Photoactive polymers

专利摘要:
The present invention relates to photoactive polymers of formula (I). Formula I In the above formula (I) P is a photoactive group that can be photoisomerized and / or photo- B represents an aromatic or alicyclic group, a nitrogen atom or -CR 2 - A, C and D independently represent an aromatic or alicyclic group, M represents a repeating monomer unit in the homopolymer or copolymer, S 1 , S 2 , S 3 , S 4 and S 5 represent a single covalent bond or a spacer unit, n 1 and n 2 are each independently a positive integer of 2 or less, provided that n 1 + n 2 is 2 or less, R 1 is a hydrogen atom or a straight or branched chain alkyl residue wherein R 2 is a hydrogen atom or lower alkyl. The photoactive polymer can be used as an alignment layer for liquid crystals and in the production of unstructured and structural optical elements and multilayer systems.
公开号:KR20010108454A
申请号:KR1020017012704
申请日:2000-03-27
公开日:2001-12-07
发明作者:자이베를레후베르트；마르끄기；뮬레르올리비에
申请人:보러 롤란드；롤리크 아게；
IPC主号:

专利说明:

Photoactive polymers {Photoactive polymers}
[1] The present invention relates to novel photoactive polymers, to alignment layers for liquid crystals and to their use in the production of unstructured and structural optical elements and in multi-layer systems.
[2] The different electro-optical effects used in a liquid crystal display (LCD) require an alignment layer with a very high pretilt angle. For example, a vertically aligned nematic (VAN) LCD requires a pre-tilt angle of 85 [deg.] To 90 [deg.] From the surface. In the case of a hybrid aligned nematic (HAN) LCD, the pretilt angle of one of the substrates is equal to the range, while the tilt angle of the remaining substrate is low (typically 0 to 10 degrees). Brushed polyimides capable of inducing high pretilt angles have known disadvantages of brushing techniques. In the case of VAN-LCDs, scratching, especially by brushing and insufficient pre-tilt angle homogenization, is a well known problem of brushing technology. On the other hand, a stable optically-alignable material for high pretilt angles to overcome the above problems is not yet known.
[3] Most known electro-optic LCD-modes exhibit residual birefringence of the liquid crystal layer resulting in reduced contrast, intrinsic hue and / or limited viewing angle. The optical retarder is applied to the LCD to offset the residual birefringence. The tilted LC-shape formed by applying a voltage to the LCD is used in most commercially available LCDs to adjust the achromatic scale. The highly asymmetric view of this tilted LC shape is optimally canceled as the optical axis of the canceling retarder tilts. A liquid crystal polymer (LCP) optically aligned by LPP-material prior to polymerization is perfectly suited for such applications because the slope of the optical axis can be adjusted to any value between 0 and 90 degrees by the adjacent alignment layer. A disadvantage of known alignment materials which induce very high pretilt angles is that their high surface tension causes wetting problems. Consequently, it is impossible to coat a homogeneous layer of LCP-prepolymer on top of this alignment layer.
[4] European Patent Publication No. 0 611 786 [ Hoffmann-La Roche AG) describes polymers having isomerization / dimerization units of the formula (Ia): < EMI ID = 4.1 >
[5]
[6] In the above formula (Ia)
[7] M _a , M _b and M _c represent monomer units for homopolymers or copolymers,
[8] x, y and z are in each case 0 < x &lt; 0 &lt; y &lt; 1 and 0 &lt; z &lt;
[9] Sa and Sb represent spacer units,
[10] Za and Zb represent molar units capable of performing photochemical isomerization / dimerization,
[11] n is from 4 to 100,000,
[12] m is 0 or 1;
[13] These linear and cyclic polymers or oligomers have photoreactive ethene groups for use as alignment layers for liquid crystals.
[14] WO A 96/10049 (F. Hofmann-La Roche) describes polymers of formula (Ib).
[15]
[16] In the above formula (Ib)
[17] M ¹ and M ² represent monomer units for homopolymers or copolymers,
[18] x and y represent, in each case, the molar fraction of comonomers with 0 < x < 1, 0 y &lt; 1 and x + y =
[19] p represents 4 to 30,000,
[20] S ¹ and S ² represent spacer units,
[21] Q ¹ represents a structural unit of formula (IIa)
[22] Q ² represents a structural unit of formula (IIb)
[23] A and B are each independently selected from the group consisting of pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane- 4-phenylene,
[24] Z ¹ and Z ² each independently represent a single covalent bond, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CONR-, -RNCO-, -COO- or -OOC-,
[25] R represents hydrogen or lower alkyl,
[26] R ¹ represents hydrogen, optionally substituted C 1 -C 12 alkyl or alkoxy, cyano, nitro or halogen,
[27] z represents 0 or 1,
[28] C represents a photochemically dimerizable coumarin or quinolinone derivative,
[29] m and n are each independently 0 or 1;
[30] _{^{-A- (Z 1 -B) Z -Z}} 2 -
[31] _{^{-A- (Z 1 -B) Z -Z}} 1 -
[32] These linear and cyclic polymers or oligomers of coumarin and quinolinone derivatives have photoreactive ethene groups and can be used as alignment layers for liquid crystals.
[33] European Patent Publication No. 0 763 552 (Rolic AG) describes a polymer composition having repeating units of formula (Ic).
[34]
[35] In formula (Ic) above,
[36] M ¹ is selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide and 2-phenylacrylamide, , Vinyl esters, styrene derivatives and siloxane groups,
[37] S ¹ is, for example, a single covalent _{bond, - (CH 2) r,} - (CH 2) r -O-, - (CH 2) r -O- (CH 2) s -, - (CH 2) r _{-O- (CH 2) s -O-,} - (CH 2) r -CO-, - (CH 2) r -CO-O-, - (CH 2) r -O-CO-, - (CH 2 ) _r -NR ² -, - (CH ₂ ) _r -CO-NR ² -, - (CH ₂ ) _r -NR ² -CO-, - (CH ₂ ) _r -NR ² -CO- CH ₂ ) _r -NR ² -CO-NR ³ , wherein the group is optionally mono- or poly-substituted by fluorine, chlorine or cyano, r and s are each 1 With the proviso that r + s is not more than 20 and R ² and R ³ are each independently hydrogen or lower alkyl,
[38] Ring A is unsubstituted or substituted with one or more substituents selected from the group consisting of fluorine, chlorine, cyano, alkyl or alkoxy, pyridin-2,5-diyl, pyrimidine- -1,4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl,
[39] Ring B is unsubstituted or substituted with one or more substituents selected from the group consisting of fluorine, chlorine, cyano, alkyl or alkoxy, pyridin-2,5-diyl, pyrimidine-2,5-diyl, 1,4- or 2,6- Dioxane-2,5-diyl, phenylene substituted by cyclohexane-1,4-diyl,
[40] Y ¹ and Y ² each independently represents a single covalent bond, - (CH ₂ ) _t , -O-, -CO-, -CO-O-, -O-OC-, -NR ⁴ -, -CO-NR ^{4 -, -R 4 N-CO-,} - (CH 2) u -O-, -O- (CH 2) u -, - (CH 2) u -NR 4 - or -NR ⁴ - (CH _{2) u} - wherein R ⁴ represents hydrogen or lower alkyl, t is an integer from 1 to 4, and u is an integer from 1 to 3,
[41] m and n each independently represent 0 or 1,
[42] Ring C is unsubstituted or substituted with at least one substituent selected from the group consisting of fluorine, chlorine, cyano, alkyl or alkoxy, pyrimidine-2,5-diyl, pyridine- Phenylene substituted with 1,4- or 2,6-naphthylene,
[43] Z is -O- or -NR &lt; ⁵ &gt; wherein R &lt; ⁵ &gt; is hydrogen, lower alkyl or a second group of formula D,
[44] D represents a straight or branched alkylene group of 1 to 20 carbon atoms optionally substituted with fluorine or chlorine or a cycloalkyl moiety having 3 to 8 carbon atoms optionally substituted by fluorine, chlorine, alkyl or alkoxy.
[45] These crosslinkable photoactive polymer materials having 3-aryl acrylate and amides are used as alignment layers for liquid crystals and can be used for the production of unstructured and structural optical elements and multilayer systems.
[46] EP-A-0 860 455 (Rolling Agent) describes a polymer of the formula Id.
[47]
[48] In the above formula (Id)
[49] M ¹ and M ^{1 '} are independently selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, optionally lower alkyl N-substituted acrylamide, methacrylamide, 2-chloroacrylamide, Amide, vinyl ether, vinyl ester, styrene derivatives and siloxane groups,
[50] M ² is selected from the group consisting of acrylates, methacrylates, 2-chloroacrylates, 2-phenyl acrylates, optionally lower alkyl N-substituted acrylamides, methacrylamides, 2-chloroacrylamide and 2-phenylacrylamide, , Vinyl esters, linear or branched alkyl esters of acrylic acid or methacrylic acid, allyl esters, alkyl vinyl ethers or esters of acrylic acid or methacrylic acid, phenoxyalkyl acrylates or anoxyalkyl methacrylates, hydroxyalkyl acrylates or hydroxy Alkyl methacrylate, phenylalkyl acrylate or phenylalkyl methacrylate (wherein the alkyl group has 1 to 20 carbon atoms, preferably 5 to 20 carbon atoms, especially 5 to 18 carbon atoms), acrylonitrile, methacrylonitrile, styrene , Repeating monomer units from 4-methylstyrene or siloxane groups Lt; / RTI &gt;
[51] w, w ¹ and w ² are molar fractions of the comonomers, ^{0 <w ≤1, 0 ≤w 1} <1 and 0 ≤w ² ≤0.5,
[52] S ¹ and S ^{1 '} independently of one another are fluorine, chlorine or cyano, straight or branched alkylene group - (CH ₂ ) _r -, or - (CH ₂ ) _r --L - (CH ₂ ) _s - , L is a single bond or ^{-O-, -COO-, -OOC-, -NR 1} -, -NR 1 -CO-, -CO-NR 1 -, -NR 1 -COO-, -OCO-NR 1 - , -NR ¹ -CO-NR ¹ -, -CH = CH- or -C≡C- (wherein R ¹ is hydrogen or lower alkyl), r and s are each 1 to 20 , With the proviso that r + s is not more than 24,
[53] D and D 'are independently of each other -O- or -NR ² -, wherein R ² is hydrogen or lower alkyl,
[54] X, X ', Y and Y' independently of one another can be optionally substituted with hydrogen, fluorine, chlorine, cyano or fluorine, and one CH ₂ group or a majority of non-adjacent CH ₂ groups can be replaced by O, -COO- , -OOC- and / or -CH = CH-, and R &lt; 2 &gt;
[55] A and A 'independently of one another are phenylene optionally substituted by fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy, pyridin-2,5-diyl, pyrimidine-2,5-diyl Dioxane-2,5-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, 1,3-dioxane- , 4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl,
[56] B and B 'independently of one another are phenylene optionally substituted by fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy, piperidin-2,5-diyl, pyrimidine-2,5 Diyl, 1,4- or 2,6-naphthylene, 1,3-dioxane-2,5-diyl or cyclohexane-1,4-diyl,
[57] C and C 'independently of one another are phenylene optionally substituted by fluorine, chlorine, cyano, alkyl, alkoxy or fluoroalkoxy, pyrimidine-2,5-diyl, pyridin- , 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene,
[58] The K and K 'are independently optionally substituted with H, F, Cl, cyano, nitro, or a fluorine, chlorine, cyano or nitro one another, CH ₂ group, or a majority of the non-adjacent CH ₂ groups -O-, - Alkyl-COO-, alkyl-CO-NR ³ or alkyl-OCO- group of 1 to 20 carbon atoms which may optionally be substituted by -O-, -CH═CH- or -C≡C-, R &lt; ³ &gt; is hydrogen or lower alkyl,
[59] Provided that at least one ring A, B, C and / or at least one ring A ', B', C 'represents a phenylene group substituted with at least one alkoxy group or fluoroalkoxy group, and K represents alkoxy or fluoroalkoxy , One or more rings A, B, C and / or one or more rings A ', B', C 'represent a phenylene group substituted with one or more additional alkoxy groups or fluoroalkoxy groups,
[60] Z, Z ', Z ¹ and Z ^1' are independently a single covalent bond to each other _{- (CH 2) t -,} -O-, -CO-, -CO-O-, -O-OC-, -NR 4 -, -CO-NR ⁴ -, -R ⁴ N-CO-, - (CH ₂ ) _u -O-, -O- (CH ₂ ) _u -, - (CH ₂ ) _u -NR ⁴ - or -NR ⁴ - (CH ₂ ) _u -, wherein R ⁴ is hydrogen or lower alkyl, t is an integer of 1 to 4 and u is an integer of 1 to 3,
[61] p, p ', n and n' independently of each other represent 0 or 1.
