crystal polymer of the invention, to processes of the preparation of that liquid crystal polymer and to its use.

Description

The liquid crystalline polymers that comprises the patternable of thio-ether units

The present invention relates to photopolymerization, patterning or the liquid crystalline polymers of patterning not, particularly liquid crystalline polymer film or liquid crystal polymer network, it comprises the thio-ether units of formula (I)

* covalent linkage, its unit with formula (I) is connected on the rest part of polymkeric substance

Wherein

LC ¹Be selected from liquid crystal residue group,

X ¹Be selected from the organic residue group of aliphatics and

n ¹Be 〉=0 integer and

m ¹Be 〉=0 integer;

Prerequisite is if n ¹Be 0, m so ¹If＞0 and m ¹Be 0, n so ¹＞0; With

It is to contain aerobic in preferred amount with 0.1≤oxygen≤50%, and more preferably the amount with 1≤oxygen≤25% contains in the oxygen-containing atmosphere of aerobic, most preferably prepares in air;

Prerequisite is the liquid crystal that does not comprise polymer dispersed.

The invention still further relates to the preparation patterning and not method and its application in optics or sealed cell of liquid crystalline polymers, liquid crystalline polymer film or the liquid crystal polymer network of patterning.

People such as Broer are at Molecular Crystal Liquid Crystal (1999), have described the synthetic of the functionalized liquid crystal of the mercaptan-alkene of formula given below in 332,259

The shortcoming of this material is that the initial orientation of the liquid crystal that this mercaptan-alkene is functionalized partial loss in the photopolymerization process causes opaque polymer liquid crystal polymeric film.Polymerization shrinkage is separated and crystallization is described macroscopical orientation interferential major cause.In order to overcome these problems, designed crosslinkable multiple functionalized mercaptan-alkene liquid crystal (face as follows):

But, point out that as Wilderbeek (J.Phys.Chem.B (2002), 106,12874) liquid crystal has low-solubility character.Low-solubility may cause serious problem in the preparation method of liquid crystal film, for example because the suitability in the method for liquid crystal on being coated on base material.And, do not obtain the easy method of this polyfunctional liquid crystal.The method for preparing them comprises several processing steps and at last uneconomic purifying.In addition, adopt so functionalized LCP compound, the described mercaptan/alkene of meticulous adjusting than aspect still do not have handiness.

GB2394718-A has described by controlled polymerization condition such as yield of radiation, atmosphere and temperature, and/or uses suitable polymerisable liquid crystal compound to obtain to have the polymeric liquid crystal film that postpones pattern.Still need to obtain the simpler method of patterned optical character to two or more different length of delays.This easily acquired all be very useful for various application.

The present invention relates to liquid crystalline polymers, it comprises the thio-ether units of the formula (I) that provides above.

Preferably, the liquid crystalline polymers that the present invention relates to provide above, it is to prepare under the situation of not using cation light initiator.

The liquid crystalline polymers that further preferably provides above, it is to prepare under the situation of not using the oxygen barrier layer of getting rid of oxygen.

In addition preferably, the liquid crystalline polymers that the present invention relates to provide above, it is to use low UV lamp power and energy to prepare.

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

Preferably, the present invention relates to the liquid crystalline polymers in above-mentioned preferential selection and restriction, it comprises the thio-ether units of formula (Ia)

* covalent linkage, its unit with formula (Ia) is connected on the rest part of polymkeric substance

(Ia)

Wherein

LC ¹, LC ²And LC ⁱBe the liquid crystal residue independently of one another,

Wherein

LC ⁱBe selected from down group: LC ³, LC ⁴, LC ⁵, LC ⁶, LC ⁷And LC ⁸, they represent the liquid crystal residue independently of one another,

X ¹And X ²Be the organic residue of aliphatics independently of one another, it does not preferably contain reactive carbon-to-carbon degree of unsaturation,

n ¹And n ²Be 〉=0 integer, the integer of preferred 1-10,

R is 〉=0 integer, and the integer of preferred 0-1000,

m ¹, m ²And m ³Be independently of one another 〉=0 integer, the integer of preferred 0-10,

Q is 0 or 1;

Prerequisite is, if q is 0, and LC so ²And LC ⁱDirectly be connected to each other; If with n ¹And n ²Be 0, at least one m so ¹, m ²Or m ³If be＞0 and m ¹, m ²And m ³Be 0, at least one n so ¹And n ²Be＞0.

More preferably, the present invention relates to the liquid crystalline polymers in above-mentioned preferential selection and restriction, it comprises the thio-ether units of formula (Ib)

* covalent linkage, its unit with formula (Ib) is connected on the rest part of polymkeric substance

(Ib)

Wherein

T ^bBe selected from down group: T ¹, T ², T ³, T ⁴, T ⁵And T ⁶, they are and the residue of representing reactive additive independently of one another,

X ¹, X ²And X ³Be independently from each other the organic residue of aliphatics, preferred divalence or the organic residue of multivalence, it does not preferably contain reactive carbon-to-carbon degree of unsaturation,

n ¹, n ²And n ³Be independently of one another 〉=0 integer, the integer of preferred 1-10,

m ¹, m ², m ³And m ⁴Be independently of one another 〉=0 integer, the integer of preferred 0-10, the more preferably integer of 0-2,

Q and q1 be independently of one another 0 or 1 and

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

Prerequisite is, if q is 0, and LC so ²And LC ⁱDirectly be connected to each other; If with n ¹, n ²And n ³Be 0, at least one m so ¹, m ², m ³And m ⁴If greater than 0 and m ¹, m ², m ³And m ⁴Be 0, at least one n so ¹, n ²And n ³Greater than 0.

The value of subscript r and s depends on described material, particularly depends on the composition of the compound that is used to prepare described liquid crystal film and prepares the processing condition of described liquid crystalline polymers.

The liquid crystalline polymers of formula (Ib) preferably,

Wherein:

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

n ¹, n ²And n ³Be the integer of 0-4 independently of one another, be more preferably 0, the integer of 1-2 most preferably is 1 or 2.

Liquid crystalline polymers is liquid crystal liquid crystal property (being total to) polymkeric substance, elastomerics, polymer gel, film or polymer network preferably, is more preferably liquid crystal polymer network or film.

Term " photopolymerization " is described below in the method for the invention.

Term " liquid crystal residue ", " reactive additive residue " and " compound residue " are illustrated respectively in the polymerized form of described liquid crystal, reactive additive or compound in the described liquid crystalline polymers.

In a preferred embodiment, the present invention relates to formula (I), (Ia) or liquid crystalline polymers (Ib), wherein be connected to liquid crystal LC ¹, LC ²And/or LC ⁱThioether bond " S-" comprise connector element, it is selected from the compound residue of compound group given below: norbornylene, vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, allyl group triazine, the isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, imide, maleimide, methacrylic ester, vinyl cyanide, vinylbenzene, diolefine, vinylamide and alkynes

And most preferably be selected from given below group compound residue: alkynes, alkene, vinyl ether, vinyl ester, allyl ethers, allyl ester, acrylate and methacrylic ester,

And most preferably be selected from given below group compound residue especially: acrylate and methacrylic ester.

The residue of liquid crystal and the residue of reactive additive have at least two polymerisable functional groups in its non-polymeric form, particularly two undersaturated C-Cs.Described undersaturated C-C preferably comprises two keys and/or triple bond, more preferably comprises two keys.

Preferably, the polymerisable functional group of described liquid crystal comprises undersaturated C-C, and it is preferably selected from the compound group that comprises following compound: norbornylene, alkynes, vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, allyl group triazine, isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, imide, maleimide, methacrylic ester, vinyl cyanide, vinylbenzene, diolefine and vinylamide; More preferably, described polymerisable functional group with unsaturated C-C is selected from the compound group that comprises following compound: alkynes, alkene, vinyl ether, vinyl ester, allyl ethers, allyl ester, acrylate and methacrylic ester; Most preferably be selected from acrylate and methacrylic ester.

The term liquid crystal of Shi Yonging is meant the material or the compound of the ability with the behavior of induced liquid crystalline phase in the context of the present invention, for example comprises one or more clavates, plate shape (board-shaped) or disc (disk-shaped) mesomorphic group.Liquid crystalline cpd with clavate or plate shape group is also referred to as the calamitic liquid crystal in the art.Liquid crystalline cpd with disc group is also referred to as the discotic liquid crystal in the art.Described compound or the material itself that comprises mesomorphic group must not show mesomorphic phase.They only with the mixture of other compound in or when described mesomorphic compound or material or their mixture are aggregated, show that the mesomorphic phase behavior also is possible.

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

The term of Shi Yonging " aliphatic organic residue " relates to organic residue of multi-thiol in the context of the present invention, in implication that provides below and the preferential range of choice.

In the context of the present invention, term " aliphatic " comprises the hydrocarbon and the saturated and undersaturated group of straight chain and branching, and wherein at least one carbon, hydrogen and/or hydrogen carbon can be by heteroatoms such as N, S, and O, OOC, COO, OCO, OCOO, OOCO, CO etc. substitute.Possible substituting group comprises alkyl, cycloalkyl aryl, and amino, cyano group, epoxy, halogen, hydroxyl, nitro, oxo etc.Can replace the possible heteroatoms of carbon atom to comprise nitrogen, oxygen and sulphur.Under the situation of nitrogen, can further be replaced by group such as alkyl, aryl and cycloalkyl.Similarly, term used herein " alkyl " and " alkylidene group " comprise the group of straight chain or branching, and saturated and undersaturated group.

In the context of the present invention, suitable multi-thiol can be any in those multi-thiols as known in the art.As multi-thiol, can use to comprise any compound that per molecule has the molecule of two or more thiol groups.Described multi-thiol has the molecular weight in the scope of about 50-about 20,000.

Preferably, multi-thiol is monomer aliphatics multi-thiol, oligopolymer multi-thiol and polymkeric substance multi-thiol.

Preferred multi-thiol relates to two-, three-, four-or polyfunctional mercaptan.

Preferred polymkeric substance multi-thiol is a polytrimethylene ether glycol two (β-Qiu Jibingsuan ester) for example, and it is prepared by polytrimethylene ether glycol (for example Pluracol P201, Wyandotte Chemical Corp.) and β-Qiu Jibingsuan by esterification.Poly--alpha mercaptoacetic acid ester or poly--β-Qiu Jibingsuan ester, particularly trimethylolpropane triester or tetramethylolmethane four esters are preferred.

The preferred functionalized compound of alkyl sulfhydryl is for example 1,2-dimercaptoethane, 1,6-dimercapto hexane, 1,10-decane two mercaptan etc.Also can use the end capped polythioether resin of mercaptan.

Preferred aliphatic two mercaptan comprise 1,2-ethane two mercaptan, butane two mercaptan, 1,3-propane two mercaptan, 1,5-pentane two mercaptan, 2,3-dimercapto-1-propyl alcohol, dithioerythritol, 3,6-two oxa-s-1,8-octane two mercaptan, 1,8-octane two mercaptan, hexane two mercaptan, dithiodiglycol, pentane two mercaptan, decane two mercaptan, 2-methyl isophthalic acid, 4-butane two mercaptan, two-mercaptoethyl phenylmethane, 1,9-nonane two mercaptan (1,9-dimercapto nonane), ethylene glycol dimercapto acetate.

Preferred oligopolymer two mercaptan comprise the oligourethane of dual functional Mercaptofunctional, it is derived from the end-blocking part of hydroxyethyl mercaptan, hydroxypropyl mercaptan, dimercaptopropane, dimercaptoethane, as described in the patent USP 5744514 of Shustack.

The compound of preferred three thiol-functionalization comprises the trimethylolethane trimethacrylate mercaptopropionic acid ester, trimethylolpropane tris mercaptopropionic acid ester (TMPTSH), the trimethylolethane trimethacrylate mercaptoacetate, with the trimethylolpropane tris mercaptoacetate, glycerine three (11-sulfydryl hendecoic acid ester), trimethylolpropane tris (11-sulfydryl hendecoic acid ester).

Preferred four functional mercaptan comprise tetramethylolmethane four mercaptopropionic acid esters, tetramethylolmethane four mercaptoacetates and tetramethylolmethane four (11-sulfydryl hendecoic acid ester).

Preferably have the 7th page of described multi-thiol that comprises the patent (WO/8802902) of Loctite greater than the multi-functional thiol of 4 functionality.

Polyfunctional mercaptan can obtain by making mercaptoalkyl carboxylic acid such as Thiovanic acid, thiohydracrylic acid and high functional alcohol, amine and thiol reactant.And polyfunctional mercaptan can obtain by making the reaction of mercaptoalkyl trialkoxy silane and silanol, and described silanol can be polymkeric substance or silicon dioxide base silanol.Other preferred multi-functional thiol uses mercaptan carboxylic acid (HS-R-COOH, wherein R=alkyl or aryl group) to obtain as the sulfydryl hendecoic acid, the COOH group of described mercaptan carboxylic acid and polyfunctional reactive alkene, alcohol, mercaptan or amine reaction.

Preferably, multi-thiol has-C ₁-C ₁₀Organic residue of alkylidene group-COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

More preferably, organic residue is oxyacetic acid (CH ₂COOH), α-Bing Suan (CH (CH ₃)-COOH and β-propionic acid (CH ₂CH ₂COOH) with the ester of polyol such as glycol, triol, tetrol, pentol or six alcohol.

Preferably-C ₁-C ₁₀Alkylidene group-COOH, preferred-C ₁-C ₄Alkylidene group-COOH, most preferably-C ₂-C ₃Organic residue of the organic ester of alkylidene group-COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

More preferably-CH ₂COOH ,-CH (CH ₃)-COOH ,-CH ₂CH ₂Organic residue of the ester of COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

Especially, most preferably from organic residue of following material: multi-thiol such as glycolate (glycolate) and propionic ester, ethylene glycol bis (mercaptoacetate) for example, ethylene glycol bis (β-Qiu Jibingsuan ester), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (β-Qiu Jibingsuan ester), tetramethylolmethane four (β-Qiu Jibingsuan ester), ethylene glycol dimercapto acetate, 1,2,6-hexanetriol tri-thiol acetic ester, the trimethylolethane trimethacrylate mercaptoacetate, tetramethylolmethane four (mercaptoacetate), trimethylolpropane tris mercaptoacetate and glyceryl mercaptoethanol acid esters; With propionic ester such as trimethylolethane trimethacrylate-(3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester) or glycol dimercaptopropionate, they all are available commercially, and maybe can obtain by methods known in the art.

The term of Shi Yonging " reactive additive " is meant polymerisable reactive additive in the context of the present invention, and it has at least one polymerisable group.For example, reactive additive is a linking agent, reactive diluent, single reaction liquid crystal, the mercaptan of simple function, for example lauryl mercaptan.

In addition, reactive additive for example is selected from the group of the following listed additive that has at least one polymerizable groups: oxidation inhibitor, promotor, dyestuff, inhibitor, activator, filler, chain transfer inhibitor, pigment, static inhibitor, fire retardant, thickening material, thixotropic agent, tensio-active agent, viscosity modifier, extending oil, softening agent, tackifier, catalyzer, sensitizing agent, stablizer, lubricant; Dispersion agent, hydrophobizing agent, tackiness agent, FLOW IMPROVERS (flow improvers), defoamer, air release agent, thinner, secondary additive, tinting material, dyestuff and pigment.