[62] These crosslinkable photoactive polymers can be used for the production of alignment layers for liquid crystals and unstructured and structural optical elements and multilayer systems.
[63] The present invention provides optically active or inert photoactive polymers of formula (I).
[64]
[65] In the above formula (I)
[66] P is a photoactive group that can be photoisomerized and / or photo-
[67] B is a cyclic, straight or branched chain alkyl residue of 1 to 18 carbon atoms which is unsubstituted or substituted by fluorine, chlorine or cyano, unsubstituted or mono- or polysubstituted by cyano or halogeno, , one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 ^{-, -NR 2 -CO-, -CO-} NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = CH-, -C≡C- or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or a lower alkyl, by reacting an aromatic or alicyclic group Or further represents a nitrogen atom or -CR ² -,
[68] A, C and D are independently of each other unsubstituted or substituted by fluorine, chlorine or cyano, cyclic, substituted or unsubstituted, mono- or polysubstituted by cyano or halogeno, straight or branched chain alkyl moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3 ^{_{) 2 -, -NR 2 -,}} -NR 2 -CO-, -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 - , -CH = CH-, -C C- or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or lower alkyl Aromatic or alicyclic group,
[69] M represents a repeating monomer unit for a homopolymer or a copolymer,
[70] S ¹ , S ² , S ³ , S ⁴ and S ⁵ are a single covalent bond, a straight or branched alkylene having 1 to 24 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, ^{-NR 2 -, -NR 2 -CO-,} -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = (-CO-, -CH-, -C C- or -O-CO-O-, with the proviso that oxygen atoms are not directly bonded to each other and R ² represents a hydrogen atom or a lower alkyl) spacer unit,
[71] n ¹ and n ² are each independently a positive integer of 2 or less, provided that n ¹ + n ² is 2 or less,
[72] R ¹ is a hydrogen atom, a straight or branched alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, wherein one or more CH ₂ groups are independently -O -, -CO-, -CO-O-, -O-CO-, -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, -NR ² -, -NR ² -CO-, -CO -NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH═CH-, -C≡C- or -O- O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or lower alkyl.
[73] The present invention also provides the use of polymers of formula I as alignment layers for liquid crystals and in the production of unstructured and structural optical elements and multilayer systems.
[74] The novel photoreactive material exhibits excellent linearity and induces a very high pretilt angle in the liquid crystal layer in the LCD.
[75] Surprisingly, these materials can be easily coated using LCP-prepolymer without wetting problems. For example, the pretilt angle of the optical longitudinal axis of the LCP-layer in the liquid crystal cell is very high. Sometimes the tilt area observed in the tilted LCP-layer does not appear.
[76] Preferred photoactive groups P carry out the ring-opening and have the following groups of formulas II and III.
[77]
[78]
[79] In the above formulas (II) and (III)
[80] The broken line represents the binding site for S ¹ ,
[81] E is unsubstituted or substituted by fluorine, chlorine or cyano, or a cyclic, linear or branched alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR ^{2 -, -NR 2 -CO-, -CO} -NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = CH- , -C≡C- or -O-CO-O-, with the proviso that the oxygen atoms do not directly bond to each other and R ² represents hydrogen atom or lower alkyl) , Further pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene or 1,4- or 2,6-naphthylene,
[82] F is -OR ⁴ , -NR ⁵ R ⁶ wherein R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or a cyclic group having 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, , Straight or branched chain alkyl residues wherein one or more CH ₂ groups may be independently replaced by -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, Oxygen atoms do not directly bond to each other), or R ⁵ and R ⁶ bond together to form an alicyclic ring having 5 to 8 atoms], or oxygen which bonds to ring E at the ortho position to form a coumarin unit &Lt; / RTI &gt;
[83] X and Y are each independently of the other hydrogen, fluorine, chlorine, cyano or alkyl of 1 to 12 carbon atoms optionally substituted with fluorine, wherein one or more non-adjacent CH ₂ groups are replaced by -O-, -CO- O-CO- and / or -CH = CH-,
[84] R ³ is a hydrogen atom, a straight or branched alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, wherein one or more CH ₂ groups are independently - O-, -CO-, -CO-O-, -O-CO-, -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, -NR ² -, -NR ² -CO-, -CO-NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH = CH-, -C≡C- or -O-CO -O-, with the proviso that the oxygen atoms do not directly bond to each other and R ² represents a hydrogen atom or a lower alkyl.
[85] Particularly preferred photoactive groups P have the following groups of formulas VI and V:
[86]
[87]
[88] In the above formulas IV and V,
[89] The broken line represents the binding site for S ¹ ,
[90] R ³ is as defined for formulas II and III,
[91] F is -OR ⁴ or -NR ⁵ R ⁶ wherein R ⁴ and R ⁵ are cyclic, linear or branched alkyl residues of 1 to 18 carbon atoms which are unsubstituted or mono- or polysubstituted by halogeno, Wherein one or more CH ₂ groups may be independently replaced with -O- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other, and R ⁶ is a hydrogen atom, Straight or branched chain alkyl residues of 1 to 18 carbon atoms, wherein one or more CH ₂ groups may be independently replaced by -O- or -CH = CH- And R &lt; ⁵ &gt; and R &lt; ⁶ &gt; together form an alicyclic ring having 5 to 8 atoms,
[92] E is a cyclic, linear or branched alkyl residue of 1 to 12 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, wherein one or more CH ₂ groups are independently -O-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other Pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene .
[93] Particularly preferred photoactive groups P are straight or branched alkyl residues of 1 to 6 carbon atoms in which E is unsubstituted or mono- or poly-substituted by fluorine, wherein one or more CH ₂ groups are independently -O-, -CO-, - CO-O-, -O-CO- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other), or further pyrimidin-2 Diyl, pyridine-2,5-diyl, 2,5-furanylene, 1,4- or 2,6-naphthylene,
[94] Wherein F is -OR ⁴ or -NHR ⁵ wherein R ⁴ and R ⁵ are unsubstituted or mono- or polysubstituted C 1 -C 18 cyclic, linear or branched alkyl residues, wherein one or more CH ₂ Group may be independently substituted with -O-, with the proviso that the oxygen atoms are not directly bonded to each other.
[95] Preferred polymers of formula (I) are those of formula (I) wherein a) B represents an aromatic or alicyclic group and n ¹ + n ² is 1,
[96] b) a polymer of formula (I) wherein B represents an aromatic or alicyclic group, and n ¹ + n ² is 0,
[97] c) group B is a group -CR²-, 0 < n^One+ n²&Lt; / RTI &gt; &lt; RTI ID = 0.0 &gt;
[98] d) optically inactive polymers of formula (I).
[99] Preferred groups B are unsubstituted or substituted by fluorine, chlorine or cyano, or cyclic, straight-chain or branched alkyl residues of 1 to 18 carbon atoms which are unsubstituted or mono- or polysubstituted by cyano or halogeno, Wherein one or more CH ₂ groups may be independently substituted with -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, , Or further represents -CR ² - (wherein R ² represents a hydrogen atom or lower alkyl).
[100] Particularly preferred group B is 1,2,5-benzenetriyl or 1,3,5-benzenetriyl group which is unsubstituted or substituted by fluorine, and spacer group S ⁵ is in 1-position.
[101] Preferred groups A, C and D are unsubstituted or mono- or polysubstituted by fluorine, chlorine or cyano, unsubstituted or mono- or polysubstituted by cyano or halogeno, cyclic, straight-chain Or branched alkyl residues wherein one or more CH ₂ groups are independently -O-, -CO-, -CO-O-, -O-CO-, -CH = CH-, -C C-, CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other, or furthermore phenylene substituted by cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, pyridine Diyl, 1,4- or 2,6-naphthylene.
[102] Particularly preferred groups A, C and D are straight or branched alkyl residues of 1 to 8 carbon atoms which are unsubstituted, substituted by fluorine, unsubstituted or mono- or polysubstituted by fluorine, wherein one or more CH ₂ groups are independently Which may be substituted by -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other , Cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 2,6-naphthylene.
[103] Preferred " spacer units " S ¹ , S ² , S ³ , S ⁴ and S ⁵ of the present invention are a single covalent bond or a monovalent or polyunsaturated moiety - (CH ₂ ) _r - a linear or branched alkylene group, or the formula _{^{-L 1 - (CH 2) r}} -L 2 - or _{^{-L 1 - (CH 2) r}} -L 2 - (CH 2) s -L 3 - in the chain Wherein L ¹ , L ² and L ³ are each independently a single bond or -O-, -CO-O-, -O-CO-, -NR ² -, -NR ² -CO-, NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH = CH-, -C≡C-, -O-CO-O - or -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, wherein R ² is a hydrogen atom or lower alkyl, and r and s are each an integer of 1 to 20 With the proviso that r + s is not more than 24 and the repeating monomer unit M is selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, optionally N-lower alkyl substituted acrylamide, De, 2-chloro acrylamide or 2-phenyl acrylic amide, vinyl ethers, in the case of combined vinyl ester, S ⁵ via a nitrogen atom or an oxygen atom M, which is defined as a part of, such as a maleic acid derivative or fumaric acid derivative, L ¹ is Represents a single bond].
[104] Especially preferred "spacer group" S ¹ of the present ^{invention, S 2, S 3, S} 4 and S ⁵ is _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO _{-, - (CH 2) r} -CO-O-, - (CH 2) r -O-CO-, - (CH 2) r -CO-NR 2 -, - (CH 2) r -NR 2 -CO _{-, - (CH 2) r} -NR 2 -, -O- (CH 2) r -, -CO-O- (CH 2) r -, -O-CO- (CH 2) r -, -NR 2 _{-CO- (CH 2) r -,} -CO-NR 2 - (CH 2) r -, -NR 2 - (CH 2) r -, -O- (CH 2) r -CO-O-, -O _{- (CH 2) r -O-} CO-, -O- (CH 2) r -CO-NR 2 -, -O- (CH 2) r -NR 2 -, -O- (CH 2) r -O _{-, -O- (CH 2) r} -NR 2 -CO-, -NR 2 - (CH 2) r -CO-O-, -NR 2 - (CH 2) r -O-, -NR 2 - ( ^{_{CH 2) r -NR 2 -,}} -NR 2 - (CH 2) r -O-CO-, -CO-NR 2 - (CH 2) r -O-, -CO-NR 2 - (CH 2) r ^{-NR 2 -, -CO-NR 2} - (CH 2) r -O-CO-, -O-CO- (CH 2) r -CO-, -O-CO- (CH 2) r -O-, _{-O-CO- (CH 2) r} -NR 2 -, -O-CO- (CH 2) r -CO-O-, -O-CO- (CH 2) r -CO-NR 2 -, -O ^{_{-CO- (CH 2) r -NR 2}} -CO-, - (CH 2) r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - _{(CH 2) r -O-CO-} (CH 2) s -, - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH ₂ ) _s -, - (CH ₂ ) _r -O- (CH ₂ ) _{s -O-, - (CH 2)} r -CO-O- (CH 2) s -O-, (CH 2) r -O-CO- (CH 2) s -O-, - (CH 2) r _{^{-NR 2 -CO- (CH 2) s}} -O-, - (CH 2) r -NR 2 -CO-O- (CH 2) s -O-, -O- (CH 2) r -O- ( _{CH 2) s -, -O- (} CH 2) r -CO-O- (CH 2) s -, -O- (CH 2) r -NR 2 -CO- (CH 2) s -, -O- ^{_{(CH 2) r -NR 2 -CO}} -O- (CH 2) s -, -O- (CH 2) r -CO-O- (CH 2) s -O-, -O- (CH 2) r -O- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -NR ² -CO- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -NR ² -CO-O _{- (CH 2) s -O-,} -CO-O- (CH 2) r -O- (CH 2) s - or _{-CO-O- (CH 2) r} -O- (CH 2) s -O -, wherein r and s are each an integer from 1 to 20, in particular from 2 to 12, with the proviso that r + s is not more than 21, in particular not more than 15, and R ² is hydrogen or lower alkyl; to be.
[105] Most preferred "spacer ^{units" S 1, S 2, S} 3, S 4 and S ⁵ is _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO-O- _{, - (CH 2) r -O} -CO-, - (CH 2) r -CO-NH-, - (CH 2) r -NH-CO-, -O- (CH 2) r -, -CO- _{O- (CH 2) r -,} -CO-NH- (CH 2) r -, -O-CO- (CH 2) r -, -O-CO- (CH 2) r -CO-O-, - _{0- (CH 2) r -O-} CO-, -O- (CH 2) r -CO-NH-, -O- (CH 2) r -NH-CO-, -CO-O- (CH 2) _{r -O-, -CO-NH- (CH} 2) r -O-, -O- (CH 2) r -O-, - (CH 2) r -NH-CO- (CH 2) s -, - _{(CH 2) r -NH-CO} -O- (CH 2) s -, - (CH 2) r -O- (CH 2) s -O-, - (CH 2) r -NH-CO- (CH _{2) s -O-, - (CH} 2) r -NH-CO-O- (CH 2) s -O-, -O- (CH 2) r -NH-CO- (CH 2) s -, - _{O- (CH 2) r -O- (} CH 2) s -O-, -O-CO- (CH 2) r -O- (CH 2) s -O-, -CO-O- (CH 2) _{r -O- (CH 2) s -O-} , -O- (CH 2) r -NH-CO- (CH 2) s -O- , or _{-O-CO- (CH 2) r} -NH-CO- (CH _{2) s} -O- straight chain alkylene group of (wherein, r and s is an integer from 2 to 12, respectively, and the sum of r and s is 15 or less).
[106] Examples of preferred "spacer units" S ¹ , S ² , S ³ , S ⁴ and S ⁵ are 1,2-ethylene, 1,3-propylene, 1,4-butylene, Hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl Butylene, 3-propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5- Pentylenecarbonyloxy, 7-heptylenoxy, 7-pentylenecarbonyloxy, 6-hexylenecyclohexyl, 5-pentylenecarbonyloxy, 7- Heptylenecarbonyloxy, 9-nonylenoxy, 9-nonylenecyclohexenyl, 8-octylenecarbonyl, 8-octylenecyclohexyl, Octylcarbonyloxy, 10-decylenecarbonyloxy, 10-decylenecarbonyl, 9-nonylenecarbonyloxy, 11-undecylenoxy, 11-undecylenecyclo- Oxy, 12-dodecyleneoxy, 12- Propyleneiminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleniminocarbonyl, 6-hexyleniminocarbonyl, 7-pentyleniminocarbonyl, -Heptyleniminocarbonyl, 8-octyleniminocarbonyl, 9-nonyleniminocarbonyl, 10-decyleniminocarbonyl, 11-undecyleniminocarbonyl, 12-dodecylenimino Propylene carbonylimino, 4-butylene carbonylimino, 5-pentylene carbonylimino, 6-hexylenecarbonylimino, 7-heptylene Octenylcarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6- (3-propyliminocarbonylamino, 6- (3-propylenoxy) hexylenoxy, 6- (3-propyliminocarbonyloxy) hexylenoxy, 6- Propyleneiminocarbonyl) hexyl, 6- (3-propyliminocarbonyl) hexyloxy, 1,2-ethylenedioxy Propylenedioxy, 1,4-butylenedioxy, 1,5-pentenedendioxy, 1,6-hexylenedioxy, 1,7-heptylenedioxy, 1,8-octenediyloxy 1,9-nonylenedioxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy, and the like.
[107] A preferred group R ¹ is a hydrogen atom, or is optionally substituted, a halogeno or poly-halogeno straight or branched chain alkyl moiety of the substituted group having 1 to 12 carbon atoms to be (where one or more CH ₂ groups are independently selected from -O-, -CO- , -CO-O-, -O-CO-, -CH = CH- or -C C-, with the proviso that the oxygen atoms are not directly bonded to each other.
[108] Particularly preferred groups R ¹ are linear or branched alkyl residues having 1 to 8 carbon atoms wherein one or more CH ₂ groups are independently -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other. For example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, allyl, -Hexyloxy, 3-methylpentyloxy, but-3-enyloxy, pent-4-enyloxy and the like, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy,
[109] Preferred repeating monomer units M are selected from the group consisting of acrylate, methacrylate, 2-chloroacrylate, 2-phenyl acrylate, optionally N-lower alkyl substituted acrylamide, methacrylamide, 2-chloroacrylamide, , Vinyl ethers, vinyl esters, styrene derivatives, siloxanes, imides, amic acid and esters thereof, amideimides, maleic acid derivatives and fumaric acid derivatives.
[110] Particularly preferred repeating monomer units M are acrylates, methacrylates, optionally N-lower alkyl substituted acrylamides, methacrylamides, vinyl ethers, vinyl esters, styrene derivatives, imides, amic acid and esters thereof and amideimides.
[111] The most preferred repeating monomer units M are acrylates, methacrylates, styrene derivatives, imides, amic acids and their esters and amide imides.
[112] Preferred imide units M in which the backbone of the branched polymer according to the invention is generally synthesized are the groups of the formulas IIIa, Va and VII and / or the homologous and acidic ester groups of the formulas IVa, VI and VIII.
[113]
[114]
[115]
[116]
[117]
[118]
[119] In formulas (IIIa) to (VIII) above,
[120] The dashed line represents the bond to S ⁵ ,
[121] T ¹ represents a tetravalent organic radical of tetracarboxylic dianhydride after removal of the two -CO-O-CO- groups, the four valences being distributed among the four different carbon atoms of the radical,
[122] T ² and T ³ are each independently an aromatic or cycloaliphatic trivalent group wherein the three valences are distributed among the three different carbon atoms of the group and the group is unsubstituted or substituted by fluorine, chlorine or cyano, Or a cyclic, straight or branched chain alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, wherein one or more CH ₂ groups are independently -O-, -CO-, - CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other,
[123] S ⁶ , S ⁷ , S ⁸ , S ⁹ and S ¹⁰ are independently a single covalent bond or a straight-chain or branched alkylene of 1 to 24 carbon atoms which is unsubstituted, mono- or polysubstituted by cyano or halogeno, moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, ^{-NR 2 -, -NR 2 -CO-,} -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = -, -CO-O-, with the proviso that oxygen atoms are not directly bonded to each other and R ² represents a hydrogen atom or a lower alkyl. And,
[124] J is a divalent, trivalent or tetravalent aromatic or alicyclic group, wherein the valencies are distributed among the different atoms of these groups, these groups being unsubstituted or substituted by fluorine, chlorine or cyano, , Cyclic, straight or branched chain alkyl residues of 1 to 18 carbon atoms, wherein one or more CH ₂ groups are independently selected from -O-, CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other Or further represents a nitrogen atom or -CR ² -, wherein R ² is a hydrogen atom or lower alkyl,
[125] K represents a radical of an aliphatic, alicyclic or aromatic diamine after removing two amino groups,
[126] G represents a monovalent organic group derived from an alcohol after removal of a hydrogen atom or a hydroxy group.
[127] The tetracarboxylic acid dianhydride based on the trivalent organic radical T ¹ may be aliphatic, alicyclic or aromatic.
[128] Preferable examples of the aliphatic or alicyclic tetracarboxylic acid anhydride are as follows:
[129] Butanetetracarboxylic acid dianhydride,
[130] - ethylene maleic anhydride,
[131] - 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,
[132] - 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,
[133] - 2,3,5-tricarboxycyclopentyl acetic acid dianhydride,
[134] - 3,5,6-tricarboxy norborniacetic acid dianhydride,
[135] - 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride,
[136] - 4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride,
[137] - 5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid dianhydride,
[138] - bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,
[139] - bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, and
[140] - 1,8-dimethylbicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.
[141] Examples of preferred aromatic tetracarboxylic dianhydrides are:
[142] - pyromellitic dianhydride,
[143] - 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride,
[144] - 4,4'-oxydiphthalic di anhydride,
[145] - 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride,
[146] - 1,4,5,8-naphthalenetetracarboxylic acid dianhydride,
[147] - 2,3,6,7-naphthalenetetracarboxylic acid dianhydride,
[148] - 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride,
[149] - 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride,
[150] - 1,2,3,4-furan tetracarboxylic acid dianhydride,
[151] - 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride,
[152] - 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,
[153] - 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride,
[154] - 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride,
[155] - ethylene glycol bis (trimellitic acid) 2 anhydride,
[156] - 4,4 '- (1,4-phenylene) bis (phthalic acid) dianhydride,
[157] - 4,4 '- (1,3-phenylene) bis (phthalic acid) dianhydride,
[158] - 4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride,
[159] - 4,4'-oxyd (1,4-phenylene) bis (phthalic acid) dianhydride, and
[160] - 4,4'-methylene di (1,4-phenylene) bis (phthalic acid) dianhydride.