The term of Shi Yonging " single reaction liquid crystal " is meant and has a polymerisable functional group, the liquid crystal of preferred unsaturated C-C in the context of the present invention.Described unsaturated C-C preferably comprises two key and/or triple bonds and more preferably comprises two keys.

Preferably, described reactive additive has at least one, preferably surpasses two polymerisable functional groups.Preferably such as unsaturated C-C, particularly acrylate and methacrylate based group, the polymerisable functional group of acrylate group and so on more especially.

Linking agent is that the technician knows.Suitable compound is described in for example patent publications EP 0331233, and WO 95/24454, and US 5,567,349, and US 5,650,534, WO00/04110, and WO 00/07975, and WO 00/48985, among WO 00/55110 and the WO 00/63154.

Reactive additive can be selected from but be not limited to have norbornylene, vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, the allyl group triazine, isocyanuric acid allyl ester, alkene, acrylate, undersaturated ester, imide, maleimide, methacrylic ester, vinyl cyanide, vinylbenzene, diolefine, the monomer of vinylamide and alkynes polymerizable groups.

Most preferably be selected from given below group: alkynes, alkene, vinyl ether, vinyl ester, allyl ethers, allyl ester, acrylate and methacrylic ester.

Especially most preferably, described polymerizable functional group with reactive additive of unsaturated C-C is acrylate or methacrylic ester, for example: Viscoat 295; Glycol diacrylate; Tetraethylene glycol diacrylate; 1,6 hexanediol diacrylate; Pentaerythritol triacrylate; Diethylene glycol diacrylate; 1,4 butanediol diacrylate; Tetramethylol methane tetraacrylate; 1,3 butyleneglycol diacrylate; Triethylene glycol diacrylate; Neopentylglycol diacrylate; 2-butylene-1, the 4-diacrylate; 1,3-two [(acryloyl-oxy ylmethyl) styroyl] tetramethyl disiloxane; Tripropylene glycol diacrylate; TriMethylolPropane(TMP) b-oxide triacrylate; 1, the 2-propylene glycol diacrylate; 1, the ammediol diacrylate; 2,2,3,3,4,4,5,5-octafluoro hexane-1,6-diacrylate; 1,5-pentanediol diacrylate; Bis-phenol a diacrylate; Bis-phenol a propoxide diacrylate; The decamethylene-glycol diacrylate; 2,2-dibromoneopentyl glycol diacrylate; 3,3 '-dimethyl bis-phenol " a " diacrylate; Dipentaerythritol five acrylate; The bis-phenol a diacrylate of ethoxylation; The tetrabromobisphenol a diacrylate of ethoxylation; Glyceryl propoxy-triacrylate; 4,4 '-(inferior hexafluoro sec.-propyl) phenylbenzene diacrylate; 1,9-nonanediol diacrylate; Dimethyl pentaerythritol acrylate; The quinhydrones diacrylate; The Sorbitol Powder diacrylate; Sorbitol Powder 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-tetrafluoro-1,4-butane diacrylate; The mercaptan diethylene glycol diacrylate; 1,1,1-trimethylolethane trimethacrylate acrylate; Isocyanuric acid three (2-hydroxyethyl) ester triacrylate; 5-ethyl-5-(hydroxymethyl)-β, beta-dimethyl--1,3-diox-2-ethanol diacrylate; 1,6-dihexyl two [oxygen (2-hydroxyl-3,1-glyceryl)] diacrylate; Kayarad r-551; Kayaradpeg400da; 1,4-hexanaphthene dimethyl 1,4-diacrylate; Glycerine propoxide triacrylate; Dipentaerythritol five-and six-acrylate; Two (TriMethylolPropane(TMP)) tetraacrylate; Neopentyl glycol b-oxide diacrylate; The pentaerythritol diacrylate monostearate; TriMethylolPropane(TMP) b-oxide methyl ether diacrylate; (3-(allanoyloxy)-5-[4-(benzamido)-2-oxo pyrimidine-1 (2h)-yl] tetrahydrofuran (THF)-2-base; Diacrylate 1, the inferior phenyl ester of 3-; The fluorescein dimethacrylate; 3-hydroxyl-2,2-dimethyl propyl 3-hydroxyl-2,2-dimethyl propylene acid esters diacrylate; 2,2 ', 6,6 '-tetrabromobisphenol " a " diacrylate; Bis-phenol a glyceride (1 glycerine/phenol) diacrylate; TriMethylolPropane(TMP) benzoic ether diacrylate; Propylene glycol glyceride diacrylate; Three (propylene glycol) glyceride diacrylate; Glycerine 1,3-two glyceride diacrylates; Hydroxyl valeryl hydroxy new pentane acid ester two [6-(acryloxy) capronate]; 1,6-hexylene glycol propoxide diacrylate; Tetramethylolmethane propoxide triacrylate; 1,6-hexylene glycol b-oxide diacrylate; 2,2,3,3,4,4-hexafluoro-1,5-amyl group diacrylate; 2,2,3,3,4,4,5,5-octafluoro-1,6-hexyl diacrylate; Three ring [5.2.1.02,6] decane dimethanol diacrylates.

More preferably, described liquid crystal has at least two polymerisable, undersaturated C-Cs of formula (II)

Wherein:

A ¹-A ⁶Be hydrogen independently of one another, polar group, unsubstituted or replace methyl group, or 2-40 carbon atom hydrocarbyl group unsubstituted or that replace, wherein one or more carbon atoms are substituted or are not substituted by heteroatoms in Sauerstoffatom mode not connected to one another by heteroatoms, or wherein one or more carbon atoms are by the unsubstituted or aromatic carbocyclic that replaces or heterocyclic group substitutes or do not substituted by aromatic carbocyclic or heterocyclic group unsubstituted or that replace; Comprise or do not comprise polymerizable functional group with unsaturated C-C with wherein said hydrocarbyl group; Prerequisite is A ¹-A ⁶In one of at least, preferred two comprise the polymerizable functional group with unsaturated C-C;

B ¹And B ²Represent singly-bound independently of one another, the hydrocarbyl group of Sauerstoffatom or the optional 1-80 carbon atom that replaces, wherein one or more carbon atoms can be substituted in Sauerstoffatom mode not connected to one another by heteroatoms;

MG ¹Implication with following formula (III)

Wherein

C ¹-C ⁴Be carbocyclic ring or heterocyclic group that replace or unsubstituted, non-aromatics or aromatics independently of one another, preferably by described bridge linkage group Z ¹-Z ³Be connected to each other in contraposition,

Z1-Z3 is independently of one another

-CH (OH)-,-CO-,-CH2 (CO)-,-SO-,-CH2 (SO)-,-SO2-,-CH2 (SO2)-,-COO-,-OCO-,-COCF ₂-,-CF ₂CO-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-CH ₂-CH ₂-,-OCH ₂-,-CH ₂O-,-CH=CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-,-CH=N-,-CH (CH ₃)=N-,-N=N-or single covalent linkage,

a ₁, a ₂And a ₃Be the integer of 0-3 independently of one another, make 1≤a ₁+ a ₂+ a ₃≤ 3,

A ⁷And A ⁸The A that has and provide above ¹-A ⁶Identical implication;

MG ²And MG ³The implication that has following formula (IV) independently of one another

Wherein

C ¹'-C ⁴', Z ^{1 '}-Z ^{3 '}, a _{1 '}, a _{2 '}And a _{3 '}Have and corresponding " alphabetical number ": C ¹-C ⁴, Z ¹-Z ³, a ₁, a ₂And a ₃Identical implication and preferential the selection;

n ₁And n ₂Be 1 or 2 independently of one another, " n wherein ₁=2 " (or " n ₂=2 ") show at described group MG ₁And MG ₂(or MG ₂And MG ₃) between have two via described group B ₁(or described group B ₂) independent connection; With

n ₃Be the integer of 0-1000, the integer of preferred 0-5, more preferably 0 or 1;

n ₄Be 0 or 1.

In the context of the present invention, term " hydrocarbon " comprises the alkylidene group of straight chain or branching, and carbocyclic ring or heterocyclic group saturated and aromatics undersaturated group and optional replacement.

Term " aromatic monocyclic " comprises the ring of 5 or 6 atoms, the monocycle of two 5 or 6 adjacent atoms, the bicyclic ring system of 8,9 or 10 atoms, perhaps three of 13 or 14 atoms ring member ring systems; Preferably, carbocyclic ring and heterocyclic group unsubstituted or that replace preferably represented in the term of Shi Yonging " aromatics " in the context of the present invention, be combined with 5,6,10 or 14 annular atomses, furans for example, benzene or phenylene, pyridine, pyrimidine, naphthalene, it can form the ring group, for example biphenylene or inferior terphenyl, its by or be not interrupted by at least one heteroatoms and/or at least one bridge linkage group; Or the condensed polycyclic system, for example luxuriant and rich with fragrance, naphthane.Preferably, aromatic group is a benzene, phenylene, biphenylene or inferior terphenyl.Preferred aromatic group is a benzene, phenylene and biphenylene.

Carbocyclic ring or heterocyclic aromatic group preferably have 5,6,10 or 14 annular atomses, as for example furans, benzene, pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or naphthane unit are such, preferably as naphthalene, phenanthrene, biphenylene or phenylene are such, more preferably as naphthalene, biphenylene or phenylene are such and most preferably as phenylene.

The carbocyclic ring of described aromatics or heterocyclic group for example are unsubstituted single or polysubstituted.The preferred substituted of carbocyclic ring or heterocyclic aromatic group is at least a halogen, hydroxyl, polar group, acryloxy, alkyl acryloxy, alkoxyl group, alkyl carbonyl oxy, alkoxyl group carbonyl oxygen base, alkyl oxo carbonyl oxygen base, methacryloxy, vinyl, vinyl oxygen base and/or allyloxy group, wherein said alkyl residue preferably has the 1-20 carbon atom, more preferably has the 1-10 carbon atom.Preferred polar group is a nitro, cyano group or carboxylic group, and/or the C of ring-type, straight chain or branching ₁-C ₃₀Alkyl, it is unsubstituted, mono-substituted or many.C ₁-C ₃₀The preferred substituted of alkyl is methyl, fluorine and/or chlorine, wherein one or more, preferably non-conterminous-CH ₂-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 furans for example, benzene, phenylene preferably, pyridine, pyrimidine.

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

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

The term of Shi Yonging " phenylene " preferably represents 1 in the context of the present invention, 2-, and 1,3-or 1, the 4-phenylene group, it is optional the replacement.Preferred described phenylene group is 1,3-or 1,4-phenylene group.1, the 4-phenylene group is particularly preferred.

Term " halogen " is meant chlorine, fluorine, bromine or iodine substituting group, preferred chlorine or fluoro substituents.

The term of Shi Yonging " polar group " mainly is meant as nitro in the context of the present invention, the group of cyano group or carboxyl.

The term of Shi Yonging " heteroatoms " mainly is meant oxygen in the context of the present invention, sulphur and nitrogen, and preferred oxygen and nitrogen preferably are being under one situation in the back-form of NH-.Nitrogen as heteroatomic situation under, it can further replace with group such as alkyl, aryl and cycloalkyl.

The term of Shi Yonging " replacement " mainly is meant by following group and replaces in the context of the present invention: low alkyl group such as C ₁-C ₆Alkyl, lower alkoxy such as C ₁-C ₆Alkoxyl group, aryl and group of naphthene base, and amino, cyano group, carboxyl, epoxy, halogen, hydroxyl, nitro, oxo and hydroxyl.

Preferably, A ¹And A ⁸In inclusion compound residue formula V one of at least independently of one another:

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

Wherein:

P is hydrogen or polar group, preferred nitro, cyano group, halogen; Or methyl group unsubstituted or that replace, or having the polymerizable functional group of unsaturated C-C, this polymerizable functional group is selected from and comprises norbornylene, vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, the allyl group triazine, isocyanuric acid allyl ester, alkene, alkynes, acrylate, undersaturated ester, imide, maleimide, methacrylic ester, vinyl cyanide, vinylbenzene, diolefine, the group of vinylamide and allyl group acid amides;

Sp is unsubstituted or the straight chain of replacement or the C of branching _1-30Alkylidene group, wherein one or more-CH ₂-group can substitute by heteroatoms and/or by polar group, and/or one or more carbon-to-carbon singly-bound substituted by carbon-to-carbon double bond or triple bond, and/or to be substituted also optional by at least one optional aromatic carbocyclic that replaces or heterocyclic group be possible,

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

X is-O--S-,-NH-,-N (CH ₃)-,-CH (OH)-,-CO-,-CH ₂(CO)-,-SO-,-CH ₂(SO)-,-SO ₂-,-CH ₂(SO ₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-CH ₂-CH ₂-,-OCH ₂-,-CH2O-,-CH=CH-,-C ≡ C-, or singly-bound,

T is the integer with value of 0 or 1.

Described C _1-30Alkylidene group or C _1-20That alkylidene group Sp can comprise branching or straight-chain alkyl-sub-group, and can be unsubstituted, or single or polysubstituted by following groups: alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro, particularly F, Cl, Br, I or CN.Alternatively or additionally, be present in the one or more CH in the described hydrocarbon chain ₂Group can be substituted by one or more groups that are selected from down group independently :-O-,-S-,-NH-, N (CH ₃)-,-CH (OH)-,-CO-,-CH ₂(CO)-,-SO-,-CH ₂(SO)-,-SO ₂-,-CH ₂(SO ₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-C ≡ C-,-(CF ₂) _R1-,-(CH ₂) _S1-or C (W ₁)=C (W ₂)-, prerequisite is that two Sauerstoffatoms directly are not connected to each other.W ₁And W ₂Represent H independently of one another, H-(CH ₂) _Q2-or Cl.Described integer r1, s2 and q2 represent 1 and 15 number independently of one another.

Preferably, Sp represents C _1-20Alkylidene group, more preferably C _1-13Alkylidene group, it is unsubstituted or uses alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro replaces, and wherein one or more-CH ₂-group can be substituted by heteroatoms; And/or alternative by the carbocyclic ring of at least one the optional aromatics that replaces or heterocyclic group, in implication that provides in the above and the preferential range of choice.

Preferably, P is a hydrogen, nitro, cyano group, halogen, the unsubstituted or methyl group that replaces, or having the polymerizable functional group of unsaturated C-C, this polymerizable functional group is selected from and comprises vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, alkene, alkynes, acrylate, the group of undersaturated ester and methacrylic ester is preferably selected from the group that comprises acrylate and methacrylic ester.

Preferably, X represents-O-, and-CO-,-COO-,-OCO-,-C=C-, and more preferably, X be-O-,-COO-or-OCO-.

Further preferably,

Sp represents C _1-20Straight-chain alkyl-sub-group, more preferably C _1-13Alkylidene group, it is unsubstituted or uses alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl or nitro replace, and wherein one or more carbon atoms can be substituted by heteroatoms and/or be substituted by the carbocyclic ring of at least one the optional aromatics that replaces or heterocyclic group;

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

P is hydrogen or the polymerizable functional group with unsaturated C-C, and this polymerizable functional group is selected from and comprises vinyl ether, vinyl ester, allyl ethers, allyl ester, acrylate, the group of methacrylic ester and preferred-O-,-COO-,-OCO-.