[161] Particularly preferred compounds are:
[162] - 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride,
[163] - 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,
[164] - 2,3,5-tricarboxycyclopentyl acetic acid dianhydride,
[165] - 5- (2,5-dioxotetrahydrofuran-3-yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride,
[166] - 4- (2,5-dioxotetrahydrofuran-3-yl) tetrahydronaphthalene-1,2-dicarboxylic acid dianhydride,
[167] - 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride, and
[168] - bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.
[169] Groups T ² and T ³ may be derived from aliphatic, cycloaliphatic or aromatic dicarboxylic anhydrides.
[170] Preferred groups T &lt; ² &gt; and T &lt; ³ &gt; are trivalent aromatic or carbocyclic groups wherein the three valences are distributed between three different carbon atoms, two of which are located at adjacent carbon atoms.
[171] Particularly preferred groups T &lt; ² &gt; and T &lt; ³ &gt; are trivalent benzene derivatives wherein the three valences are distributed between three different carbon atoms, two of which are in ortho positions relative to one another.
[172] Preferred "spacer units" S ⁶ in the present invention are - (CH ₂ ) _r -, - (CH ₂ ) _r -O-, - (CH ₂ ) _r -CO-, - (CH ₂ ) _{r- , - (CH 2) r -O} -CO-, - (CH 2) r -CO-NR 2 -, - (CH 2) r -NR 2 -CO-, - (CH 2) r -NR 2 -, _{- (CH 2) r -O- (} CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - (CH 2) r -O-CO- (CH 2) s _{-, - (CH 2) r} -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH 2) s -, - (CH 2) r -O _{- (CH 2) s -O-,} - (CH 2) r -CO-O- (CH 2) s -O-, - (CH 2) r -O-CO- (CH 2) s -O-, ^{_{- (CH 2) r -NR 2}} -CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO-O- (CH 2) s -O-, - (CH 2) r A straight or branched alkylene group of -O- (CH ₂ ) _s -CO-O- or - (CH ₂ ) _r -O- (CH ₂ ) _s -O-CO- wherein r and s are each 1 - 20, in particular an integer from 2 to 12, with the proviso that r + s is not more than 21, in particular not more than 15, and R ² is hydrogen or lower alkyl.
[173] Examples of preferred " spacer units " S ⁶ are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, Octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl- Propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentenyleneoxy, 5-pentenyleneoxycarbonyl, Hexylenecarbonyl, 6-hexylenecarbonyl, 5-pentylenecarbonyloxy, 7-heptylenoxy, 7-heptylenecyclohexyl, 6-hexylenecarbonyl Octylenecarbonyloxy, 8-octylenecarbonyloxy, 9-nonylenecyclohexyl, 8-octylenecarbonyloxy, 10-decylenecarbonyloxy, Decylcyclohexyloxy, 12-dodecylenecoxy, 12-dodecylenecoxy, 10-decylcyclohexyl, 10-decylcyclohexyl, Oxycarbonyl, Propyleneiminocarbonyl, 5-pentyleneiminocarbonyl, 6-hexyleneiminocarbonyl, 7-heptyleneiminocarbonyl, 7-heptyleneiminocarbonyl, N-octyleniminocarbonyl, 9-nonyleniminocarbonyl, 10-decyleniminocarbonyl, 11-undecyleniminocarbonyl, 12-dodecyliminocarbonyl, 2- Propylene carbonylimino, 5-pentylene carbonylimino, 6-hexylenecarbonylimino, 7-heptylenecarbonylimino, 8-hexylenecarbonylimino, Octylene carbonate carbonylimino, 6- (3-propyleneiminocarbonyloxy) hexylene, 6-ethylhexylcarbonylimino, 10-decylene carbonylimino, Propyleneiminocarbonyloxy) hexylenoxy, 6- (3-propylenimino) hexylenoxy, 6- (3-propylenimino) Hexylene, 6- (3-propyleneiminocarbonyl) hexylenoxy, and the like.
[174] Preferred "spacer units" S ⁷ and S ¹⁰ of the present invention _{- (CH 2) r -,} -O- (CH 2) r -, -CO- (CH 2) r -, -CO-O- (CH 2 _{) r -, -O-CO- (} CH 2) r -, -NR 2 -CO- (CH 2) r -, -NR 2 - (CH 2) r -, -CO-NR 2 - (CH 2) ^{_{r -, -NR 2 -CO- (CH}} 2) r -, -O- (CH 2) r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s _{-, - (CH 2) r} -O-CO- (CH 2) s -, - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO _{-O- (CH 2) s -,} -O- (CH 2) r -O- (CH 2) s -, -O- (CH 2) r -CO-O- (CH 2) s -, -O _{- (CH 2) r -O-} CO- (CH 2) s -, -O- (CH 2) r -NR 2 -CO- (CH 2) s -, -O- (CH 2) r -NR 2 _{-CO-O- (CH 2) s} -, -O-CO- (CH 2) r -O- (CH 2) s - or _{-CO-O- (CH 2) r} -O- (CH 2) s - in which r and s are each an integer from 1 to 20, in particular from 2 to 12, with the proviso that r + s is not more than 21, in particular not more than 15, and R ² is hydrogen or lower alkyl; to be.
[175] Examples of preferred "spacer units" S ⁷ and S ¹⁰ are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6- Octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 2 -Oxy-ethylene, 3-oxypropylene, 4-oxybutylene, 5-oxypentylene, 6-oxyhexylene, 7-oxyheptylene, (Oxycarbonyl) ethylene, 3- (oxycarbonyl) propylene, 4- (oxycarbonyl) butylene, 5- (oxycarbonyl) (Oxycarbonyl) heptylene, 8- (oxycarbonyl) octylene, 9- (oxycarbonyl) nonylene, 10- (oxycarbonyl) (Carboxymethyl) propylene, 4- (carbonyloxy) butylene, 2- (carbonyloxy) ethylene, 3- 5- (carbonyloxy) pentylene, 6- (carbonyloxy) hexylene, 7- (carbonyloxy) heptene (Carbonyloxy) dodecylene, 11- (carbonyloxy) undecylene, 12- (carbonyloxy) dodecene, (Carbonylimino) propylene, 4- (carbonylimino) butylene, 5- (carbonylimino) pentylene, 6- (carbonylimino) (Carbonylimino) hexylene, 7- (carbonylimino) heptylene, 8- (carbonylimino) octylene, 9- (carbonylimino) - (carbanylimino) undecylenes, 12- (carbonylimino) dodecylene, 2-iminoethylene, 3-iminopropylene, 4-iminobutylene, 5-iminopentylene, Iminodecylene, 2-iminocarbonylethylene, 3-iminodecylene, 10-iminodecylene, 11-imino-undecylene, But are not limited to, iminocarbonylpropylene, 4-iminocarbonylbutylene, 5-iminocarbonylpentylene, 6-iminocarbonylhexylene, Iminocarbonyldodecylene, 2- (2-ethylenoxy) ethylene, 2- (2-ethylhexyloxy) ethylene, (3-propyleneiminocarbonyloxy) hexylene, 6- (3-propyleneiminocarbonyloxy) ethylene, 2- Propyleneiminocarbonyl) hexylene, and the like.
[176] Preferred "spacer units" S ⁸ and S ⁹ of the present invention _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO-, - (CH 2) r -CO _{-O-, - (CH 2) r} -O-CO-, - (CH 2) r -CO-NR 2 -, - (CH 2) r -NR 2 -CO-, - (CH 2) r -NR _{^{2 -, -O- (CH 2)}} r -, -CO-O- (CH 2) r -, -O-CO- (CH 2) r -, -NR 2 -CO- (CH 2) r -, _{^{-CO-NR 2 - (CH 2}} ) r -, -NR 2 - (CH 2) r -, -O- (CH 2) r -CO-O-, -O- (CH 2) r -O-CO _{-, -O- (CH 2) r} -CO-NR 2 -, -O- (CH 2) r -NR 2 -, -O- (CH 2) r -O-, -O- (CH 2) r ^{-NR 2 -CO-, -NR 2 - (} CH 2) r -CO-O-, -NR 2 - (CH 2) r -O-, -NR 2 - (CH 2) r -NR 2 -, - _{^{NR 2 - (CH 2) r}} -O-CO-, -CO-NR 2 - (CH 2) r -O-, -CO-NR 2 - (CH 2) r -NR 2 -, -CO-NR 2 _{- (CH 2) r -O-} CO-, -O-CO- (CH 2) r -CO-, -O-CO- (CH 2) r -O-, -O-CO- (CH 2) r ^{-NR 2 -, -O-CO- (} CH 2) r -CO-O-, -O-CO- (CH 2) r -CO-NR 2 -, -O-CO- (CH 2) r -NR _{^{2 -CO-, - (CH 2)}} r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - (CH 2) r -O-CO- _{- (CH 2) s -,} - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH 2) s -, - ( CH ₂ ) _r -O- (CH ₂ ) _s -O-, - (CH ₂ ) _r -CO-O- _{(CH 2) s -O-, -} (CH 2) r -O-CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO- (CH 2) s -O-, ^{_{- (CH 2) r -NR 2}} -CO-O- (CH 2) s -O-, -O- (CH 2) r -O- (CH 2) s -, -O- (CH 2) r - CO- O- (CH ₂ ) _s -, -O- (CH ₂ ) _r -NR ² -CO- (CH ₂ ) _s -, -O- (CH ₂ ) _r -NR ² -CO- ₂ ) _s- , -O- (CH ₂ ) _r -CO-O- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -O- (CH ₂ ) _s -O-, (CH ₂ ) _r -NR ² -CO- (CH ₂ ) _s -O-, -O- (CH ₂ ) _r -NR ² -CO-O- (CH ₂ ) _s -O-, (CH ₂ ) _r -O- (CH ₂ ) _s - or -CO-O- (CH ₂ ) _r -O- (CH ₂ ) _s -O- wherein r and s are Each being an integer from 1 to 20, in particular from 2 to 12, with the proviso that r + s is not more than 21, in particular not more than 15, and R ² is hydrogen or lower alkyl.
[177] Examples of preferred "spacer units" S ⁸ and S ⁹ are 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6- Octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, 1,12-dodecylene, 3-methyl-1,4-butylene, 3 Propyleneoxy, propyleneoxy, 3-propyleneoxycarbonyl, 2-ethylenecarbonyloxy, 4-butyleneoxy, 4-butyleneoxycarbonyl, 3-propylenecarbonyloxy, 5-pentylenoxy, Heptylenecyclohexyl, 6-hexylenecyclohexyl, 5-pentylenecarbonyloxy, 7-heptylenoxy, 7-heptylenecyclohexyloxycarbonyl, 6-hexylenecyclohexyl, Octylenecarbonyloxy, 10-octylenecarbonyloxy, 8-octylenecarbonyloxy, 9-nonylenecyclohexyl, 8-octylenecarbonyloxy, 12-decenylcarbonyloxy, 12-dodecylenecoxy, 12-decylcyclohexyloxy, 11-undecylenecyloxy, 11-undecylenecyloxycarbonyl, - Dodecylenoxy Propyleniminocarbonyl, 4-butyleneiminocarbonyl, 5-pentyleniminocarbonyl, 6-hexyleniminocarbonyl, 7-heptylenylene, Dicyaniminocarbonyl, 11-undecyleniminocarbonyl, 12-dodecyliminocarbonyl, 2-octenyliminocarbonyl, 8-octenyliminocarbonyl, Propylene carbonylimino, 5-pentylene carbonylimino, 6-hexyleniminocarbonyl, 7-heptylenecarbonylimino, 3-propylenecarbonylimino, , 8-octylenecarbonylimino, 9-nonylenecarbonylimino, 10-decylenecarbonylimino, 11-undecylenecarbonylimino, 6- (3-propyliminocarbonyloxy) hex Hexyleneoxy, hexyleneoxy, 6- (3-propyleneoxy) hexylene, 6- (3-propyleneoxy) hexyleneoxy, 6- (3- propyleneiminocarbonyloxy) Propyliminocarbonyl) hexyloxy, 1,2-ethylenedioxy, 1,3-propylenedioxy, Hexylenedioxy, 1,7-heptylenedioxy, 1,8-octylenedioxy, 1,9-nonylenedioxy, Oxy, 1,10-decylenedioxy, 1,11-undecylenedioxy, 1,12-dodecylenedioxy, and the like.
[178] The radical K is a divalent group which can be derived from an aliphatic, alicyclic or aromatic diamine by removal of the amino group.
[179] Preferable examples of such aliphatic and cycloaliphatic diamines are ethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine, 1,5-pentylene diamine, 1,6-hexylene diamine, Diamine, 1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine, 1,11-undecylenediamine, 1,12-dodecylenediamine, diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl) methylamine, 1,2-diaminocyclohexane, 4,4'-diamino Dicyclohexylmethane, 1,3-bis (methylamino) cyclohexane and 4,9-dioxadodecane-1,12-diamine.
[180] Preferable examples of the aromatic diamines include 3,5-diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid hexyl ester, 3,5-diaminobenzoic acid dodecyl ester, 3,5-diaminobenzoic acid isopropyl ester, 4'-ethylenedianiline, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetramethylbenzidine, 4,4'- Diaminodiphenylsulfone, 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4- Diaminobenzophenone, 4,4'-diamino-2,2'-dimethylbibenzyl, 2,2-bis [4- (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, ) Benzene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) -fluorene, 4,4'-methylenebis Phenoxy) biphenyl , 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'- (1,4-phenylene isopropylidene) -bisaniline, 4,4 '- (1,3- Propylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) -phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane, (4-aminophenyl) hexafluoropropane, 2,2'-bis [4- (4-amino-2- Bis (trifluoromethyl) biphenyl and 4,4'-bis [(4-amino-2-phenylethyl) phenyl] hexafluoropropane, 4,4'- -Trifluoromethyl) phenoxy] -2,3,5,6,2 ', 3', 5 ', 6'-octafluorobiphenyl.
[181] The divalent, trivalent or tetravalent group J basically acts as a group for bonding the polymer backbone to the side chain comprising all of the general formula (I) except M. The two valences in J act as a bond shown in formulas III-VII through S ⁶ through S ¹⁰ in the main chain. The third and optionally the fourth valence function as a bond to one or two side chain (s) of formula I (formula I except M). However, the polymer chain may also comprise building blocks of formulas (III) to (VIII) without the side chain of formula (I), indicating that group J is only divalent. The proportion of building blocks of formulas III to VIII wherein J is divalent indicates that there are no crosslinking side chains of the formula J present and is generally not more than 75%, preferably not more than 50%, more particularly not more than 30%. The trivalent and tetravalent group J is preferably a trivalent group containing one or two cross-linkable side chains of formula (I), meaning that this group is bonded to only one cross-linkable side chain of formula (I).
[182] The photoactive polymer of formula (I) may be a homopolymer or a copolymer. However, copolymers are preferred.
[183] It is preferred that at least 50% of the monomer building blocks forming the backbone of the photoactive polymer of formula (I) are bonded to one or two side chains comprising the entire compound of formula (I) except M. Particularly preferred are polymers wherein at least 70% of the monomer building blocks forming the backbone are bonded to one or two side chains.
[184] Preferably, the monomer building blocks comprising the side chains each bind to only one side chain.
[185] The building blocks of the formulas IV, VI and VIII are a group of amic acid or a group of amic acid esters (i.e., carboxamide-carboxylic acid group or carboxamide-carboxylic acid ester group) which can be generated by incomplete imidization in the polymer. On the other hand, polymers consisting only of building blocks of the formula (IV), (VI) or (VIII) which represent polymerized acids or polymeric acid esters are in accordance with the invention and are also important precursors for the preparation of the polyamides included in the present invention. These polymers containing groups of the formula IV, VI or VIII are obtained as polymers in which G is hydrogen, indicating that these polymers consist entirely of polyamic acid groups or contain some polyamic acid groups.
[186] The term " phenylene " of the present invention includes 1,2-, 1,3- or 1,4-phenylene which is unsubstituted or monosubstituted or polysubstituted. Preferably 1,3- or 1,4-phenylene, especially 1,4-phenylene.
[187] Quot; refers to an unsubstituted, halogeno or polyhalogeno-substituted cyclic, straight or branched alkyl residue of 1 to 12 carbon atoms in which one or more CH ₂ groups are independently -O-, -CO-, -CO-O -, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms do not directly bond to each other "means for example methyl, ethyl, Butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Propyl, butynyl, pentynyl, methoxy, ethoxy, propoxy, iso-propyl, butoxy, Butoxy, tert-butoxy, pentyloxy, isopentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy, di Chillax city, undecity city, road 3-ethylhexyloxy, cyclohexylmethoxy, cyclopentylmethoxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, , Isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, cyclopentyloxycarbonyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, , Propylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, propylcarbonyloxy, propylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, Butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, tert-butylcarbonyloxy, , Pentylcarbonyloxy, isopentylcarbonyloxy, cyclopentylcarbonyloxy, hexylcarbonyloxy, cyclohexylcarbonyloxy, octylcarbonyloxy, nonylcarbonyloxy, decylcarbonyloxy, undecylcarbonyloxy, Propylcarbonyl, isopropylcarbonyl, butylcarbonyl, isobutylcarbonyl, butylcarbonyl, isobutylcarbonyl, isobutylcarbonyl, isobutylcarbonyl, Decylcarbonyl, dodecylcarbonyl, methoxyacetoxy, isopropoxycarbonyl, naphthylcarbonyl, naphthylcarbonyl, naphthylcarbonyl, naphthylcarbonyl, Methoxy-2-propoxy, 3-methoxy-1-propoxy, 2-methoxyethoxy, 2-isopropoxyethoxy, Propyloxyhexyl, 6-propyloxyhexyloxy, 2-fluoroethyl, trifluoromethyl, 4-pentyloxy, 4-pentyloxy, 5-chloro-1-pentyne, 4-pentenecarbonyloxy, , 2,2,2-tri (Perfluorobutyl) ethyl, 2- (perfluorobutyl) ethyl, 1H, 1H, 3H, 5H-dodecafluoroheptyl, Perfluorohexyl, perfluorononyl, 1-fluoropropoxy, 1-fluoropropoxy, perfluorohexyl, perfluorohexyl, perfluorohexyl, Fluoropentyloxy, 2-fluoropropoxy, 2,2-difluoropropoxy, 3-fluoropropoxy, 3,3-difluoropropoxy, 3,3,3- Trifluoromethoxy, and the like.
[188] The term " aliphatic " includes straight or branched chain and saturated or unsaturated alkyl groups, unless otherwise stated. Possible substituents include alkyl, aryl (obtained as an araliphatic group), cycloalkyl, amino, cyano, epoxy, halogen, hydroxy, nitro, oxo and the like. Possible heteroatoms which may substitute carbon atoms are nitrogen, oxygen and sulfur. In addition, in the case of nitrogen, the substituents are groups such as alkyl, aryl and cycloalkyl.
[189] The term " alkyl " includes straight or branched chain and saturated or unsaturated alkyl groups, unless otherwise stated.
[190] The term " lower alkyl " refers to straight or branched saturated hydrocarbon radicals of 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as methyl, ethyl,
[191] The term " aromatic " includes carbocyclic and heterocyclic groups that are unsaturated or saturated by one or more groups.
[192] The side chain polymers according to the invention may be present in the form of copolymers as well as homopolymers. The term " copolymer " is understood to mean a specific statistical copolymer.
[193] The polymers of formula (I) are characterized by their ease of use. Methods of manufacture are known to those skilled in the art.
[194] Compounds of formula (I) having acrylate, methacrylate and styrene derivatives as repeating monomer units can be prepared according to two different processes. There is also the possibility of polymer-homologous reactions of reactive photoactive derivatives with functional polymers in addition to direct polymerization of the previously processed monomers.
[195] For direct polymerization, monomers and comonomers are first prepared separately from the respective components. The formation of the polymer is then carried out by methods known in the art by irradiation with ultraviolet light or heat or by the action of radicals or ionic catalysts. Potassium peroxodisulfate, dibenzoyl peroxide, azobisisobutyronitrile or di-tert-butyl peroxide are examples of radical initiators. The ionic catalyst is an alkaline-organic compound such as phenyl lithium or naphthyl sodium or a Lewis acid such as BF ₃ , AlCl ₃ , SnCl ₃ or TiCl ₄ . The monomers can be polymerized in solution, suspension, emulsion or substrate.
[196] In addition, the second step of the polymer of formula (I) may be prepared by polymer-homologous reaction from a previously worked functional polymer and a suitable functional photoactive derivative. For example, many known methods such as esterification, trans-esterification, amidation or etherification are suitable for polymer-homologous reactions.
[197] The polymer has a molecular weight (Mw) of from 1 000 to 5 000 000, preferably from 5 000 to 2 000 000, particularly preferably from 10 000 to 1 000 000.
[198] The preparation of the polyamic acid and polyimide of the present invention is generally described in Plast. Eng. 36 (1996) " Polyimides, fundamentals and applications ".
[199] For example, the polycondensation reaction for the production of polyamic acid may be carried out in a polar aprotic organic solvent such as -Butyrolactone, N, N-dimethylacetamide, N-methylpyrrolidone or N, N- Lt; / RTI &gt; In most cases, equimolar amounts of dianhydrides and diamines are used, representing one amino group per anhydride group. If stabilization of the polymer molecular weight is desired, it is possible to add one of the two components in excess or substoichiometrically, or to add monofunctional compounds in the form of dicarboxylic monohydrate or monoamine, as appropriate. Examples of such mono-functional compounds are maleic anhydride, phthalic anhydride, aniline, and the like. The reaction is preferably carried out at a temperature of less than 100 &lt; 0 &gt; C.