Preferably, B ¹And/or B ²The group that comprises formula (VI) independently of one another:

(X ⁴) _t2-(Sp ²) _k2-(X ⁵) _t3?????(VI)

Wherein:

Sp ²Expression C _1-20Alkylidene group;

X ⁴And X ⁵Expression-O-independently of one another ,-S-,-NH-, N (CH ₃)-,-CH (OH)-,-CO-,-CH ₂(CO)-,-SO-,-CH ₂(SO)-,-SO ₂-,-CH ₂(SO ₂)-,-COO-,-OCO-,-OCO-O-,-S-CO-,-CO-S-,-SOO-,-OSO-,-SOS-,-CH ₂-CH ₂-,-OCH ₂-,-CH ₂O-,-CH=CH-,-C ≡ C-or singly-bound;

K2 is an integer, has 0 or 1 value;

T2 and t3 are integers, have 0 or 1 value independently of one another;

Prerequisite is that Sauerstoffatom is not connected to each other.

Preferably, B ¹And B ²The group of expression (VI) independently of one another, wherein:

X ⁴And X ⁵Expression-O-independently of one another ,-CO-,-COO-,-OCO-,-C ≡ C-, or singly-bound, particularly-and O-,-COO-,-OCO-or singly-bound; With

Sp ₂Expression C _1-20Straight-chain alkyl-sub-group, particularly ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, inferior undecyl or inferior dodecyl.

A kind of particularly preferred polymkeric substance is B wherein ¹And B ²The group and the A of expression (VI) independently of one another ¹-A ⁸The polymkeric substance of representing the group of formula V independently of one another.

Preferably, C ¹-C ⁴Be selected from:

Wherein:

L is-CH ₃,-COCH ₃,-NO ₂,-CN or halogen,

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

U2 is 0,1,2, or 3,

U3 is 0,1, or 2.

More preferably, C ¹-C ⁴Be selected from: cyclohexylidene, phenylene, naphthylidene or phenanthrylene.

Most preferably, C ¹-C ⁴Be selected from: phenylene

Preferably, Z ¹-Z ³Expression-COO-independently of one another ,-OCO-,-CH ₂-CH ₂-,-OCH ₂-,-CH ₂O-,-CH=CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-or single covalent linkage.

More preferably, Z ¹-Z ³Expression-COO-,-OCO-,-CH=CH-COO-,-OCO-CH=CH-or single covalent linkage independently of one another.

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

Wherein:

A ¹, A ², A ⁷, C ¹, C ², C ³, Z ¹And Z ²And a1 has identical implication and preferential selection that provides above with a2.

The further compound of formula (VII) especially most preferably, wherein:

-A ₁And A ₂Be the compound formula V independently of one another:

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

Wherein

P is the polymerizable functional group with unsaturated C-C, it is selected from and comprises vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, alkene, alkynes, acrylate, the group of undersaturated ester and methacrylic ester is preferably selected from the group that comprises acrylate and methacrylic ester;

Preferably, at A ¹And A ²Middle P is identical;

Sp represents C _1-20Alkylidene group, more preferably C _1-13Alkylidene group, it is unsubstituted or uses alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro replaces, and wherein one or more-CH ₂-group can be substituted by heteroatoms; And/or alternative by at least one optional aromatic carbocyclic that replaces or heterocyclic group, in implication that provides in the above and the preferential range of choice;

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

K is the integer with value of 0-4,

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

-A ⁷Have the identical implication and preferential selection that provide above; Preferably, A ⁷Be hydrogen or polar group, preferred nitro, cyano group, halogen, the unsubstituted or methyl group that replaces, or the polymerizable functional group in implication that provides in the above and the preferential range of choice with unsaturated C-C; Preferably, A ⁷Be hydrogen or polar group, preferred nitro, cyano group, halogen, the unsubstituted or methyl group that replaces and/or

-C ¹, C ²And C ³Identical identical meanings that provides above and preferential the selection; Especially, C ¹, C ²And C ³It is phenylene; And/or

-Z ¹And Z ²Be identical, and have identical implication and preferential selection that provides above; Preferably, Z ¹And Z ²Be-COO--OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound; If Z ¹And Z ²One of be singly-bound, so another Z preferably-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH-.

In addition, most preferred A ¹And A ²Be identical.

In addition, the liquid crystalline polymers of the present invention of formula (VIII) most preferably

Wherein:

A ¹, A ², A ⁵, A ⁶, C ¹, C ², C ³, B ¹, Z ¹And Z ², C ¹', C ²', C ³', Z ¹' and Z ²' and a1, a2, a1 ' has identical implication and preferential selection that provides above with a2 '.

The further compound of formula (VIII) especially most preferably, wherein

-A ¹, A ², A ⁵, A ⁶Be compound residue formula V independently of one another:

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

Wherein

P is the polymerizable functional group with unsaturated C-C, it is selected from and comprises vinyl ether, vinyl ester, allyl ethers, allyl ester, propenyl ether, alkene, alkynes, acrylate, the group of undersaturated ester and methacrylic ester and be preferably selected from the group that comprises acrylate and methacrylic ester; Preferably at A ¹, A ², A ⁵, A ⁶In P be identical;

Sp represents C _1-20Alkylidene group, more preferably C _1-13Alkylidene group, it is unsubstituted or replaces with alkyl, aryl, cycloalkyl, amino, cyano group, epoxy, halogen, hydroxyl, nitro, and wherein one or more-CH ₂-group can be substituted by heteroatoms; And/or alternative by at least one optional aromatic carbocyclic that replaces or heterocyclic group, in implication that provides in the above and the preferential range of choice;

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

K is the integer with value of 0-4,

T is the integer with value of 0 or 1;

Preferred A ¹, A ², A ⁵, A ⁶Be identical;

And/or

-B ¹The group that comprises formula (VI):

(X ⁴) _t2-(Sp ²) _k2-(X ⁵) _t3??????????(VI)

Wherein:

Sp ²Expression C _1-20Alkylidene group;

K2 is an integer, has 0 or 1 value;

T2 and t3 are integers, have 0 or 1 value independently of one another;

Prerequisite is that Sauerstoffatom is not connected to each other;

Preferably, B ¹The group of expression (VI), wherein:

Sp ²Expression C _1-20Straight-chain alkyl-sub-group, particularly ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, inferior undecyl or inferior dodecyl; And/or

-C ₁', C ₂' and C ₃' and C ₁, C ₂And C ₃Be identical and have the identical implication that provides above and preferential the selection; Especially, C ₁', C ₂' and C ₃' and C ₁, C ₂And C ₃It is phenylene; And/or

-Z ¹And Z ²And Z ¹' and Z ²' be identical, and have identical implication and preferential selection that provides above; Preferably, Z ¹And Z ²And Z ¹' and Z ²' be-COO--OCO-,-CH=CH-COO-,-OCO-CH=CH-or singly-bound; If Z ¹And Z ²One of be singly-bound, so another Z preferably-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH-, and if Z ¹' and Z ²' one of be singly-bound, so another Z preferably-COO-,-OCO-,-CH=CH-COO-or-OCO-CH=CH.

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

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

Wherein

X ^aBe aliphatic organic residue,

n ^tBe 〉=2 integer, the integer of preferred 2-10, more preferably 3 or 4 and

B) at least a liquid crystal with at least two polymerizable functional groups and

C) randomly at least a reactivity and/or non-reacted additive and

D) randomly at least a initiator and

E) randomly at least a solvent.

Composition preferably of the present invention does not wherein comprise tetramethylolmethane four (β-dodecyl sulfydryl) propionic ester.

Composition more preferably of the present invention, wherein said liquid crystalline cpd is to exist to the amount of described composition total weight greater than 50 weight %.

In addition, preferably, the liquid crystalline polymers that the present invention relates to provide above, it does not contain cation light initiator.

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

In an embodiment preferred of the present invention, described composition comprises initiator.

Described liquid crystal, multi-thiol, aliphatic organic residue, polymerisable functional group and non-reacted additive have identical implication and preferential selection that provides above.

Particularly preferably, X ^aBe-C ₁-C ₁₀The organic residue of multivalence aliphatics of the organic ester of alkylidene group-COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

More preferably, X ^aBe oxyacetic acid (CH ₂COOH), α-Bing Suan (CH (CH ₃)-COOH and β-propionic acid (CH ₂CH ₂COOH) with the ester of polyol such as glycol, triol, tetrol, pentol or six alcohol.

HS-C preferably ₁-C ₁₀Alkylidene group-COOH, preferred HS-C ₁-C ₄Alkylidene group-COOH, most preferably HS-C ₂-C ₃The multi-thiol of the organic ester of alkylidene group-COOH and polyol such as glycol, triol, tetrol, pentol or six alcohol.

Thiovanic acid (HS-CH more preferably ₂COOH), alpha-mercapto propionic acid (HS-CH (CH ₃)-COOH and β-Qiu Jibingsuan (HS-CH ₂CH ₂COOH) with the multi-thiol of the ester of polyol such as glycol, triol, tetrol, pentol or six alcohol.

Especially, most preferred multi-thiol is ethyl glycolate and propionic ester, ethylene glycol bis (mercaptoacetate) for example, ethylene glycol bis (β-Qiu Jibingsuan ester), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (β-Qiu Jibingsuan ester), tetramethylolmethane four (β-Qiu Jibingsuan ester), ethylene glycol dimercapto acetate, 1,2,6-hexanetriol tri-thiol acetic ester, the trimethylolethane trimethacrylate mercaptoacetate, tetramethylolmethane four (mercaptoacetate), trimethylolpropane tris mercaptoacetate and glyceryl mercaptoacetate; And propionic ester, trimethylolethane trimethacrylate-(3-mercaptopropionic acid ester) for example, tetramethylolmethane four (3-mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester) or glycol dimercaptopropionate, all these is available commercially, and perhaps can obtain by methods known in the art.

Polymerization can with or carry out without initiator, preferably use initiator to carry out.Whether use initiator to depend on the kind and the processing parameter of parent material.Can select the initiator of the outer any kind of decationize light trigger.Radical initiator preferably.Described initiator can be heat or light trigger or its combination.Free radical photo-initiation more preferably.

Usually, light trigger has absorption at the wavelength place of actinic radiation.When polymerization utilizes UV light to carry out, can use under the UV irradiation and decompose to produce the free radical or the ionic light trigger of starting polyreaction.The UV light trigger is preferred, particularly free radical UV light trigger.The example of free radical photo-initiation or maleimide light trigger is described by people such as Dias (SurfaceCoatings International, JOCCA 2000,10,502-506 and WO-01/27040).

As the light trigger of the standard that is used for radical polymerization, can use for example to be available commercially

907,

651,

369,

184,

1173 or

4205 (all deriving from Ciba SpecialtyChemicals).

Non-reacted additive for example relates to oxidation inhibitor, promotor, dyestuff, inhibitor, activator, filler, pigment, static inhibitor, fire retardant, thickening material, thixotropic agent, tensio-active agent, viscosity modifier, extending oil, softening agent, tackifier, catalyzer, sensitizing agent, stablizer, for example phenol derivatives, for example 4-thanatol or 2,6 di tert butyl 4 methyl phenol (BHT), lubricant; Dispersion agent, hydrophobizing agent, tackiness agent, FLOW IMPROVERS, defoamer, air release agent, thinner, curing inhibitors, secondary additive, tinting material, dyestuff, describe among pigment or EP1 090 325 B can photic orientation monomer or oligopolymer or polymkeric substance;

Especially, if require colored filter, dyestuff can be added in the composition of the present invention.

Thereby can be used to stablize component or curable compositions and prevent that the curing inhibitors of the routine that premature solidification begins or stopper from can comprise quinhydrones; P-tert-butyl catechol; 2,6-di-t-butyl-p-methyl phenol; Phenothiazine; N-phenyl-2-ALPHA-NAPHTHYL AMINE.

Described composition is a solid, or is diluted in the solvent with the form of solution, gel, dispersion or emulsion, and described solvent is organic solvent and/or water.

Preferably, described composition is transparent solution.Described solvent of Shi Yonging or solvent mixture can be any compounds that can dissolve liquid-crystal composition of the present invention in this application.Can use at least a solvent, for example common polar solvent or non-polar solvent.Particularly preferred solvent is good coating or those of printing of solution on applied base material that cause described material.

Non-polar solvent is to have low specific inductivity and not miscible with a water compound, hexane for example, benzene, toluene, ether, chloroform, ethyl acetate, methylene dichloride.

Polar solvent is non-proton or proton.

Polar aprotic solvent is to have the ion dissolving power of protonic solvent but the solvent that do not have acidic hydrogen.These solvents have high specific inductivity and high polarity usually.Example is 1,4-diox, tetrahydrofuran (THF) (THF), acetone, acetonitrile (MeCN), dimethyl formamide (DMF), methyl-sulphoxide (DMSO), N-Methyl pyrrolidone (NMP), ethyl pyrrolidone, the N-vinyl pyrrolidone, butoxy ethanol (BC), gamma-butyrolactone (BL), N-methylmorpholine, gamma-butyrolactone, acetonitrile, ethyl carbitol, butylcarbitol, diethylene glycol monoethyl ether acetate, ethylene glycol, propylene glycol monoacetate, propylene-glycol diacetate, dipropylene glycol, and DPGME, chlorobenzene, tetrahydrofuran (THF), ethylene glycol butyl ether, cyclopentanone (CP), methyl ethyl ketone (MEK), ethyl acetate (EA), methyl-phenoxide (AN), pimelinketone (CHN), methyl iso-butyl ketone (MIBK) (MIBK), 1-methoxyl group-2-propyl alcohol acetic ester (MPA), N, N-dimethyl-methane amide (DMF), methylene dichloride, gamma-butyrolactone (BL) and their mixture.

Polar aprotic solvent is the solvent that contains dissociable H+, for example hydrogen fluoride.The molecule of such solvent can provide H+ (proton).On the contrary, aprotic solvent can not give hydrogen bond.The total characteristic of protonic solvent is the signify hydrogen bonding, has acidic hydrogen (although they may be very weak acid), can stabilizing ion (by not sharing unbound electron to stable cationic, stablizing negatively charged ion by hydrogen bond).Example is an acetate, propyl carbinol, Virahol, n-propyl alcohol, ethanol, methyl alcohol, formic acid and water.

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

Preferred solvent is but is not limited to:

-ketone, acetone for example, cyclopentanone (CP), pimelinketone (CH), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone (MEK),

-acid amides, N for example, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), the N-ethyl pyrrolidone, the N-vinyl pyrrolidone, N,N-dimethylacetamide,

-carbamate,

-ether, methyl-phenoxide (AN) for example, tetrahydrofuran (THF) (THF), ethylene glycol, dipropylene glycol, butylcarbitol, diethylene glycol monoethyl ether acetate, DPGME,

-ester, ethyl acetate (EA) for example, 1-methoxyl group-2-propyl alcohol acetic ester (MPA), gamma-butyrolactone (BL), the propylene glycol monoacetate, propylene-glycol diacetate, DPGME,

-alcohol, butoxy ethanol (BC) for example, ethyl cellosolve, ethylene glycol butyl ether,

-methyl-sulphoxide (DMSO),

-halohydrocarbon, methylene dichloride for example, chlorobenzene,

-non-polar solvent, such as but not limited to hydrocarbon, hexane for example, heptane, toluene, sherwood oil,

With their mixture.