[200] Polymerization of the polyamic acid to form polyimide can be carried out by heating, which indicates condensation using water removal or other imidization reactions using reagents. Imitation of the polyamic acid is not always complete when performed with purely heat, indicating that the resulting polyimide still contains some of the polyamic acid. Generally, the imidization reaction is carried out at a temperature of 60 to 250 ° C, preferably less than 200 ° C. To achieve imidization at lower temperatures, additional reagents are added to facilitate the removal of water in the reaction mixture. Such reagents include, for example, acid anhydrides such as acetic anhydride, propionic anhydride, phthalic anhydride and trifluoroacetic anhydride and tertiary amines such as triethylamine, trimethylamine, tributylamine, pyridine, N, N - dimethylaniline, lutidine, collidine, etc.). The amount of reagent used in such a case is preferably at least 2 equivalents of amine and 4 equivalents of acid anhydride per equivalent of the condensed polyamic acid.
[201] The imidization reaction may be carried out before or after the application to the support. The latter is particularly preferable when the polyimide has low solubility in a conventional solvent.
[202] The polyamic acid and polyimide of the present invention have an intrinsic viscosity of 0.05 to 10 dL / g, more preferably 0.05 to 5 dL / g. Herein, the intrinsic viscosity ( _Inh = ln _Rel / C) is determined by measuring the viscosity of the solution containing the polymer at a concentration of 0.5 g / 100 ml at 30 占 폚 using N-methyl-2-pyrrolidone as a solvent .
[203] The number of monomer building blocks synthesized from polymer chains according to the present invention may vary within a wide range. Generally 2 to 2000, in particular 3 to 200.
[204] The polymers according to the present invention may contain additives such as silane-containing compounds and epoxy-containing cross-linking agents to improve the adhesion of the polymer to the substrate. Examples of silane adhesion promoters are described in Plast. Eng. 36 (1996) " Polyimides, fundamentals and applications ". The epoxy-containing crosslinking agent is preferably 4,4'-methylene bis (N, N-diglycidyl aniline), trimethylolpropane triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid 1 , 2: 4,5-N, N'-diglycidyldiimide, polyethylene glycol diglycidyl ether, N, N-diglycidylcyclohexylamine, and the like.
[205] The polymers according to the invention may contain additives such as photosensitizers, photoradicals and / or cationic photoinitiators. Examples of such additives include mixtures of 2,2-dimethoxyphenylethanone, diphenylmethanone and N, N-dimethylbenzeneamine or ethyl 4- (dimethylamino) benzoate, xanthone, thioxanthone, IRGACURE ^TM 184, 369, 500, 651 and 907 from Ciba, Michler's ketone, triarylsulfonium salts and the like.
[206] The polymers according to the invention can be used as homopolymers, or as mixtures with other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and / or photoactive monomers. Therefore, a part of the layer can be modified according to the purpose. For example, an induced pretilt angle, good surface wettability, high pressure holding rate, specific fixed energy, etc. can be obtained.
[207] Thus, the polymer according to the invention can be applied as a support and crosslinked by radiation using linear deflected light, after all imidization steps which may be required, by the reaction of the side chain of the side chain containing the photoactive group, Is obtained according to the direction of deflection of the irradiated light, preferably the orientation and direction of the tilt angle to the liquid crystal in contact with the orientation layer. By spatially selective irradiation of the molecular units according to the invention, they can be aligned in very specific surface areas and provide a defined tilt angle. At the same time, the resulting orientation layer is stabilized by the ring moiety.
[208] Accordingly, the present invention relates to the use of the polymer according to the present invention as an alignment layer for a liquid crystal, and its use in the production of optical components, particularly hybrid layer components.
[209] This orientation layer can be applied, for example, to a support (e.g., a glass plate coated with indium-tin oxide (ITO)) optionally coated with a support in a spin-coating apparatus to produce a uniform layer of 0.05 to 50 탆 thickness To produce a solution of the resulting polymeric material. Subsequently, or optionally before imidation, the portion to be oriented can be irradiated, for example using a high-pressure mercury vapor lamp, a xenon lamp or a pulsating ultraviolet laser, using a deflector and optionally a mask for the production of a structural feature. The irradiation time depends on the output of each lamp, and can vary from a few seconds to several hours. However, it is also possible to carry out dimerization by irradiation of a uniform layer using, for example, a filter through which a suitable radiation is transmitted for a crosslinking reaction.
[210] A further aspect of the invention relates to an optical or electro-optical device having a) at least one orientation layer characterized by comprising a polymer according to formula I, and
[211] b) Structures of unstructured and structured optical components and their use in multi-layer systems.
[212] The polymers according to the invention are illustrated in more detail by the following examples. In the examples, Tg represents the glass temperature, C represents the crystalline phase, N represents the nematic phase, I represents the isotropic phase, and p represents the number of repeating units in the polymer. Relative molecular weights are determined by gel permeation chromatography (GPC) at 30 占 폚 using THF with polystyrene standards as solvent.
[213] Example 1
[214] Benzoyloxy) benzoyloxy] undecyloxycarbonyl] - (2-methoxy-benzoyloxy) 1-methylethylene]
[215]
[216] To a solution of (E) -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] -2- (4-propylbenzoyloxy) benzoic acid 11- (2-methylacryloyl) benzoic acid in 2.45 ml of anhydrous tetrahydrofuran (THF) A mixture of 0.89 g (1.22 mmol) of n-hexylisocyanate and 2.0 mg (0.012 mmol) of α, α'-azoisobutyronitrile (AIBN) is degassed in a sealable tube. The tube is then sealed under argon and stirred at 60 &lt; 0 &gt; C for 17 hours. The polymer is diluted in 2.5 ml of THF, precipitated with 500 ml of diethyl ether and collected. The polymer from THF (7.0 mL) was reprecipitated with 750 mL of methanol to give poly- [1- [11- [5- [4 - [(E) -2- methoxycarbonylvinyl] benzoyloxy] (4-propylbenzoyloxy) benzoyloxy] undecyloxycarbonyl] -1-methylethylene] of 0.71 g (80%); M _n = 7.4 x 10 ⁴ , pdi = 6.59, Tg = 49.5 ° C, cl.p. (N / I) 127.3 ° C.
[217] (2-methylacryloyloxy) benzoyl] -2- (4-propylbenzoyloxy) benzoic acid 11- (2-methylacryloyloxy) undecyl The ester is prepared according to the following method:
[218] (E) -4-Carboxylic &lt; / RTI &gt; cinnamic acid methyl ester
[219]
[220] 10.0 g (66.6 mmol) of 4-carboxybenzaldehyde was dissolved in 100 ml of toluene, and 23.6 g (69.9 mmol) of [(methoxycarbonyl) methyl] triphenylphosphorane was added. The reaction is a weak exothermic reaction. The thick suspension is diluted with 50 ml of toluene. After 18 hours at room temperature, the product is collected by filtration and is warmed to 100 ml of isopropyl alcohol at reflux for 1 hour. The solid was then filtered off at 0 캜 and dried under vacuum at 45 캜 overnight to yield 8.9 g (65%) of (E) -4-carboxyl cinnamic acid methyl ester as a white powder.
[221] 2-methylacrylic acid 11-bromoundecyl ester
[222]
[223] 19.2 g (76.4 mmol) of 11-bromo-1-undecanol, 7.2 g (84.1 mmol) of methacrylic acid and 1.03 g (8.4 mmol) of 4-dimethylaminopyridine are dissolved in 157 ml of dichloromethane. The solution is then cooled to 0 C and a solution of 17.4 g (84.2 mmol) of dicyclohexylcarbodiimide in 80 ml of dichloromethane is added dropwise at 0 &lt; 0 &gt; C for 45 minutes. The reaction was allowed to warm to room temperature, stirred for 19 h, and filtered. The filtrate is concentrated by evaporation. The residue was chromatographed on 170 g of silica gel with toluene to give 19.3 g (98.4%) of 2-methyl acrylate 11-bromoundecyl ester.
[224] Dihydroxybenzoic acid 11- (2-methylacryloyloxy) ester
[225]
[226] 8.46 g (54.9 mmol) of 2,5-dihydroxybenzoic acid are suspended in acetonitrile at 55 占 폚. 8.24 ml (54.9 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (1,5-5) (DBU) is added dropwise over 10 minutes. The reaction temperature is raised to 40 占 폚. 19.3 g (60.4 mmol) of 2-methyl-acrylic acid 11-bromo-undecyl ester are added at room temperature and the mixture is heated at reflux temperature for 17.5 hours. The reaction mixture is cooled and then partitioned between diethyl ether and water, and the organic phase is washed with water, 1N sulfuric acid and water again, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was recrystallized first by a mixture of diethyl acetate (17 ml) and hexane (100 ml) followed by a mixture of tert-butyl methyl ether (50 ml) and hexane (100 ml) 17.1 g (79%) of dihydroxybenzoic acid 11- (2-methylacryloyloxy) ester was obtained.
[227] (E) -2-hydroxy-5- [4- (2-methoxycarbonylvinyl) benzoyloxy] benzoic acid 11- (2-methylacryloyloxy)
[228]
[229] (12.1 mmol) 2,5- dihydroxybenzoic acid 11- (2-methylacryloyloxy) ester, 2.50 g (12.1 mmol) of (E) -4-carboxylate cinnamic acid methyl ester, and 4-dimethylaminopyridine 0.37 g (3.0 mmol) is dissolved in 30 ml of dichloromethane. 2.32 g (12.1 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride and 25 ml of dichloromethane are added dropwise over 1 hour. After 1.5 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was chromatographed on 240 g of silica gel with cyclohexane: ethyl acetate (9: 1) to give (E) -2-hydroxy-5- [4- (2-methoxycarbonylvinyl) benzoyloxy ] -Benzoic acid 6.1 g (87%) of 11- (2-methylacryloyloxy) -undecyl ester was obtained. Melting point: 51 캜.
[230] (E) -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] -2- (4-propylbenzoyloxy) benzoic acid 11- (2-methylacryloyloxy)
[231]
[232] (1.72 mmol) of 11- (2-methylacryloyloxy) undecyl ester of 4- (2-methoxyethyl) 0.37 g (2.24 mmol) of propylbenzoic acid and 58 mg (0.47 mmol) of 4-dimethylaminopyridine are dissolved in 20 ml of dichloromethane. A suspension of 0.43 g (2.24 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride and 10 ml of dichloromethane is added dropwise over 45 minutes. After 65 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was chromatographed over 120 g of silica gel with cyclohexane: ethyl acetate (4: 1) and then crystallized with 50 ml of isopropyl alcohol to give (E) -5- [4- (2-methoxycarbonyl (79%) of 11- (2-methoxyacryloyloxy) undecyl ester as a colorless oil. Melting point (C / N) 86.8 캜, cl.p (N / I) 102.8 캜.
[233] The following compounds are prepared in a similar manner:
[234] - poly [1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4- pentylbenzoyloxy) benzoyloxy] undecyloxycarbonyl] M _n = 6.9 x 10 ⁴ , pdi = 5.08, Tg = 45.9 ° C, cl.p. (N / I) 127.3 ° C.