Preferred solvent is an acetone, cyclopentanone (CP), pimelinketone (CH), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone (MEK), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), N-ethyl pyrrolidone, the N-vinyl pyrrolidone, N,N-dimethylacetamide, (AN), tetrahydrofuran (THF) (THF), ethylene glycol, dipropylene glycol, butylcarbitol, diethylene glycol monoethyl ether acetate, DPGME, ethyl acetate (EA), 1-methoxyl group-2-propyl alcohol acetic ester (MPA), gamma-butyrolactone (BL), the propylene glycol monoacetate, propylene-glycol diacetate, DPGME, methyl-sulphoxide (DMSO).

Cyclopentanone (CP) most preferably, pimelinketone (CH), methyl iso-butyl ketone (MIBK) (MIBK), methyl ethyl ketone (MEK), ethyl acetate (EA), 1-methoxyl group-2-propyl alcohol acetic ester (MPA), methyl-sulphoxide (DMSO).

The described reactivity in described composition or the amount of non-reacted additive are by the mesomorphic phase restriction of the film that is prepared by described composition (XX), and described mesomorphic phase must be held.Usually, the amount of described reactivity or non-reacted additive is the 0.1-50 weight % of described composition, is preferably the 1-30 weight % of described composition, even the 1-10 weight % of described composition more preferably.

Comprise at composition of the present invention under the situation of stablizer, stablizer is usually with 0.01-5 weight %, and the amount of preferred 0.1-1 weight % exists, based on described composition meter.

Initiator is with effectively amount use for the curing that causes described compound.Described significant quantity depends on the character of processing parameter and starting raw material.Typically, described amount is in the scope of 0.1-10 weight %, preferably in the scope of 0.5-8 weight %, more preferably in the scope of 1-5 weight %, with respect to the gross weight meter of described composition.Also can use the combination of two or more initiators (light trigger or thermal initiator).

Preferred liquid crystalline polymers of the present invention (I), (Ia) or (Ib) by preparation of compositions, the mol ratio of the thiol group of multi-thiol and unsaturated C-C is less than 2 in the said composition, preferably in the scope of about 0.005-1, more preferably in the scope of 0.001-0.5, most preferably in the scope of 0.002-0.5.

The purposes that depends on expection, it may be favourable adding solvent.The typical concentration of described composition that places solvent between 2 and 50%, preferably between 10 and 40%, in activeconstituents as multi-thiol, liquid crystal and optional polymerization agent, initiator and additive as described in weight concentration in the solvent.

In another embodiment, the present invention relates to composition of the present invention (XX) and be used to prepare elastomerics, liquid crystalline polymers gel, liquid crystalline polymers, the application of liquid crystal polymer network or liquid crystalline polymer film.

Compound of the present invention can use method well known to those skilled in the art (for example at Houben-Weyl, Methoden der Organischen Chemie, Thieme-Verlag, those methods of Stuttgart or record in U.S. Patent number 6630076 or WO 2005/054406) preparation easily.

Diverse ways can be used to begin to form liquid crystal film or the liquid crystal network that needs by described polymerisable composition (XX).Can use base material such as glass or plastic basis material, described base material can randomly be coated with tin indium oxide (ITO).In order to prepare liquid crystal film or network, particularly importantly avoid the formation of defective or ununiformity.Therefore, preferred substrate comprises glass or plastics, particularly comprises those of both alignment layers (for example layer of the photopolymer (LPP) of the layer of Mo Ca polyimide or polyamic acid or photic orientation).Use described layer to allow the homogeneous orientation of liquid crystal compound.The homogeneous orientation can also realize by other method known in the art.Described polymerisable composition (XX) is coated on the base material and polymerization.Preferably, the composition of described polymerisable coating (XXI) be this means to make and uses up that preferred UV light solidifies it, to provide crosslinked liquid crystalline polymers (LCP) film by photopolymerization.Depend on the reactivity of described polymerizable material set time among others, the thickness of the layer of coating, the power of the type of polymerization starter and UV lamp.According to the present invention, especially preferably no longer than 5 minutes, very particularly preferably be shorter than 2 minutes preferably no longer than 10 minutes described set time.For production in enormous quantities, 1 minute or still less, very preferably 1 minute or still less, particularly be preferred the set time of 10 seconds or weak point still less.After being exposed to light and temperature, described film is the machinery tolerance.

In the context of the present invention, term " radiation curing " and " photopolymerization " are used as synonym.

The invention still further relates to the method for preparation liquid crystalline polymers, particularly liquid crystal film or liquid crystal network, this method comprises:

Contain aerobic in the preferred amount with 0.1≤oxygen≤50%, more preferably the amount with 1≤oxygen≤25% contains in the oxygen-containing atmosphere of aerobic, most preferably in air,

A) coating composition (XX), wherein said composition have identical meanings and preferential selection that provides above; Then

B) randomly dry and then

C) be aggregated in the composition (XXI) of the described coating that obtains after step a) or the step b), it is film preferably.

Preferably, the method that the present invention relates to provide is not above wherein used the oxygen barrier layer of getting rid of oxygen.

In addition, preferably the present invention relates to the liquid crystalline polymers that provides above, it is to use low UV lamp power and energy preparation.

In addition, the composition that the present invention relates to be coated with (XXI), it can be according to processing step described above b a) and randomly) obtain.

Common described composition is by general coating known in the art and printing process coating.Coating process is for example spin coating, air doctor blade, blade coating (blade coating), blade applies (knifecoating), contrary roller coat cloth, angle stripper coating, the gravure roll coating, touch print roll coating, casting is coated with, spraying, slotted opening coating (slot-orifice coating), calendering coating, galvanic deposit coating (electrodepositing coating), dip-coating or die orifice coating (diecoating).

Printing process for example is: letterpress, for example flexographic printing, ink jet printing; Intaglio printing, for example directly intaglio printing or intaglio printing (offset gravure printing) indirectly; Lithography, for example offset printing; Or silk screen printing, for example screen printing.

Whether carry out the denseness that drying step depends on described composition.

If described composition comprises solvent, common dry described composition after described application step.

Usually, " drying " is to extract described solvent, for example by applying the air that was heated, uses the air logistics (convection drying or convection drying) that for example applies described heat by convection current and take away solvent vapour.Dry very fast under higher temperature; But the mesomorphic phase of the composition of described coating (XXI) must be held, and this has limited the temperature that can apply, and preferably is lower than the clear point of the composition (XXI) of described coating.In addition, determining when carrying out the dry temperature that is applied, also must consider the quality of product or film.Other possibility is: vacuum-drying, and wherein by contact conduction or radiation (or microwave) heat supplied, produced simultaneously steam is removed by vacuum system; Indirectly or contact drying (by the hot wall heating), drum dried for example, vacuum-drying; Radio-frequency drying (radio frequency or microwave are absorbed in described material); Lyophilize or freeze-drying; The mechanical extraction of solvent.

The initiator of described reactivity and/or non-reacted additive and described composition usually before described method or in the process with described polymerizable liquid-crvstalline or multi-thiol pre-mixing.

In an embodiment preferred of the present invention, described method comprises the composition (XXI) of the described coating of photopolymerization.

Described photopolymerization is undertaken by radiation.

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

Preferably unpolarized light, but under concrete situation also can apply polarising or partial polarization, the light of linear, circle or elliptical polarization.

Usually, lamp is used for photopolymerization.The intensity that is used for the lamp of described irradiation should preferably be higher than 0.2mW/cm ², more preferably be higher than 10mW/cm ², most preferably be higher than 20mW/cm ², especially most preferably be higher than 50mW/cm ²Most probable ground, described polyreaction can cause by any photochemical light source.Usually, be aggregated under the common room temperature condition and finish.The actinic radiation of other form of finding usually in the ray that can be used for a class actinic light of the present invention and be UV-light and send by the sun or by source of artificial light such as RS type fluorescent lamp, carbon lamp, xenon arc lamp, mercury vapor lamp, tungsten halide lamp etc.If described photo curable polyenoid/multi-thiol composition contains suitable photopolymerization accelerator, uv-radiation can use most effectively.By suitable selection ultraviolet source, photopolymerization accelerator and its concentration, the reactive group functionality of temperature and molecular weight and described polymerizable liquid-crvstalline and multi-thiol, can be adjusted to very short set time, and therefore commercial be economical.

Described liquid crystalline polymers can also be passed through electron beam (EB) and obtain.This curing needn't require initiator.

Randomly, described photopolymerization can be carried out under the situation that does not adopt light trigger in the mode that is similar to the Bowman description, wherein use specific UV light source with strong emission (people such as Bowman, Macromolecules 2002,35,5361-5365), and can described in EP0618237, use maleimide to carry out.

The invention still further relates to liquid crystalline polymers, preferred formula (I), (Ia) or liquid crystalline polymers (Ib), it can obtain by above-described the inventive method, and particularly the polymerization by the present composition obtains.

Preferably, the present invention relates to liquid crystalline polymers, preferred formula (I), (Ia) or liquid crystalline polymers (Ib), it can obtain by above-described the inventive method, particularly the polymerization by the present composition obtains, and prerequisite is the liquid crystal that does not comprise polymer dispersed.

The invention still further relates to described liquid crystalline polymers (I), the application in preparing optics patterning or patterning or sealed cell and system's (particularly multilayer system) or device of the liquid crystal film of the composition of described coating (XXI) or network.

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

Sealed cell, system or device move by the optical property that is changed material by electric field.Therefore, it relates to the interaction between electricity (electronics) attitude of electromagnetism (light) and material.

Optics patterning or patterning or sealed cell can be used to (but being not limited to): waveguide; safety or trademark protection element; barcode; grating; spectral filter; delayer (retarder); compensation film; reflective polarizer films; the absorptivity polarizing coating, anisotropic scattering film, compensation and phase shift films; the phase shift films that reverses (twisted retarder film); cholesteric liquid crystal film, guest of honour's type liquid crystal film, monomer ripple film; the smectic liquid crystal film; polarizer, piezoelectricity pond (piezoelectric cell), the film of demonstration nonlinear optical property; ornamental optical element; brightness improves film, is used for the element of wavelength band selectivity compensation, is used for the element of multizone compensation; the element of multi-view angle LCD; colour killing delayer (achromaticretarder), polarization state correction/adjusting film, the element of optics or photo-sensor; brightness improves the element of film; the element that is used for light base telecommunication device has the G/H-polarizer of the patterning of anisotropic absorption device, the reflectivity circuit polarizer of patterning; the reflective linear polarizer of patterning, the MC of patterning (monomer ripple film).

Preferably safety element, loop expansion pipe and phase shift films.

Another aspect of the present invention provides optics or sealed cell and multilayer system, and it comprises liquid crystalline polymers of the present invention, liquid crystalline polymer film or network.

Preferably, patterning is meant the patterning of birefringence patternization and/or thickness patterning and/or optic axis orientation, and/or the patterning of the polymerization degree.Double refraction is meant the difference between the extra-ordinary index of refraction and common specific refractory power.

The invention still further relates to the liquid crystalline polymers of preparation patterning, the method of birefringent film particularly, this method comprises the composition (XXI) of the described polymerisable coating of patterning, the patterning of preferred birefringence patternization and/or thickness patterning and/or optic axis orientation, and/or the patterning of the polymerization degree and also preferably include photopolymerization.

In addition, the present invention relates to liquid crystalline polymers (I), particularly birefringent film of patterning, or comprise the network and the optical element of the liquid crystalline polymers of such patterning.

In the context of the present invention, the liquid crystalline polymers of patterning (I) film of patterning preferably.

More preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, this method comprises planar two-dimensional patterned, or in the space three-D patternization, described thus pattern is periodic or acyclic.Three dimensional form is for example specific surface relief structure (relief structure), that for example tilt or crooked liquid crystalline polymers structure, for example microlens or micro-prism structure.

The method of the liquid crystalline polymers of described preparation patterning (I) provides preparation to have the means easily of the birefringent film of specific surface relief structure such as microlens or micro-prism structure.

More preferably, patterning is meant the method for the composition (XXI) that comprises the described coating of radiation curing.Most preferably, the present invention relates to the polymerization degree and the method for preparing the liquid crystalline polymers of patterning of remaining not polymerisable liquid crystal or the component by the described liquid-crystal composition of rinsing randomly then by producing patterning, the step of the polymerization degree of described generation patterning comprises that the present composition (XXI) the one or many ground that makes coating is exposed to radiation by one or more masks, the radiation of preferred parallel, and/or be exposed to the radiation of sweep beam form.

The partial polymerization degree can be passed through in the measurement of the local proportion of unreacted polymerizable groups quantification in liquid-crystal composition after the polymerization.

If wish to realize the high resolving power of described patterning, it is favourable using parallel radiation.

By radiation-induced polymerization, preferred radical polymerization realizes the regioselectivity polymerization, wherein composition (XXI) (the being wet film) quilt of being made up of polymerisable liquid crystal not of coating is passed through shadow mask board (shadow mask) or gray masks (gray mask) radiant exposure, and/or utilizes flying spot bundle radiant exposure.

In the context of the present invention, polymerization is meant any reaction that can obtain polymkeric substance according to it.Polymerization is for example any polyreaction, curing and crosslinking reaction.Term curing is meant polymerization.

Especially, most preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, this method is included in single step of exposure or in a plurality of step of exposure,

A) by black/white or ash or spectral selectivity mask, or black/white or ash or spectral selectivity mask by can between step of exposure, reapposing, or black/white or ash or spectral selectivity mask by between step of exposure, being replaced;

And/or

B) radiation by the sweep beam form

The present composition of the described polymerisable coating of polymerization (XXI).

In the context of the present invention, the black/white mask is meant that described mask is by fully the zone of transmission and the zone of blocking are fully formed for each radiation.The grey mask is meant the zone that also has the transmissivity with by-level.

More preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning by birefringent patterning.

Processing condition can be utilized birefringent influence, with composition (XXI) patterning with described coating.The order parameter (order parameter) that depends on liquid crystal molecule in the composition (XXI) or the double refraction in the liquid crystalline polymers (I) of described polymerisable coating.Described order parameter for example can be by the temperature effect of composition of described polymerisable coating (XXI) or liquid crystalline polymers (I).Temperature is to the influence of described order parameter and therefore described birefringent influence is depended on the polymerization degree.Complete unpolymerized liquid-crystal composition has shown the strong dependency of double refraction to temperature.Along with the polymerization degree improves, described dependency dies down.Therefore, the patterning of the above-mentioned polymerization degree can be used to induce birefringent patterning by making described liquid-crystal composition be exposed to a certain temperature.So the birefringent pattern that produces can fix by using second polymerization procedure.

Most preferably, the present invention relates to prepare by birefringent patterning the method for the liquid crystalline polymers (I) of patterning, this method comprises

A) make the composition (XXI) of described polymerisable coating or liquid crystalline polymers (I) be exposed to radiation, and/or one or many is exposed to the radiation of sweep beam form by one or more mask one or many,

With

B) subsequently at elevated temperatures, preferably second polymerization under the temperature of the clear point that is higher than described composition.Hot or photoinduced polymerization all is possible, preferably photopolymerization or light and heat inductive polymeric combination.

Perhaps, can by partly under different conditions the described film of polymerization produce birefringent pattern.The birefringent condition that can influence liquid crystal film in the patterning polymerization procedure is the temperature of described film, is used to cause described polymeric radiating intensity, dosage, spectrum, stores the atmosphere of described film in polymerization process.The combination of these conditions also is possible.Described local polymerization under different condition can realize by the repeatedly radiant exposure through mask different or that reappose, perhaps is used to cause described polymeric flying spot bundle and realizes.

Double refraction can utilize the induced reaction art pattern CADization of locally variable in addition.Described radiation preferably is made up of electromagnetic radiation, preferably is made up of visible light and/or UV light and/or X-ray and/or electron beam.Described radiation can apply by black/white, ash or wavelength selectivity mask, perhaps applies by the scanning of bundle of rays on the birefringent film zone.Randomly, described reaction can be by carrying out simultaneously or with the temperature of after-applied rising and/or in atmosphere reactive.

Most preferably, the present invention relates to prepare by birefringent patterning the method for the liquid crystalline polymers (I) of patterning, this method comprises by under different processing condition, preferably under different temperature; And/or (preferably be higher than 1mJ/cm at the different energy of the radiating that is used to expose ², more preferably at 1mJ/cm ²-5J/cm ²Scope in), under intensity or the spectrum; And/or under different atmosphere, make described polymerizable liquid-crvstalline or polymerizable liquid-crvstalline composition one or many be exposed to the radiation that radiation and/or one or many be exposed to the sweep beam form and come producing pattern aspect the polymerization degree by one or more masks.

Most preferably, the present invention relates to utilize radiation, the composition (XXI) by described polymerisable coating or the birefringent patterning of liquid crystalline polymers (I) prepare the method for the liquid crystalline polymers (I) of patterning.

Preferably, the radiometer that is used for described method is shown in the electromagnetic radiation and/or the bombardment of visible and/or UV and/or x-ray scope, as electronics and/or atom and/or ion and/or molecular radiation, most preferably UV radiation causes the radiation-induced physics or the chemical reaction of locally variable thus.Described radiation-induced reaction changes local birefringence.In an embodiment preferred of the present invention, the change that the polymerization degree is passed through in described radiation-induced reaction realizes.

In another embodiment of the invention, the component of one or more radiation activatable in described polymerizable liquid-crvstalline composition of the present invention (XX) makes and can rely on partial radiation to handle the double refraction of regulating described liquid-crystal composition.The component of radiation activatable can be the component that for example can be transformed into a kind of different isomeric forms (for example anti-along isomerization) from a kind of isomeric forms, depends on the Local treatment of carrying out with radiation.Preferably, the radioactivation process of described patterning is carried out before the polymerization of described liquid-crystal composition.Be used for to apply or applying by black/white, ash or wavelength selectivity mask by the scanning of bundle of rays on described liquid-crystal composition zone in the described radiation of the activatory that switches between different isomer.Randomly, described radiating effect can be by simultaneously or thermal treatment subsequently or improve by the storage of described liquid-crystal composition in particular atmosphere.Handling the described different isomer that produces according to described partial radiation influences order in the liquid crystal film by different way, and therefore can realize birefringent local modulation.Preferably, the process of described photoisomerization is separated with the initiation of described polymerization process.Described birefringent pattern can be fixed by the polymerization that causes described liquid-crystal composition subsequently.

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

Most preferably, the present invention relates to utilize the means of the photoisomerization of the present composition (XXI) of radiation by using coating to prepare the method for the liquid crystalline polymers (I) of patterning, the present composition of described coating (XXI) but contain the component of photoisomerization.

But the compound of preferred photoisomerization comprises N=N, C=C or C=N unit.

Most preferably, the patterning of thickness that the present invention relates to the present composition (XXI) of the patterning of the thickness by birefringent patterning or polymerizable liquid-crvstalline (I) or polymerisable coating prepares the method for the liquid crystalline polymers (I) of patterning.

This can remove by regioselectivity (preferably rinse or dissolve), and the part of mould material uniformly realized.

Usually, for example, sample removes unpolymerized part in the solvent by being immersed in, perhaps polymerization is carried out at elevated temperatures, and polymerization subsequently can be passed through photochemistry or/and thermal initiation preferably causes under the temperature of the clarifying temp that surpasses described unpolymerized liquid crystal material thus.In both cases, produced and had or the digital pattern in the zone of high or low optical delay value.In the former case, because the removal of unpolymerized material has formed thickness profile; Under one situation of back, realized more or less film uniformly, its part is birefringent or non-birefringent, perhaps local have or high or low double refraction.

For example, in one embodiment, according to the top polymerization degree that produces patterning in the first step that is described in.In second step, utilize the described liquid-crystal composition of suitable solvent develop with polymerization degree of patterning, promptly use the described film of described solvent rinsing, perhaps described film is immersed in the described solvent.Because the amount of the solvability of described material and the material therefore removed can depend on the polymerization degree, therefore the pattern with the design transfer film forming thickness of the polymerization degree is possible.Use the described developing method of solvent to carry out at elevated temperatures.

Be used for the suitable solvent of described developing method and select, and be acetone for example, methyl-phenoxide according to the relative solvability of the component of the composition (XXI) of described polymerisable coating and described solidified liquid crystal film (I), butylacetate, butyl methacrylate, butyl glycol (ethylene glycol butyl ether), gamma-butyrolactone, pimelinketone, cyclopentanone, Diethylene Glycol-Anaesthetie Ether, Diethylene Glycol, diethylene glycol dimethyl ether (Diglyme), N, dinethylformamide, dipropylene glycol dimethyl ether, DPGME ， diox, ethyl acetate, ethyl lactate, glycol diacetate, acetate 2-ethoxyethyl group ester, ethyl-3-oxyethyl group-propionic acid-ethyl ester, ethylene glycol, ethanol, 4-hydroxy-4-methyl-2 pentanone, Virahol, 2-propyl alcohol, methylene dichloride, methyl ethyl ketone, 4-methyl-2 pentanone, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl alcohol acetic ester, methyl propyl ketone, 1-Methyl-2-Pyrrolidone, propyl acetate, 2-Pyrrolidone, the propylene glycol propyl ether, tetrahydrofuran (THF), toluene, dimethylbenzene.

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

Especially most preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, this method comprises

Under different processing condition, make described polymerizable liquid-crvstalline film one or many ground by the preparation of the composition (XXI) of described coating be exposed to radiation and/or be exposed to the radiation of sweep beam form by one or more masks,

With

Utilize solvent develop subsequently, and/or the temperature polymerization by raising.

The liquid crystalline polymers (I) of the polymerization degree with patterning that produces by aforesaid method can also be patterned in addition, wherein realizes the layer thickness of patterning by the uniform material ablation that utilizes particle and/or electromagnetic radiation.Described bombardment can be by ion, atom, and molecule and/or electronics are formed, and described electromagnetic radiation can be by IR, and as seen, UV light or x-ray are formed.

In another embodiment, for even polymeric liquid crystalline polymers (I), described material ablation is carried out in the mode of patterning.The ablation of described patterning applies particle and/or electromagnetic radiation and realizes by inhomogeneous.Described inhomogeneous applying by described birefringence liquid crystal composition realized to described liquid-crystal composition by the rapid exposure of the single or multistep of one or more black/whites or ash or wavelength selectivity mask and/or by the bundle of rays that applies scanning.Described bombardment can be by atom, molecule, and ion and/or electronics are formed, and described electromagnetic radiation can be by IR, and as seen, UV light or x-ray are formed.

Another method that produces the film thickness of patterning is that described material area optionally is deposited on the base material.Described deposition is preferably finished by printing process.The printing process of typical types is ink jet printing, spin coating, offset printing, intaglio printing, flexographic printing etc.

Another the inventive method that is used for the film thickness patterning is the use of regioselectivity manufacturing process, for example impression, punching press or method of moulding.Described manufacturing process can be applied in unpolymerized, partially polymerized or complete polymeric birefringent film.

The another kind of method of the film thickness of patterning birefringent film is to use lithographic plate printing method.Described lithographic plate printing method can comprise the steps: to be coated with photoresist material, with radiation pattern exposure, development step, etching step and strip step.Described lithographic plate printing method preferably is applied in partially or completely polymeric birefringent film.

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

Especially most preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, by

A) make described polymerizable liquid-crvstalline film one or many ground by the preparation of the composition (XXI) of described coating be exposed to radiation and/or be exposed to the radiation of sweep beam form by one or more masks,

With

B) utilize uniform bombardment and/or electromagnetic radiation uniformly subsequently, preferably use the non-homogeneous solidified liquid crystal film of the radiation ablation of patterning by composition (XXI) preparation of described coating.

In addition, especially most preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, by

A) the described material area selectivity of regioselectivity ground printing, and/or

B) regioselectivity ground impression, punching press or molded described material, and/or

C) the described material of planography.

Another embodiment of the invention is the method that comprises the optic axis of the described liquid crystalline polymers of patterning (I).

Under the situation of alignment, by the visible and/or UV light of partial polarization, the exposure of the inclination of non-polarized light is perhaps passed through in inclination or the vertical exposure of the light of preferred partial linear, circle or elliptical polarization, and described orientation function is introduced both alignment layers.

The patterning of described optic axis can be realized by means of the both alignment layers of the patterning below liquid crystal film.Described both alignment layers makes and the azimutal orientation of the patterning of optic axis can be introduced liquid crystal film, perhaps the pitch angle of patterning is introduced in the liquid crystal molecule at the interface between described both alignment layers and described liquid crystal film.The type that depends on both alignment layers, described orientation function can produce by being exposed to radiation, and wherein said radiation can be electromagnetic radiation, particularly visible and/or UV light, or bombardment, particularly atom, molecule, ion and/or electronics.In addition, described orientation can be by the mechanical treatment of both alignment layers, and the described layer that for example rubs, the groove that stretches described layer and/or introduce submicron in described layer are induced.The function of base material and both alignment layers can be combined, and promptly depends on the type of base material, and itself can functionalised described base material, to introduce orientation in the liquid crystal film that is coated on described base material top.All above-mentioned methods of orientation function of inducing can also directly be put on such suitable substrates.

The another kind of mode of patterned optical axle orientation is to use additive in liquid crystal film (I), preferred reactive additive, described additive depend on described slant characteristic of their properties influence (tilt profile) and/or position angle alignment features (azimuthal alignmentprofile).Such additive is for example to transform polarity that the activation back changes them, their pKa constant, their additive of screw twisted merit (helical twisting power) etc.

The conversion activation of described additive can be exposed to radiation, and preferred electromagnetic radiation more preferably takes place behind UV and/or the visible light.

By combined to change also that envrionment conditions activates as temperature and/or surrounding atmosphere also be possible with being exposed to radiation.

Patterning can by in described compound in different reactive additive activation condition lower areas each district of polymerization optionally, perhaps the patterning of the conversion by described additive before polymerization activates and realizes.

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

Most preferably, the present invention relates to prepare the method for the polymeric birefringent film of patterning by both alignment layers.

Especially most preferably, the present invention relates to by prepare the method for the liquid crystalline polymers (I) of patterning with both alignment layers patterning liquid crystal, described both alignment layers shows to tilt and/or azimutal orientation.

Especially most preferably, the present invention relates to prepare the method for the liquid crystalline polymers (I) of patterning, described liquid crystalline polymers (I) comprises liquid crystal and additive, the preferred reactive additive; And/or chiral dopant.

In an embodiment preferred of the present invention, additive represents to influence inclination and/or the additive of azimutal orientation and the chiral dopant that chiral dopant represents preferably to have variable torsional work.

Especially most preferably, the present invention relates to the method for the polymeric liquid crystalline polymers (I) of the combined preparation patterning by the method that provides above and/or additive.

In the context of the present invention, the radiation of patterning is meant the incident light of the part change that is radiated on the target compound.

In the context of the present invention, both alignment layers is meant the layer of the function of inducing orientation in the liquid crystal layer that has on being coated on described both alignment layers.

In the context of the present invention, chiral dopant can be used as additive, be preferably used as reactive additive, it makes that described polymerizable liquid-crvstalline film is thermochromism, the thermochromism mode make by the pitch of said composition reflection and therefore wavestrip can select the temperature when promptly depending on partly that by the color of described film reflection described film is cured (described in US6117920 for example) by temperature variation.Described chiral dopant for example can be selected from the n-nonanoic acid cholesterol ester (CN) that is available commercially, CB15, and R/S-811, R/S-1011, R/S-2011, R/S-3011 or R/S-4011 (Merck KGaA, Darmstadt) or derive from BASF's LC756.Specially suitable is to comprise chirality glycosyl doping agent group, that have high torsional work, particularly two anhydrous hexitol (dianhydrohexitol) derivatives, the for example derivative of Sorbitol Powder, mannitol or iditol, very preferably disclosed sorbitol derivatives among the WO98/00428.Further preferably: GB 2,348, the disclosed doping agent that comprises the benzyleneglycol group in 207, disclosed chiral binaphthyl radical derivative among the WO 02/94805, disclosed chirality bis-phenol acetal derivant among the WO 02/34739, disclosed chirality TADDOL derivative among the WO 02/06265, have the chiral dopant that at least one fluoridizes linking group and end or central chirality group with disclosed among WO 02/06196 and the WO 02/06195, 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, U.S. Patent number 5,360, disclosed chiral dopant in 577.

In the context of the present invention, optical delay is by the long-pending definition of the thickness of double refraction and birefringent film.Double refraction is defined as poor between the extra-ordinary index of refraction and common specific refractory power.

In the context of the present invention, the position angle alignment direction is meant the azimutal orientation of unusual axle in the plane of described layer.In addition, alignment features (profile) is meant the variation along the thickness direction of described birefringent film of position angle and/or polarity alignment direction, as for example in reversing delayer (retarder).

In the context of the present invention, tilt to be meant the angle between the orientation of membrane plane and liquid crystal molecule, and slant characteristic indicates the depth direction change of described pitch angle along described film, and wherein in some cases, described slant characteristic can be similar to by specifying average slope angle.

In the context of the present invention, ' A plate ' is meant the optical delay of the layer that utilizes the single axial birefringence material, and the unusual axle of described single axial birefringence material is parallel to the planar orientation of described layer.

In the context of the present invention, ' C plate ' is meant the optical delay of the layer that utilizes the single axial birefringence material, and the unusual axle of described single axial birefringence material is perpendicular to the planar orientation of described layer.

In the context of the present invention, ' O plate ' is meant the optical delay of the layer that utilizes the single axial birefringence material, and the unusual axle of described single axial birefringence material is with respect to the angular orientation of plane to tilt of described layer.