[235] - poly [l- [11- [5- [4- (E) -2-methoxycarbonyl-vinyl] -benzoyloxy] -2- (4-heptylbenzoyloxy) benzoyloxy] -undecyloxycarbonyl ] -1-methylethylene], M _n = 1.00 x 10 ⁵ , pdi = 7.04, Tg = 41.7 ° C, cl.p. (N / I) 123.6 ° C.
[236] - poly [1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-propylcyclohexanoyloxy) benzoyloxy] undecyloxycarbonyl ] -1-methylethylene], M _n = 7.2 x 10 ⁴ , pdi = 4.29, Tg = 45.4 ° C, cl.p. (N / I) 113.6 ° C.
[237] Benzoyloxy) - &lt; / RTI &gt; benzoyloxy) octyloxycarbonyl] - M _n = 1.68 x 10 ⁵ , pdi = 2.96, Tg = 62.7 ° C, cl.p. (N / I) 132.6 ° C.
[238] - poly- [1- [6- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-propylbenzoyloxy) benzoyloxy] hexyloxycarbonyl] _{1-methyl-ethylene], M n = 1.17 x 10} 5, pdi = 2.61, Tg = 62.7 ℃, cl.p. (n / I) 138.8 ℃.
[239] (4-propylbenzoyloxy) benzoyloxy] undecyloxycarbonyl] - &lt; / RTI &gt; M _n = 4.7 x 10 ⁴ , pdi = 2.31, Tg = 54.8 ° C, cl.p. (N / I) 124.3 ° C.
[240] Example 2
[241] Poly- [1- [11- [2- [4-pentylbenzoyloxy] -5- [6- [2-methoxy-4- (methoxycarbonylvinyl) -phenoxy] oxyhexyl] benzoyloxy] Siloxycarbonyl] -1-methylethylene]
[242]
[243] (E) -2- [4-pentylbenzoyloxy] -5- [6- [2-methoxy-4- (methoxycarbonylvinyl) phenoxy] oxyhexyl] benzoic acid 11- [1- [11- [2- [4-pentylbenzoyloxy] -5- [2- (4-fluorophenyl) to afford 6- [2-methoxy-4- (methoxycarbonyl nilbin d) phenoxy] hexyl-oxy] benzoyloxy] undecyl-oxy-carbonyl] -1-methyl-ethylene] 0.84g (84%): M n = 7.3 x 10 ⁴ , pdi = 4.40, Tg = 34.0 ° C, cl.p. (N / I) 54.2 &lt; 0 &gt; C.
[244] (E) -2- [4-pentylbenzoyloxy] -2- [5- [2-methoxy-4- (methoxycarbonylvinyl) -phenoxy] oxyhexyl] benzoic acid 11- 2-methyl acryloyloxy) undecyl ester is prepared as follows:
[245] (E) -4-hydroxy-3-methoxycinnamic acid methyl ester
[246]
[247] 25 g (0.13 mol) of (E) -4-hydroxy-3-methoxycinnamic acid was dissolved in 180 ml of methanol and 5 ml of concentrated sulfuric acid was added. The solution is heated to reflux for 2 hours. Subsequently, most of the methanol (about 150 ml) is distilled off and the remaining residue is taken up in 500 ml of ice water. The precipitated ester is filtered off with suction, washed successively with cold water, a small amount of cold sodium bicarbonate solution and again with water, and dried at 50 캜 under water-jet vacuum. Chromatography on 250 g of silica gel using dichloromethane: diethyl ether (9: 1) yields 21.78 g of (E) -4-hydroxy-3-methoxycinnamic acid methyl ester as a pale yellow oil.
[248] (E) -4- (6-hydroxyhexyloxy) -3-methoxycinnamic acid methyl ester
[249]
[250] (25.2 mmol) of 1,6-hexanediol vinyl ether was added to a solution of 5.0 g (24.0 mmol) of (E) -4-hydroxy-3-methoxycinnamic acid methyl ester and 6.61 g (25.2 mmol) solution. The colorless solution is then cooled to 0 &lt; 0 &gt; C and 11.5 ml (25.3 mmol) of a 40% solution of azodicarboxylic acid diethyl ester in toluene is added dropwise over 30 minutes. The mixture is then reacted first at 0 DEG C for 30 minutes and then at room temperature for 22.5 hours. 150 ml of methanol and 10 drops of concentrated sulfuric acid are then added to the reaction solution, and the mixture is stirred for 1.5 hours. The reaction mixture is then partitioned between ethyl acetate and water, and the organic phase is washed with saturated sodium bicarbonate, repeatedly washed with saturated sodium chloride solution, then dried over magnesium sulfate, filtered and concentrated by evaporation. The residue was chromatographed on 470 g of silica gel with toluene: ethyl acetate (1: 1) and then crystallized from ethyl acetate: hexane (3: 5) to give 4- (6-hydroxyhexyloxy) 6.13 g of cisaminic acid methyl ester is obtained.
[251] (E) -2- hydroxy-5- [6- [2-methoxy-4- (methoxycarbonylvinyl) phenoxy] oxyhexyl] benzoic acid 11- (2-methylacryloyloxy)
[252]
[253] 1.27 g (3.24 mmol) of 2,5-dihydroxybenzoic acid 11- (2-methylacryloyloxy) ester and 1.0 g (3.24 mmol) of 4- (6-hydroxyhexyloxy) mmol) and triphenylphosphine (0.89 g, 3.40 mmol) are dissolved in 20 ml of tetrahydrofuran. The colorless solution is then cooled to 0 C and then 1.48 ml (3.40 mmol) of a 40% solution of azodicarboxylic acid diethyl ester in toluene is added dropwise over 10 minutes. The mixture is then allowed to react at 0 DEG C for 3 hours. The reaction mixture is then partitioned between ethyl acetate and water and the organic phase is washed repeatedly with saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated by evaporation. The residue is allowed to warm to room temperature in a mixture of methanol and water (3: 2). The solid is then filtered off and dried overnight at 45 &lt; 0 &gt; C under vacuum. The solid was chromatographed on 150 g of silica gel with toluene: ethyl acetate (1: 1) to give (E) -2-hydroxy-5- [6- [2-methoxy- Nylvinyl) phenoxy] oxyhexyl] benzoic acid 1.45 g (65%) of 11- (2-methylacryloyloxy) undecyl ester was obtained.
[254] (E) -2- [4-pentylbenzoyloxy] -5- [6- [2-methoxy-4- (methoxycarbonylvinyl) -phenoxy] oxyhexyl] benzoic acid 11- Yloxy) undecyl ester
[255]
[256] (E) -2- hydroxy-5- [6- [2-methoxy-4- (methoxycarbonylvinyl) phenoxy] oxyhexyl] benzoic acid 11- (2-methylacryloyloxy) 0.42 g (2.20 mmol) of 4-pentylbenzoic acid and 64 mg (0.52 mmol) of 4-dimethylaminopyridine are dissolved in 30 ml of dichloromethane. A suspension of 0.42 g (2.20 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride and 3 ml of dichloromethane is added dropwise over 15 minutes. After 20 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was chromatographed over 150 g of silica gel with cyclohexane: ethyl acetate (4: 1) and then crystallized from 20 ml of isopropyl alcohol to give (E) -2- [4-pentylbenzoyloxy] -5 - [6- [2-methoxy-4- (methoxycarbonylvinyl) phenoxy] oxyhexyl] benzoic acid 1.40 g (78%) of 11- (2-methylacryloyloxy) undecyl ester was obtained.
[257] Example 3
[258] Polyimide
[259] 96.6 mg (0.493 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added to a solution of 3,5-diaminobenzoic acid 11- [2- [4-pentylbenzoyloxy] -5- [ To a solution of 0.434 g (0.547 mmol) of 4- (2-methoxycarbonylvinyl) benzoyloxy] -benzoyloxy] undecyl ester was added. Then, the mixture is stirred at 0 ° C for 2 hours. 10.7 mg (0.055 mmol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride is added. The mixture is then reacted at room temperature for 69 hours. The polymer mixture is diluted in 3.0 ml of THF, precipitated in 150 ml of diethyl ether and collected. The polymer was reprecipitated in 500 ml of water from THF (10 ml) and dried at room temperature under vacuum to obtain 0.51 g of polyamic acid A as a beige powder. [ ] = 0.51 dL / g.
[260] Benzoyloxy] undecyl ester of 3,5-diaminobenzoic acid, which is used as a starting material, can be obtained by reacting 3,5-diaminobenzoic acid 11- [2- [4-pentylbenzoyloxy] -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] Prepare according to the method:
[261] 3,5-dinitrobenzoic acid 11-Bromoundecyl ester
[262]
[263] 11.4 g (45.4 mmol) of 11-bromo-1-undecanol, 11.0 g (47.7 mmol) of 3,5-dinitrobenzoyl chloride and 54 mg of 4-dimethylaminopyridine are dissolved in 94 ml of dichloromethane. The solution is then cooled to 0 &lt; 0 &gt; C and 18.3 ml (227 mmol) of pyridine are added dropwise over 25 minutes. After 4.5 h at 0 C, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was chromatographed over 200 g of silica gel with toluene to give 18.1 g (90%) of 3,5-dinitrobenzoic acid 11-bromoundecyl ester as a yellow powder.
[264] 3,5-dinitrobenzoic acid 11- [2,5-dihydroxybenzoyloxy] undecyl ester
[265]
[266] 2.78 g (18.0 mmol) of 2,5-dihydroxybenzoic acid is dissolved in 36 ml of dimethylformamide. 2.96 ml (19.8 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene (1,5-5) (DBU) is added dropwise over 15 minutes. After the reaction temperature was raised to 30 占 폚, 8.83 g (19.8 mmol) of 3,5-dinitrobenzoic acid 11-bromoundecyl ester was added in part. The mixture is then heated at 80 DEG C for 2 hours. The reaction mixture is cooled and then partitioned between dichloromethane and 1N hydrochloric acid and the organic phase is washed twice with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. Chromatography of the residue on 200 g of silica gel with toluene gave 5.28 g (57%) of 3,5- dinitrobenzoic acid 11- [2,5-dihydroxybenzoyloxy] undecyl ester as yellow powder.
[267] Synthesis of 3,5-dinitrobenzoic acid 11- [2-hydroxy-5- [4- (2-methoxycarbonylvinyl) -benzoyloxy] benzoyloxy]
[268]
[269] (4.82 mmol) of 3,5- dinitrobenzoic acid 11- [2,5-dihydroxybenzoyloxy] undecyl ester, 0.99 g (4.82 mmol) of methyl E) -4-carboxylate cinnamate and 4- 0.15 g (1.20 mmol) of dimethylaminopyridine are dissolved in 12 ml of dichloromethane. A suspension of 0.92 g (4.82 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride and 10 ml of dichloromethane is added dropwise over 45 minutes. After 3 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporator. The residue was chromatographed on 100 g of silica gel with toluene to give 3,5-dinitrobenzoic acid 11- [2- hydroxy 5- [4- (2-methoxycarbonyl-vinyl) benzoyloxy] benzoyloxy ] Undecyl ester (77%).