Comprise and have positive A-, C-and O-plate birefringent, the uniaxial birefringent material of optics and be also referred to as "+A/C/O plate " or " positive A/C/O plate ".Comprise and have negative A-, C-and O-plate birefringent, the uniaxial birefringent material film of optics and be also referred to as " A/C/O plate " or " negative A/C/O plate ".

In the context of the present invention, term " radiation curing " is meant by radiation-induced polymerization or crosslinked or process.

In an embodiment preferred of the present invention, the liquid crystalline polymers of patterning (I) is three-dimensional or two-dimensional patterned liquid crystalline polymers.

In addition, the liquid crystalline polymers of patterning preferably, the liquid crystalline polymers of preferred formula (I), it can obtain by method of the present invention, and particularly it can preferably obtain by photopolymerization by polymerization.

Preferably, the present invention relates to liquid crystalline polymers (I) by the patterning of the composition (XXI) of described coating preparation.

Preferably, the present invention relates to liquid crystalline polymers (I), it has the performance of at least a transverse patternization, and wherein said pattern can be periodic or acyclic.

" transverse patternization " in above-mentioned definition is meant that the character of described birefringent film changes in the plane of described film.

Described liquid crystalline polymers (I) also can obtain by electron beam (EB).This curing needn't require initiator.

Preferably, the present invention relates to optics or sealed cell, it comprises the delayer film that reverses and/or cholesteric liquid crystal film and/or the guest of honour's type liquid crystal film and/or the smectic liquid crystal film of the liquid crystalline polymers (I) that contains patterning.

Described birefringent film is tolerance (resistant) when being exposed to light and temperature, and can be used to make device, safety element for example, compensate film, phase shift films, spectral filter, polarizer, grating, waveguide, photocell, the film of piezoelectricity pond or demonstration nonlinear optical property.Preferably compensate and phase shift films.

In addition, preferably, the delayer film that the present invention relates to reverse, it comprises the liquid crystalline polymers of the present invention (I) of patterning.

In addition, preferably, the present invention relates to cholesteric liquid crystal film, it comprises the liquid crystalline polymers of the present invention (I) of patterning.Preferably, described cholesteric liquid crystal film is the A-plate that reverses, and shows wavelength and polarization selectivity luminous reflectance, and wherein Fan She light wavelength band depends on along the pitch or the pitch gradient of thickness direction and depends on the birefringence of described liquid crystalline polymers (I).

In addition, preferably, the present invention relates to guest of honour's type liquid crystal film, it comprises the liquid crystalline polymers of the present invention (I) of patterning.Preferably, described guest of honour's type liquid crystal film comprises the molecule of additional anisotropic absorption, and described molecule preferably is arranged essentially parallel to indicator (director) orientation of described liquid crystal.

Preferably, the molecule of anisotropic absorption shows different absorbent properties for the light of the different polarization states in about 150-2000nm wavelength region typically.

The molecule of normally used described anisotropic absorption has the two keys of carbon-to-carbon, carbon-nitrogen or nitrogen-nitrogen.

The molecule of described anisotropic absorption is an azoic dyestuff for example, anthraquinone, mericyanine, methane, 2-phenylazothiazole (2-phenylazothiazole), 2-phenylazobenzthiazole (2-phenylazobenzthiazole), 1, the 2-toluylene, 1, two (2-phenyl vinyl) benzene of 4-, 4,4 '-two (arylazo) stilbene Lei ， perylene, 4, the 8-diaminostilbene, the 5-naphthoquinone dyestuff has the diaryl ketone with two aromatic ring conjugated ketone parts or ketone derivatives, the benzophenone of Qu Daiing for example, benzophenone imines, phenyl hydrazones and semicarbazone class or laurate.

The preparation of the material of the anisotropic absorption of listing above is well-known, as people such as for example Hoffman at U.S. Patent number 4,565,424, people such as Jones are at U.S. Patent number 4,401,369, Cole, people such as Jr. are at U.S. Patent number 4,122,027, people such as Etzbach are at U.S. Patent number 4,667,020 and people such as Shannon at U.S. Patent number 5, disclosed in 389,285.

The molecule of preferred anisotropic absorption is an arylazo, anthraquinone, poly-(arylazo), stilbene and diaryl ketone derivative and laurate.

More preferably arylazo, stilbene, diaryl ketone and laurate.

The molecule of described anisotropic absorption can be by covalent bonding in trunk polymer, they can be used as side-chain radical by covalent bonding on main chain, perhaps their solutes of can be used as nonbonding exist in the polymkeric substance.

Polymkeric substance is for example represented polyacrylic ester, polymethacrylate, and polyimide, polyamic acid, poly maleimide, poly--2-propenyl chloride acid esters, poly--the 2-phenyl acrylate; Unsubstituted or use C ₁-C ₆The polyacrylamide that alkyl replaces, PMAm, poly--2-propenyl chloride acid amides, poly--the 2-Phenyl Acrylamide, polyvingl ether, polyvinylesters, polystyrene derivative, polysiloxane, the straight chain of polyacrylic acid or polymethyl acrylic acid or branched alkyl ester; Polyacrylic acid phenoxyalkyl ester, polymethyl acrylic acid phenoxyalkyl ester, polymethyl acrylic acid phenylalkyl ester with alkyl residue of 1-20 carbon atom; Polyacrylonitrile, polymethacrylonitrile, polystyrene, poly--4-vinyl toluene or their mixture.

Preferably, the invention still further relates to the application of optics not patterning of the present invention or patterning or sealed cell, be used for as phase shift films and/or compensate film and/or reflective polarizer films and/or absorbing polarization film and/or anisotropic scattering film

(a) stable twisted nematic (TN) liquid-crystal display, the nematic of hydridization orientation (HAN) liquid-crystal display, the double refraction of electric control (ECB) liquid-crystal display, STN Super TN type (STN) liquid-crystal display, the double refraction of optical compensation (OCB) liquid-crystal display, π-pond liquid-crystal display, copline is switched (IPS) liquid-crystal display, fringing field switches (FFS) liquid-crystal display, (VA) liquid-crystal display of vertical orientation; All aforementioned display device types are with transmission or reflection or the application of saturating reflection (transflective) pattern;

(b) produce 3-D view or the indicating meter of the image that changes with the visual angle;

(c) safety or trademark protection device;

(d) ornamental optics;

(e) brightness improves film;

(f) optical pickocff;

(e) light base telecommunication device.

In addition, preferably, the present invention relates to monomer ripple film (monomer corrugatedfilm).

In addition, preferably, the present invention relates to comprise the smectic liquid crystal film of described liquid crystalline polymers (I).

The smectic liquid crystal film is meant the polymeric liquid crystal film in smectic phase, and wherein the liquid crystal molecule in smectic phase also has certain position degree of order along a direction except that having ordered orientation.

In addition, preferably, the stacked body of the device that the present invention relates to provide above.

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

Safety element,

Wavelength band selectivity compensation: birefringence-compensated film, it is by RGB (being red, green and blue) sub-pix (subpixels) patterning according to liquid-crystal display, so that the compensation character that adapts to best by the wavelength band separately of described sub-pix transmission to be provided,

Multizone (for example permeable reflective liquid crystal display device) compensation: have according to by the birefringence-compensated film of the character of the lateral variation character patterning of compensating device,

The element of multi-view angle LCD: as the compensation or the phase shift films of display device, described indicating meter provides different images for different visual angles,

The element of three-dimensional liquid-crystal display: be used as the compensation or the phase shift films of the element of the liquid-crystal display that three-dimensional image information is provided,

Achromatic delayer: the delayer film, different with simple chromatic delayer, this delayer film provides the similar change of polarization state for the wavelength band (for example whole visible wavelength range) of broad,

Polarization state correction/adjusting film: birefringent film, it is used to revise or regulate polarization state, and purpose is to make function can bring into play or improve the performance of optics,

The element of the element of optics or photo-sensor, particularly polarization sensitivity/selective sensor,

Brightness improves the element of film,

Safety device or ornamental optics,

Be used for light base telecommunication device, particularly based on the element of the device of polarized light.

Another embodiment of the invention relates to the device of the G/H-polarizer with anisotropic absorption agent that comprises patterning.

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

Another embodiment of the invention relates to the device of the reflectivity circuit polarizer that comprises patterning.

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

Another embodiment of the invention relates to the device of the reflection linear polarization that comprises patterning.

Preferably, the reflection linear polarization of described patterning is that brightness improves film, safety device or ornamental optics.

Another embodiment of the invention relates to the Beam Control device, and it comprises optics or sealed cell, is preferred for the compensation and the phase shift films of wavefront modification device.

Another embodiment of the invention relates to the device of MC (the being the monomer ripple) film that comprises patterning.

Preferably, the monomer ripple film of described patterning is the anisotropic scattering film, the anisotropic emission body, and anti-reflective film has birefringent film, safety device or the ornamental optics of raising.

In the present invention, particularly preferably be for example following device: the nematic that reverses (TN) liquid-crystal display, the nematic of hydridization orientation (HAN) liquid-crystal display, the double refraction of electric control (ECB) liquid-crystal display, STN Super TN type (STN) liquid-crystal display, the double refraction of optical compensation (OCB) liquid-crystal display, π-pond liquid-crystal display, copline is switched (IPS) liquid-crystal display, and fringing field switches (FFS) liquid-crystal display, (VA) liquid-crystal display of vertical orientation; All aforementioned display device types are used with transmission or reflection or saturating reflective-mode, and they can be used to produce 3-D view or the indicating meter of the image that changes with the visual angle; The Beam Control device; Light base telecommunication device; Optical pickocff; The stacked body of device.

In the present invention, found the liquid crystal compound of novel patternable, its by simple method provided obtain patterned optical character to two or more different length of delays by way of.This easily acquired all be very useful for various application.

The result, since when adopting the acrylate LCP of standard with regard to exposure dose and the very limited process window of temperature, but to compare with the method for the LCP material that adopts the described air curing that comprises the component with the mercaptan described among the present invention or thio-ether units be suitable difficulty to described delay patterning method.Solvability contrast gradient (developing method) is only arranged or postpone contrast gradient (having) in the second polymeric method more than the clear point and the resolving power of described pattern between compromise can being conditioned.But the major advantage of LCP mixture aspect patterning of air curing is to use the exposure dose that causes the reasonable polymerization degree to be adjusted in the possibility of the transition of polymerization in the LCP film and non-polymeric interregional good qualification.

Embodiment

Wt% % weight

The photopolymerizable polymkeric substance of LPP linearity

The LCP liquid crystalline polymers

The LC liquid crystal

Min minute

Rpm rev/min

The FTIR fourier-transform infrared

IR is infrared

T _ANAnnealing temperature

T _cClarifying temp

The CP cyclopentanone

The MIBK methyl iso-butyl ketone (MIBK)

The CHN pimelinketone

The AN methyl-phenoxide

LCP (1) 2,5-two [4-6-acryloxy hexyloxy) benzoyloxy] phenylformic acid amyl group ester, what be available commercially derives from ROLIC Technologies, Switzerland or be similar to U.S. Patent number 5,593,617 route 1,2,3,4 preparations

LCP (2) has the implication of the liquid crystalline cpd of following formula

LCP (2) can know by those skilled in the art

The preparation method obtain.Preferably, the method for describing among the embodiment of LCP (2) by WO 95/24454 obtains.

LCP (3) has the implication of the liquid crystalline cpd of following formula

LCP (3) can know by those skilled in the art

The preparation method obtain.Preferably, LCP (3) by WO 00/55110 route 1 and 2 and embodiment in the method described obtain.

LPP has the implication of " can linear photic polymeric polymkeric substance ".

In order to prepare the LPP both alignment layers, suitable LPP material for example is described in patent publications EP 0611786, among WO 96/10049 and the EP 0763552, and comprises cinnamic acid derivative and ferulic acid derivative.For example, following LPP material ROP-103 is selected.

ROP-103 is commercially available alignment material

(ROLIC?Technologies，Switzerland)。This alignment polymer-based carbon is in the laurate as photoreactive group.The polymer backbone of described alignment material is an acrylate type.

Embodiment 1 (composition M1):

Polymerisable composition M1 is prepared as follows:

At room temperature stirred the 30wt% solution of described composition M1 in cyclopentanone 30 minutes.

The preparation of both alignment layers

For both alignment layers is spun on the base material, ROP-103 is dissolved in the cyclopentanone with the solids concn of 2 weight %.At room temperature stirred described LPP solution 30 minutes.

Base material (glass baseplate) is with the spin coating of described LPP solution (under 2000rpm 1 minute).180 ℃ of dryings after 10 minutes, sample is used from having the polarized light of spectral filter with the high pressure Hg Jupiter of selecting the 300-330nm spectral range (100mJ/cm for example ², adopt Schott UG11 and WG 295) and irradiation.

Then with the solution of mixture M 1 by spin-on deposition on this LPP substrates coated, and 39 ℃ of annealing 2 minutes down.The clarifying temp of M1 is 44 ℃.Adopt unpolarized UVA light to make described film photopolymerization (500mJ/cm under air atmosphere at room temperature subsequently ², lamp intensity=50mW/cm ², time=10s), to provide the tack-free LC film of polymeric (thickness=2.44 μ m).Refer to that viscosity (finger tack) is by touching tested sample and writing down described sample and sensuously how to glue (being viscosity) and test with forefinger.Described film can be called as tack-free (touching dried), although may not be completely crued.

In order to characterize the orientation performance of described liquid crystal material, use polarizing microscope to measure the contrast gradient of described crosslinked liquid crystal layer with crossed polarizers, described polarizing microscope further is furnished with the photorectifier that is used for luminous intensity measurement.Described contrast gradient is calculated as along the ratio of the light intensity of the optic axis mensuration of the described crosslinked fluid crystal layer that is 45 ° and 0 ° orientations with respect to one of described polarizer.4000: 1 high-contrast has confirmed the orientation performance of the excellence of M1.

Use FTIR (ATI Mattson Genesis Series FTIR Spectrometer) partly to determine the chemical conversion rate for described alkene.The layer that 2.65 μ m of described reactive composition are thick is spin-coated on the silicon chip.The thickness of described film is measured with Tencor alpha-stepper 500 at last.The infrared spectra of the described film of mensuration before curing and after solidifying.At 810cm ^-1Less being subjected to of bands of a spectrum (corresponding to C=C-H deformation peak) influence with other bands of a spectrum eclipsed, therefore be selected for the measurement of described transformation efficiency.The formula that calculates described unsaturated C-C transformation efficiency is as follows: transformation efficiency (%)=(A ₀-A _t)/A ₀, A wherein ₀And A _tBe illustrated in before the UV exposure and UV exposure back (500mJ/cm ²) at 810cm ^-1The IR bands of a spectrum.

Described 810cm ^-1Bands of a spectrum are with respect to as interior target 1510cm ^-1Bands of a spectrum (v (1,4-C ₆H ₄) bands of a spectrum of aromatics) normalization method.

The transformation efficiency of described unsaturated C-C is 68%.

Comparative Examples 1 (composition C1)

Polymerizable liquid-crvstalline composition C1 is prepared as follows:

Coating is to carry out with similar mode described in the embodiment 1.LC annealing was carried out under 50 ℃ 2 minutes.The clarifying temp of Ca-M1 is 55 ℃.Subsequently described film is used isotropy UVA light photopolymerization (500mJ/cm under air atmosphere at room temperature ², lamp intensity=50mW/cm ², time=10s), obtain the film of viscosity.The transformation efficiency very low (42%) of described alkene part.

Comparative Examples 2 (composition C2)

Polymerizable liquid-crvstalline composition C2 is prepared as follows:

Coating is to carry out with similar mode described in the embodiment 1.LC annealing was carried out under 43 ℃ 2 minutes.The clarifying temp of Ca-M1 is 47 ℃.Subsequently described film is used isotropy UVA light photopolymerization (500mJ/cm under air atmosphere at room temperature ², lamp intensity=50mW/cm ², time=10s), obtain the film of viscosity.The transformation efficiency very low (41%) of described alkene part.

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

Comparative Examples 3 (composition C1)

The coating of C1 is to carry out with similar mode described in the embodiment 1.LC annealing was carried out under 50 ℃ 2 minutes.The clarifying temp of M1 is 55 ℃.Subsequently with described film isotropy UVA light photopolymerization (500mJ/cm under nitrogen atmosphere ², lamp intensity=50mW/cm ², time=10s), obtain the tack-free LC film of polymeric (thickness=2.57 μ m).The transformation efficiency of described alkene part is 70%.

Comparative Examples 4 (composition M1)

The coating of M1 is to carry out with similar mode described in the embodiment 1.LC annealing was carried out under 39 ℃ 2 minutes.Subsequently with described film isotropy UVA light photopolymerization (500mJ/cm under nitrogen atmosphere ², lamp intensity=50mW/cm ², time=10s), obtain the tack-free LC film of polymeric (thickness=2.44 μ m).The transformation efficiency of described alkene part is 79%.

Embodiment 5 (composition M2)

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

Coating is to carry out with similar mode described in the embodiment M1.LC annealing was carried out under 30 ℃ 2 minutes.The clarifying temp of M3 is 33 ℃.Subsequently described film is used isotropy UVA light at room temperature photopolymerization (500mJ/cm under air atmosphere ², lamp intensity=50mW/cm ², time=10s), obtain tack-free LC film (thickness=2.45 μ m).The transformation efficiency of described alkene part is 62%.

This embodiment for example understands the use of the reactive additive (being Dipentaerythritol five acrylate) that participates in network formation here.

Embodiment 6

The influence of mercaptan structure and concentration

The preparation of film

Unless otherwise mentioned, use following coating condition.

For both alignment layers is spin-coated on the base material, described ROP-103 is dissolved in the cyclopentanone with the solids concn of 2 weight %.Described LPP solution was at room temperature stirred 30 minutes.

Base material (glass baseplate) is with the spin coating of described LPP solution (under 2000rpm 1 minute).180 ℃ of dryings after 10 minutes, with the polarized light of sample from high pressure Hg Jupiter (100mJ/cm for example with spectral filter ², spectral range is 300-330nm) and irradiation.

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

Described solution was at room temperature stirred 30 minutes, by spin coating (2500rpm-3000rpm, 1min; The about 1.20 μ m of mean thickness) be deposited on this LPP substrates coated, and at T _AN(annealing temperature) annealing 2 minutes.The clarifying temp of described mixture is T _c(in table, providing).Adopt unpolarized UVA light to make described film photopolymerization under air atmosphere at room temperature (500 or 1000mJ/cm subsequently ², lamp intensity=60mW/cm ²), to provide polymeric LC film.Refer to that viscosity is by touching tested sample and writing down described sample and sensuously how to glue (being viscosity) and test with forefinger.Orientation performance and chemical conversion rate are measured as previously described.

Table (I)

Embodiment 7

Additive is to the influence of curing performance

The preparation of film

With described LPP solution spin coating (under 2000rpm 1 minute) base material (glass baseplate).180 ℃ of dryings after 10 minutes, with the polarized light of sample from high pressure Hg Jupiter (100mJ/cm for example with spectral filter ², spectral range is 300-330nm) and irradiation.

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

Described solution was at room temperature stirred 30 minutes, by spin coating (2000rpm-3000rpm, 1min; The about 1.20 μ m of mean thickness) be deposited on this LPP substrates coated, and at T _AN(annealing temperature) annealing 2 minutes.The clarifying temp of described mixture is T _c(in table, providing).Adopt unpolarized UVA light to make described film photopolymerization under air atmosphere at room temperature (500 or 1000mJ/cm subsequently ², lamp intensity=60mW/cm ²), to provide polymeric LC film.Refer to that viscosity is by touching tested sample and writing down described sample and sensuously how to glue (being viscosity) and test with forefinger.Orientation performance and chemical conversion rate are measured as previously described.

Embodiment 8

LCP " alkene " part and functionality are to the influence of curing performance

The preparation of film

Explanation

??A??Al.p.???P???√??0??++??+??0

But the orientation performance multi-thiol (weight %) of air curing but air curing can not air curing the good no contrast gradient of contrast gradient (＜500) of extraordinary contrast gradient (＞500)

Embodiment 9

Studied the art methods of describing by Philips (Journal of SID 12/3,2004), compared with method of the present invention.In order to reappear the result of described prior art, used the acrylate polymerizable LC mixture (composition as listed is in Table A) of standard, and being aggregated in the nitrogen atmosphere of patterning carried out.In order to prevent the polymerization in zone wide (area-wide), must use very little exposure energy according to the description of described prior art.

4 samples have been prepared according to the processing condition of in table B, listing.Washed D263 sheet glass is used as base material.By the spin coating solid content is the solution of ROP-103 (the alignment material of ROLICTechnologies) in cyclopentanone of 2 weight %, has prepared the both alignment layers that dried thickness is about 60nm.Described both alignment layers is subsequently by in thermal treatment 10 minutes under 180 ℃ temperature on the hot plate.Then, make described alignment layer vertically be exposed to linear polymerization UVB light (wavelength 280 and 320nm between).With 3mW/cm ²Intensity apply 150mJ/cm ²Dosage.In next step, will be spin-coated on above the described functionalized alignment layer according to the polymerisable liquid crystal compound based on acrylate Table A (a), standard.Use 25 weight % solution in methyl-phenoxide for this reason.Realize the build of about 800nm by this way.Carry out then the thermal treatment under 40 ℃ of temperature on the hot plate 10 minutes.Then, carry out the radiation curing of patterning.For this reason, make described film be exposed to collimated light by black and white mask with 100 microns bar patens.Described mask is maintained at the surperficial about 15 microns distance apart from described liquid crystal layer.By through described mask with 1,5,10 and 500mJ/cm ²The UV dose exposure come the polymerization sample.Then, carry out developing process, be about to described sample and be immersed in the ethyl acetate 10 seconds, to remove unpolymerized material.Fig. 1 has shown adopted 1mJ/cm in nitrogen atmosphere ²The thickness profile of measurement of dosage polymeric sample (Alpha-stepper 500, and KLA-TencorCorporation), Fig. 2 has shown adopt 10mJ/cm in nitrogen atmosphere ²Dosage polymeric sample thickness profile and Fig. 3 shown and in nitrogen atmosphere, adopted 500mJ/cm ²Dosage polymeric sample thickness profile.

Described in principle patterning is also according to art methods work.But two basic shortcomings are conspicuous:

(1) if the increase of polymerization dosage then lateral resolution reduce (1mJ/cm ²: having and not having the zone of transition between the district of LCP is 7 microns; 5mJ/cm ²: 30 microns zone of transition; 10mJ/cm ²: 45 microns zone of transition), for 500mJ/cm ²To such an extent as to, the polymerization degree of the material in the unexposed area is too high in the developing process process, can not remove fully described material and

(2) if polymerization dosage reduces, then the solvability contrast gradient is quite low, the not inadvertently dissolved (1mJ/cm of promptly quite most polymeric material ²: residual thickness 600nm; 10mJ/cm ²: residual thickness: 800nm).

Therefore, this method only allows to be adjusted in the compromise between the lateral resolution of solvability contrast gradient and pattern.

Prepare another sample according to the present invention.Adopt previously described identical method.But, use and contain the acrylate compound that the unitary liquid crystal compound of mercaptan replaces described standard.The component of described mixture indicates in Table A (b).In order to carry out the exposure of patterning, use 500mJ/cm ²UV dosage.In this case, developing process only causes very little material unaccounted-for (MUF) (＜5%) in the exposure area of described sample, and is removed fully in the developing process process at the described material of unexposed area, and promptly the solvability contrast gradient is very high.And lateral resolution is very high (zone of transition is 5 microns), and shows the much lower dependency to actual processing conditions.Described sample thickness profile is presented among Fig. 4.Processing parameter indicates in table C.

Table A: the component of polymerizable liquid-crvstalline mixture

(a) the acrylate mixture of standard:

(b) acrylate/mercaptan mixture:

Table B: the processing parameter that is used for the acrylate mixture of standard

Base material:	Washed D263 glass (Schott AG)
Base material:	Washed D263 glass (Schott AG)	Both alignment layers:
Material:	ROP-103 (the alignment material derives from ROLIC Technologies)	Both alignment layers:
Material:		Solution:	2%, in cyclopentanone
Spin coating:	2000rpm60 second	Solution:	2%, in cyclopentanone
Spin coating:	2000rpm60 second	Thermal treatment:	180 ℃ 10 minutes, on hot plate
The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²	Thermal treatment:	180 ℃ 10 minutes, on hot plate
The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²	The polymerizable liquid-crvstalline material:
Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃	The polymerizable liquid-crvstalline material:
Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃	Solution:	25%, in methyl-phenoxide
Spin coating:	800rpm60 second	Solution:	25%, in methyl-phenoxide
Spin coating:	800rpm60 second	Thermal treatment:	40 ℃ 10 minutes, on hot plate
The radiation curing of patterning:	1,5,10 and 500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light	Thermal treatment:	40 ℃ 10 minutes, on hot plate
The radiation curing of patterning:		(a) developing method:	Sample be immersed in ethyl acetate bathe in about 10 seconds
(b) second radiation curing at elevated temperatures:	??500mJ/cm ²(UVA and UVB), 50mW/cm ², non-collimated light does not have second radiation curing exposure of mask, and 60 ℃ of temperature in air: ≈ apply and pass through hot plate	(a) developing method:

Table C: the processing parameter that is used for acrylate/mercaptan mixture.

Base material:
Base material:		Both alignment layers:	With identical among the table B
The polymerizable liquid-crvstalline material:		Both alignment layers:	With identical among the table B
The polymerizable liquid-crvstalline material:		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With identical among the table B	The radiation curing of patterning:
(a) developing method:	With identical among the table B	(b) second radiation curing at elevated temperatures:	With identical among the table B

Embodiment 10

Method is according to embodiment 9, and prerequisite is not carry out developing method, but is applying second polymerization (parameter indicates in table B) under the temperature of the clear point that is higher than unexposed LCP zone.

Adopt the acrylate material of described standard, the restriction of low exposure dose is caused such problem, promptly only can realize difference very little between the polymerization degree of exposure area and unexposed area (and therefore the very little difference of clear point).Therefore, be very difficult on the described zone of described sample, make the temperature in unexposed zone just be higher than described clear point and described partially polymerized zone still is lower than described clear point with enough tolerance range controlled temperature.

If described first exposure, promptly the patterned exposure of the acrylate LCP film of described standard adopts 10mJ/cm ²Dosage carry out, and use more the situation of low dosage to compare resolving power significantly to reduce.But on the other hand, the contrast gradient of clear point has been sizable between exposure and unexposed area.Yet, found the unexposed striped and the interfringe contrast gradient of exposure that reduce.Be aggregated under the situation of carrying out under 50 ℃ the temperature described second, find residual birefringence in described unexposed striped, it is isotropic by inference.If apply lower exposure dose as 5 or 1mJ/cm ²To improve described lateral resolution, this shortcoming becomes even is more outstanding.

For the described polymerizable liquid-crvstalline mixture that contains mercaptan, can realize the contrast gradient of clear point between very high exposure and unexposed area.Therefore the 2nd UV exposure at elevated temperatures easily provides have birefringent zone (exposed areas in the patterning polymerization process of the described the first step) and the zone (in the patterning polymerization process of the described the first step not exposed areas) that do not have any residual birefringence.

The result, since when adopting the acrylate LCP of standard with regard to exposure dose and the very limited process window of temperature, employing comprises that but the delay patterning method of LCP material of the air curing of the component with mercaptan or thio-ether units is quite easy, and causes obviously better resolving power.Solvability contrast gradient (developing method) is only arranged or postpone contrast gradient (having) in the second polymeric method more than the clear point and the resolving power of described pattern between compromise can being conditioned.But the major advantage of LCP mixture aspect patterning of air curing is to use the exposure dose that causes the reasonable polymerization degree to be adjusted in the possibility of the transition of polymerization in the LCP film and non-polymeric interregional good qualification.

Embodiment 11: at plastic basis material is that the last patterning of cellulose triacetate (TAC) contains mercaptan The method of the polymerisable liquid crystal compound of component

Processing conditions is listed in table D.

The thickness profile of measuring 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:	TAC (cellulose triacetate) with solvent barrier layer
Base material:	TAC (cellulose triacetate) with solvent barrier layer	Both alignment layers:
Material:	ROP-103 (the alignment material derives from ROLIC Technologies)	Both alignment layers:
Material:		Solution, spin coating:	2%, in MEK, 2000rpm60 second
Thermal treatment:	60 ℃ 10 minutes, on hot plate	Solution, spin coating:	2%, in MEK, 2000rpm60 second
Thermal treatment:	60 ℃ 10 minutes, on hot plate	The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²
The polymerizable liquid-crvstalline material:		The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²
The polymerizable liquid-crvstalline material:		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With ethyl acetate rinsing sample about 10 seconds	The radiation curing of patterning:

Embodiment 12: patterning contains gathering of thiol component on as the silicon wafer of base material Close the liquid crystal compound.

Processing conditions is listed among the table E.

Table E: processing conditions: the patterning on silicon wafer

Base material:	The Si wafer
Base material:	The Si wafer	Both alignment layers:
Material:	ROP-103 (the alignment material derives from ROLIC Technologies)	Both alignment layers:
Material:		Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	The LPUV exposure:	??150mJ/cm ²(UVB), at 3mW/cm ²Down
The polymerizable liquid-crvstalline material:		The LPUV exposure:	??150mJ/cm ²(UVB), at 3mW/cm ²Down
The polymerizable liquid-crvstalline material:		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With ethyl acetate rinsing sample about 10 seconds	The radiation curing of patterning:

Embodiment 13: by the polyimide layer that uses friction make contain thiol component can The patterning of polymerisable liquid crystal compound orientation

At first, with the orientation of polymerizable liquid-crvstalline compound, and carry out patterning method subsequently.Processing conditions is listed among the table F.Can realize perfect orientation by this method.The thickness profile of measuring after development confirms that described patterning method works in a preferred manner.

Table F: processing conditions: have the polyimide that rubbed patterning on glass as both alignment layers

Base material:	Washed D263 glass
Base material:	Washed D263 glass	Both alignment layers:
Material:	??Nissan?SE-150	Both alignment layers:
Material:	??Nissan?SE-150	Spin coating:	2000rpm60 second
Thermal treatment:	80 ℃ 15 minutes, 250 ℃ 50 minutes	Spin coating:	2000rpm60 second
Thermal treatment:	80 ℃ 15 minutes, 250 ℃ 50 minutes	Friction treatment
The polymerizable liquid-crvstalline material:		Friction treatment
The polymerizable liquid-crvstalline material:		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With sample be immersed in ethyl acetate bathe in about 10 seconds	The radiation curing of patterning:

Embodiment 14: come orientation directly to be coated on the TAC base material by the TAC base material that uses friction On the patterning of the polymerisable liquid crystal compound that contains thiol component

At first, with the orientation of polymerizable liquid-crvstalline compound, and carry out patterning method subsequently.Processing conditions is listed among the table G.Can realize perfect orientation by this method.The thickness profile of measuring after development confirms that described patterning method works in a preferred manner.

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

Base material:	TAC (cellulose triacetate)
Base material:	TAC (cellulose triacetate)	Both alignment layers:
Material:	No extra play	Both alignment layers:
Material:	No extra play	Friction treatment
The polymerizable liquid-crvstalline material:		Friction treatment
The polymerizable liquid-crvstalline material:		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??500mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With sample be immersed in ethyl acetate bathe in about 10 seconds	The radiation curing of patterning:

15: two or three different length of delays (isotropy or certain Δ nd) of embodiment Method of patterning

The binary of using according to embodiment 15 in the stacked body of two polymeric liquid crystal layers (one is to be patterning with one uniformly) postpones patterning method, and two kinds of different length of delays can be conditioned (delay that the delay of the first layer and the delay of the first layer add the second layer).In this embodiment, do not require additional alignment layer, because described additional LCP can be by the direct orientation of LCP layer of following even orientation.

But, the additional alignment layer that is used for described second liquid crystalline polymer layer is brought additional degrees of freedom, it for example allows to regulate three kinds of different length of delays, if described alignment layer is with the mode LPUV of patterning exposure, optionally to shift 0 ° and 90 ° of orientations liquid crystal molecule extremely atop of optic axis.Described three kinds of different length of delays provide by following means: 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 delay of the second layer.This method has been represented the combination of digital delay patterning and azimutal orientation patterning in two LCP layer methods.

Be shown among Fig. 5 with the digital delay patterning of the azimutal orientation patterning of the 2nd LCP layer combination.Contrast with the description among Fig. 5, the alignment of the patterning by LPP1 come the azimutal orientation of patterning the one LCP layer and then the delay of the 2nd LCP layer of the even orientation of patterning also be possible.In this way, also can regulate three kinds of different length of delays.In addition, a described LCP layer can have the variable azimutal orientation that identical optical delay level is arranged.If the value of the azimutal orientation of described patterning is not limited to 0 ° and 90 °, can regulate the different local birefringence character that surpasses three kinds or four kinds.The photic orientation of the patterning by allowing two LCP layers and the additional delay patterning of the second layer, described degree of freedom is further increased.Be not developed at described film under the situation of (i.e. part remove), use complanation (planarization) layer to cover if perhaps described film is developed subsequently, the patterning of the delay of two LCP layers also be possible.

The method that use is developed in ethyl acetate and prepared sample according to the above polymeric method of clear point that the working method in table 8 and 9 is described in unexposed area.

Table H: processing conditions: the delay patterning with two LCP layers: the orientation of the 2nd LCP layer is perpendicular to the orientation of the first layer

Base material:	Washed D263 glass
Base material:	Washed D263 glass	Both alignment layers: the first layer
Material:	ROP103 (the alignment material derives from ROLIC)	Both alignment layers: the first layer
Material:	ROP103 (the alignment material derives from ROLIC)	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	The LPUV exposure:	150mJ/cm ²(UVB)，3mW/cm ²
Polymerizable liquid-crvstalline material: the first layer		The LPUV exposure:	150mJ/cm ²(UVB)，3mW/cm ²
Polymerizable liquid-crvstalline material: the first layer		Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃
Solution, spin coating:	40%, in methyl-phenoxide, 1000rpm60 second	Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃

Thermal treatment:	40 ℃ 10 minutes, on hot plate
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Radiation curing:	??5J/cm ²(UVA and UVB), 50mW/cm ², non-collimated light, no mask is in nitrogen atmosphere
Both alignment layers: the second layer		Radiation curing:
Both alignment layers: the second layer		Material:	ROP103 (the alignment material derives from ROLIC)
Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second	Material:	ROP103 (the alignment material derives from ROLIC)
Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second	Thermal treatment:	180 ℃ 10 minutes
The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ², perpendicular to the first both alignment layers orientation	Thermal treatment:	180 ℃ 10 minutes
The LPUV exposure:		Polymerizable liquid-crvstalline material: the second layer
Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃	Polymerizable liquid-crvstalline material: the second layer
Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃	Solution, spin coating:	25%, in methyl-phenoxide, 800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Solution, spin coating:	25%, in methyl-phenoxide, 800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??1J/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:		The radiation curing of patterning:
(a) developing method:			With sample be immersed in ethyl acetate bathe in about 10 seconds
(b) second radiation curing at elevated temperatures:
(b) second radiation curing at elevated temperatures:		Radiation curing:	??500mJ/cm ²(UVA and UVB), 50mW/cm ², the no mask of non-collimated light second radiation curing exposure is in air
Temperature:	60 ℃ of ≈ utilize hot plate to apply	Radiation curing:

In an example, use second alignment layer, prepare the vertical optic axis (table H) of this second alignment layer to induce first and second liquid crystalline polymer layer.In this embodiment, the observations of the sample between crossed polarizers shown corresponding to by the given delay of the difference between the delay level of described two LCP films than dark areas and corresponding to the delay of described (promptly not patterning) uniformly liquid crystalline polymer film only than bright area.

In second example, between described 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 the described first polymeric film orientation.Observations between orthogonal polarizer shows, produced to have corresponding to the zone of the higher delay value of two length of delay sums of described two liquid crystalline polymer film and have zone corresponding to the low length of delay of the length of delay of the liquid crystalline polymer film of the not patterning below only.

If the alignment direction of the second layer is utilized LPUV exposure (0 ° or the 90 °) definition in addition of the patterning of alignment layer, can realize having the film of the arbitrary graphic pattern of three kinds of different optical delay values.

Table I: processing conditions: the delay patterning with two LCP layers: the orientation of the 2nd LCP layer is perpendicular to the orientation of the first layer.

Base material:	Washed D263 glass
Base material:	Washed D263 glass	Both alignment layers:
Material:	ROP103 (the alignment material derives from ROLIC)	Both alignment layers:
Material:	ROP103 (the alignment material derives from ROLIC)	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²
Polymerizable liquid-crvstalline material: the first layer		The LPUV exposure:	??150mJ/cm ²(UVB)，3mW/cm ²
Polymerizable liquid-crvstalline material: the first layer		Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃
Solution:	40%, in methyl-phenoxide	Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃
Solution:	40%, in methyl-phenoxide	Spin coating:	1000rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	1000rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Radiation curing:	??5J/cm ²(UVA and UVB), 50mW/cm ², non-collimated light, no mask is in nitrogen atmosphere
Polymerizable liquid-crvstalline material: the second layer		Radiation curing:
Polymerizable liquid-crvstalline material: the second layer		Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	30%, in methyl-phenoxide	Material:	Acrylate/mercaptan mixture (Table A (b)), T _c≈44℃
Solution:	30%, in methyl-phenoxide	Spin coating:	1000rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	1000rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??1J/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air atmosphere
(a) developing method:	With sample be immersed in ethyl acetate bathe in about 10 seconds	The radiation curing of patterning:
(a) developing method:		(b) second radiation curing at elevated temperatures:	??500mJ/cm ²(UVA and UVB), 50mW/cm ², 60 ℃ of non-collimated light temperature: ≈ utilize hot plate to apply

Embodiment 16: the delay patterning that adopts grey mask radiation curing

Allowing patterned retardation to the simple method of two or more different length of delays all is very useful for various application.Because the advantage above-mentioned of described acrylate/mercaptan patterning method, the several methods with such patterning of variable delay value is feasible.

A kind of possibility is to use the horizontal mask of grey, and the local pattern of its transmitted radiation intensity is to the liquid crystal monomer film that is aggregated.So the intensity pattern that produces causes the pattern of the polymerization degree on described sample area.First method that the pattern that is used to shift the described polymerization degree becomes the pattern of optical delay is to carry out second radiation curing at elevated temperatures.Depend on the polymerization degree, the optical delay in each part (partition) of described film will reduce certain amount.Strong polymeric zone will show only little reduction, and weak polymeric zone will experience sizable reduction or lose optical delay fully.In order to allow to regulate the optical delay value of described hope, the possibility that this method requires accurate controlled temperature and accurately regulate described temperature on described sample area.

Another possibility is described film to be immersed in to develop in the suitable solvent utilize the horizontal mask polymeric of grey film.In this embodiment, the LCP material will be removed according to the local polymerization degree, and therefore shows the pattern of optical delay.

Present embodiment comprises described second method.The application technology Argument List is in table J and K.Each sample is made up of four zones, and specified different exposure dose polymerization among the table J is adopted in described zone.Be aggregated under the situation of carrying out in the nitrogen atmosphere described, described patterning method is invalid.But adopt acrylate/thiol material, described patterning method effect is fine.Four kinds of different delay levels can be conditioned.The described sample that comprises the value of the value of exposure dose of described acrylate/mercaptan mixture and optical delay is displayed among Fig. 6.Described result shows that by this method, described delay can be by the intermittent patternization with non-constant width.Depend on application, the post polymerization method behind described developing method may need, to improve the overall polymerization degree.

Table J: processing conditions: the delay patterning that adopts grey mask radiation curing: the acrylate liquid crystal polymer material of standard

Base material:	Washed D263 glass
Base material:	Washed D263 glass	Both alignment layers: the first layer
Material:	ROP103 (the alignment material derives from ROLIC)	Both alignment layers: the first layer
Material:	ROP103 (the alignment material derives from ROLIC)	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	Solution, spin coating:	2%, in cyclopentanone, 2000rpm60 second
Thermal treatment:	180 ℃ 10 minutes	The LPUV exposure:	??150mJ/cm ²(UVB)，mW/cm ²
Polymerizable liquid-crvstalline material: the second layer		The LPUV exposure:	??150mJ/cm ²(UVB)，mW/cm ²
Polymerizable liquid-crvstalline material: the second layer		Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃
Solution:	25%, in methyl-phenoxide	Material:	The acrylate mixture of standard (Table A (a)), T _c≈55℃
Solution:	25%, in methyl-phenoxide	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	Spin coating:	800rpm60 second
Thermal treatment:	40 ℃ 10 minutes, on hot plate	The radiation curing of patterning:	??1J/cm ², 6,1 and 0mJ/cm ²(UVA and UVB), 8mW/cm ², collimated light is in air
(a) developing method:	With sample be immersed in ethyl acetate bathe in about 10 seconds	The radiation curing of patterning:

Table K: processing conditions: the delay patterning that adopts grey mask radiation curing: acrylate/mercaptan mixture

The same process conditions that provides among the table J, prerequisite is to use described acrylate/mercaptan mixture (Table A (b)), and in order to carry out the radiation curing of patterning, uses air atmosphere to replace nitrogen atmosphere

Claims

Photopolymerization, patterning or the liquid crystalline polymers of patterning not, it comprises the thio-ether units of formula (I)

* covalent linkage, its unit with formula (I) is connected on the rest part of polymkeric substance

Wherein

LC ¹Be selected from liquid crystal residue group,

X ¹Be selected from the organic residue group of aliphatics and

n ¹Be 〉=0 integer and

m ¹Be 〉=0 integer;

Prerequisite is if n ¹Be 0, m so ¹If＞0 and m ¹Be 0, n so ¹＞0; With

It prepares in oxygen-containing atmosphere;

Prerequisite is the liquid crystal that does not comprise polymer dispersed.
2. the described liquid crystalline polymers of claim 1, the residue of wherein said liquid crystal is the polymerized form of liquid crystal, its not polymerized form have at least two polymerizable functional groups with undersaturated carbon-to-carbon or carbon-nitrogen bond.
3. composition (XX), it comprises:

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

Wherein

X ^aBe aliphatic organic residue,

n ^tBe 〉=2 integer and

B) at least a liquid crystal with at least two polymerizable functional groups and

C) randomly at least a reactivity and/or non-reacted additive and

D) randomly at least a initiator and

E) randomly at least a solvent.
4. the method for preparing the described liquid crystalline polymers of claim 1, this method comprises

A) the coating described composition of claim 3 (XX) and then

B) randomly dry and then

C) in oxygen-containing atmosphere, be aggregated in the composition (XXI) of the described coating that obtains after step a) or the step b).
5. Tu Bu composition (XXI), it can be according to the described processing step of claim 4 b a) and randomly) obtain.
6. liquid crystalline polymers, it can obtain in accordance with the method for claim 4.
7. the method for liquid crystalline polymers of preparation patterning, this method comprise claim 5 is described and according to composition (XXI) patterning of the coating of the described preparation of claim 4.
8. the described method of claim 7 comprises the patterning of birefringence patternization and/or thickness patterning and/or optic axis orientation and/or the patterning of the polymerization degree.
9. claim 7 or 8 described methods comprise photopolymerization.
10. the liquid crystalline polymers of patterning, it can obtain by the method described in the claim 7-9.
11. claim 1 or 6 is described or according to the liquid crystalline polymers of the described preparation of claim 4, or the described composition of claim 3 (XX), or the composition of the described coating of claim 5 (XXI), or the liquid crystalline polymers of the described patterning of claim 10 is in preparation patterning and the not optics of patterning or the purposes in sealed cell, system or the device.
12. the not optics of patterning or patterning or sealed cell, system or device, it is described or according to the liquid crystalline polymers of the described preparation of claim 4 that it comprises claim 1 or 6, or the liquid crystalline polymers of the described patterning of claim 10, or the liquid crystalline polymers of the described patterning of claim 7-9.
13. the optics or the sealed cell of described not patterning of claim 12 or patterning are used for waveguide, safety or trademark protection element, barcode; grating, spectral filter, delayer; compensate film, reflective polarizer films, absorbing polarization film; compensation of anisotropic scattering film and phase shift films, the delayer film that reverses, cholesteric liquid crystal film; guest of honour's type liquid crystal film; the monomer ripple film, smectic liquid crystal film, polarizer; the piezoelectricity pond; the film that shows nonlinear optical property, ornamental optical element, brightness improves film; the element that is used for the compensation of wavelength band selectivity; the element that is used for the multizone compensation, the element of multi-view angle LCD, colour killing delayer; polarization state correction/adjusting film; the element of optics or photo-sensor, brightness improves the element of film, is used for the element of light base telecommunication device; G/H-polarizer with patterning of anisotropic absorption agent; the reflection circle polarizer of patterning, the reflection linear polarization of patterning, the purposes of the MC of patterning (monomer ripple film).
14. comprise the described not patterning of claim 12 or the optics of patterning or the device of sealed cell.