[270] Benzyloxy] benzoyl] undecarboxylic acid ethyl ester (prepared according to the method described in &lt; RTI ID = 0.0 &gt;
[271]
[272] (1.86 mmol) of 3,5- dinitrobenzoic acid 11- [2- [4-pentylbenzoyloxy] -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] benzoyloxy] 0.34 g (2.05 mmol) of 4-propylbenzoic acid and 63 mg (0.51 mmol) of 4-dimethylaminopyridine are dissolved in 26 ml of dichloromethane. A suspension of 0.39 g (2.05 mmol) of N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide hydrochloride and 11 ml of dichloromethane is added dropwise over 40 minutes. After 27.5 hours at room temperature, the reaction mixture is partitioned between dichloromethane and water and the organic phase is washed repeatedly with water, dried over sodium sulfate, filtered and concentrated by rotary evaporation. The residue was first chromatographed over 50 g of silica gel using toluene, then toluene: ethyl acetate, and crystallized from 300 ml of isopropyl alcohol to give 3,5-dinitrobenzoic acid 11- [2- [4-pentylbenzoyl Oxy] -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] benzoyloxy] undecyl ester (77%).
[273] 3,5-diaminobenzoic acid To a solution of 11- [2- [4-pentylbenzoyloxy] -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] benzoyloxy]
[274]
[275] (1.44 mmol) of 3,5-dinitrobenzoic acid 11- [2- [4-pentylbenzoyloxy] -5- [4- (2- methoxycarbonyl-vinyl) benzoyloxy] benzoyloxy] And 0.31 g (5.76 mmol) of ammonium chloride are suspended in 15 ml of a mixture of methanol: water (9: 1). Then, 1.88 g (28.8 mmol) of zinc is added in part. After 0.5 hours at room temperature, 20 ml of a mixture of methanol: water (9: 1) is added to the dark suspension. After a further 21 hours, the reaction suspension is partitioned between dichloromethane and water. The resulting suspension is filtered, the organic phase is washed with saturated sodium bicarbonate and washed repeatedly with water. The organic phase is then dried over sodium sulfate, filtered and concentrated by evaporation. The residue was chromatographed on 25 g of silica gel with toluene, toluene: ethyl acetate (9: 1) and toluene: ethyl acetate (1: 1) and then extracted twice from a mixture of ethyl acetate (5 ml) and hexane Crystallization was performed to obtain 3,5-diaminobenzoic acid 11- [2- [4-pentylbenzoyloxy] -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] benzoyl] 0.434 g (38%) is obtained.
[276] Example 4
[277] Examples of Copolymers
[278] Benzoyloxy) benzoyloxy] undecyloxycarbonyl] - (2-methoxy-benzoyloxy) Methylethylene-co-1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-pentylbenzoyloxy) benzoyloxy] undecyl Oxycarbonyl] -1-methylethylene]
[279]
[280] 0.89 g (1.22 mmol) of (E) -5- [4- (2-methoxycarbonylvinyl) benzoyloxy] -2- (4-propylbenzoyloxy) benzoic acid 11- mmol), (E) -5- [4- (2-methoxy-carbonylvinyl) benzoyloxy] -2- (4-pentylbenzoyloxy) benzoic acid 11- (2-methylacryloyloxy) The preparation was carried out analogously to example 1 using 0.10 g (0.13 mmol) and , '- azoisobutyronitrile (0.013 mmol) to give poly- [1- [11- [5- [4- [ (E) -2-methoxycarbonylvinyl] benzoyl] -2- (4-propylbenzoyloxy) -benzoyloxy] undecyloxycarbonyl] -1-methylethylene-co-1- [ - [4 - [((E) -2-methoxy-carbonylvinyl] benzoyloxy] -2- (4-pentylbenzoyloxy) benzoyloxy] undecyloxycarbonyl] -1-methylethylene] .
[281] The following copolymers can be synthesized in a similar way:
[282] - poly- [1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-propyl-benzoyloxy) benzoyloxy] undecyloxycarbonyl ] -1-methylethylene-co-1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-heptylbenzoyloxy) benzoyloxy] Undecyloxycarbonyl] -1-methylethylene]
[283] Benzyloxy] -2 - (4-pentylbenzyloxy) benzoyloxy] undecyloxycarbonyl] - &lt; RTI ID = 0.0 & -1-methylethylene-co-1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-heptylbenzoyloxy) benzoyloxy] Siloxycarbonyl] -1-methylethylene]
[284] - poly- [1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-propyl-benzoyloxy) benzoyloxy] undecyloxycarbonyl ] -1-methylethylene-co-1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy- 2- (4-propyl- cyclohexanoyloxy) Benzoyloxy] undecyloxycarbonyl] -1-methylethylene]
[285] Benzoyloxy) benzoyloxy] octyloxycarbonyl] -2-oxo-2- (4-methyl- -1-methylethylene-co-1- [8- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-heptylbenzoyloxy) benzoyloxy] octyl Oxycarbonyl] -1-methylethylene]
[286] Benzoyloxy) - &lt; / RTI &gt; benzoyloxy) octyloxycarbonyl] - 1-methylethylene-co-1- [11- [5- [4 - [(E) -2-methoxycarbonylvinyl] benzoyloxy] -2- (4-heptylbenzoyloxy) benzoyloxy] undecyl Oxycarbonyl] -1-methylethylene]
[287] Example 5
[288] A 2 wt% solution S1 of photoactive polymer A is prepared using cyclopentanone as solvent. The solution is stirred at room temperature for 30 minutes.
[289] Photopolymer A:
[290]
[291] Solution S1 is spin-coated at 2,000 rpm on two ITO (indium-tin oxide) coated glass plates and then dried at 180 DEG C for 10 minutes.
[292] The two substrates are then exposed to polarized ultraviolet light from a 200 W high-pressure mercury bulb for 6 minutes. The ultraviolet intensity measured in the light propagating perpendicular to the surface is 1.6 mW / cm ² . Polaroid-based film polarizer HNP'B is used to polarize ultraviolet light. During spinning, the substrate is tilted at 70 ° to the direction of the incident light, respectively.
[293] As the coated side faces inward, the two plates are assembled into parallel cells using 20 microns of glass fibers as spacers. The cell is immediately charged with a nematic liquid crystal mixture MLC12000-000 (Merck) at a temperature slightly higher than the nematic-isotropic transition temperature of 89 [deg.] C. After charging, cool the cell slowly.
[294] The pretilt angle of the liquid crystal cell measured using the crystal rotation technique is 88 [deg.].
[295] Example 6
[296] Manufactured M_LCP The mixture comprises the following liquid crystal diacrylate monomers:
[297] Monomer 1
[298]
[299] Monomer 2
[300]
[301] Monomer 3
[302]
[303] In addition to the diacrylate monomer, photoinitiator IRGACURE ^TM 369 (Ciba SC) acting as an inhibitor and BHT are added to the mixture. Thus, the components of the mixture M _LCP are as follows:
[304] Monomer 1 77 wt%
[305] Monomer 2 14.5 wt%
[306] Monomer 3 4.7 wt%
[307] IRGACURE ^TM 369 1.9 wt%
[308] BHT 1.9 wt%
[309] Finally, Solution S (LCP) is prepared by dissolving 20 wt% of the mixture M _{LCP in} anisole.
[310] Similar to Example 5, Solution S1 is spin-coated on a glass plate, dried and then exposed to polarized ultraviolet light at an incident angle of 70 degrees. The diacrylate solution S (LCP) is then spin-coated at 800 rpm for 2 minutes on top of the irradiated LPP layer. To crosslink the diacrylate, the plate is exposed to isotropic ultraviolet radiation for 5 minutes under a nitrogen atmosphere.
[311] Among the cross-linked polarisers, it has been found that the LCP layer is well aligned along the direction of the LPP-polarized UV radiation. It was concluded that the optical axis of the LCP layer was very skewed from the strong asymmetry time dependent on the LCP-retarder.
[312] In order to calculate the tilt angle averages of the optical axes, the effective optical anisotropy [Delta] n is measured as [Delta] _neff = 0.033 from measurements of layer thickness d and retardation [Delta] nd when viewed vertically through the layer. The average tilt angle of the optical axis from the known [Delta] n = 0.13 of the LCP material is calculated to be 58 [deg.].

权利要求:
Claims (36)
[1" claim-type="Currently amended] A photoactive polymer of formula (I).
Formula I

In the above formula (I)
P is a photoactive group that can be photoisomerized and / or photo-
B is a cyclic, straight or branched chain alkyl residue of 1 to 18 carbon atoms which is unsubstituted or substituted by fluorine, chlorine or cyano, unsubstituted or mono- or polysubstituted by cyano or halogeno, , one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 ^{-, -NR 2 -CO-, -CO-} NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = CH-, -C≡C- or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or a lower alkyl, by reacting an aromatic or alicyclic group Or further represents a nitrogen atom or -CR ² -,
A, C and D are independently of each other unsubstituted or substituted by fluorine, chlorine or cyano, cyclic, substituted or unsubstituted, mono- or polysubstituted by cyano or halogeno, straight or branched chain alkyl moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3 ^{_{) 2 -, -NR 2 -,}} -NR 2 -CO-, -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 - , -CH = CH-, -C C- or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or lower alkyl Aromatic or alicyclic group,
M represents a repeating monomer unit for a homopolymer or a copolymer,
S ¹ , S ² , S ³ , S ⁴ and S ⁵ are a single covalent bond, a straight or branched alkylene having 1 to 24 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, ^{-NR 2 -, -NR 2 -CO-,} -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = (-CO-, -CH-, -C C- or -O-CO-O-, with the proviso that oxygen atoms are not directly bonded to each other and R ² represents a hydrogen atom or a lower alkyl) spacer unit,
n ¹ and n ² are each independently a positive integer of 2 or less, provided that n ¹ + n ² is 2 or less,
R ¹ is a hydrogen atom, a straight or branched alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, wherein one or more CH ₂ groups are independently -O -, -CO-, -CO-O-, -O-CO-, -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, -NR ² -, -NR ² -CO-, -CO -NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH═CH-, -C≡C- or -O- O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² is a hydrogen atom or lower alkyl.
[2" claim-type="Currently amended] The polymer of claim 1, wherein the group P is a photocyclized group of formula (II) and (III).
(II)

(III)

In the above formulas (II) and (III)
The broken line represents the binding site for S ¹ ,
E is a cyclic, straight or branched chain alkyl residue of 1 to 18 carbon atoms which is unsubstituted or substituted by fluorine, chlorine or cyano, unsubstituted or mono- or polysubstituted by cyano or halogeno, , one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, -NR 2 ^{-, -NR 2 -CO-, -CO-} NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = CH-, -C≡C- or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other and R ² represents a hydrogen atom or a lower alkyl, 2,5-diyl, pyridin-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene or 1,4- or 2,6-naphthylene,
F is -OR ⁴ , -NR ⁵ R ⁶ wherein R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or a cyclic group having 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, , Straight or branched chain alkyl residues wherein one or more CH ₂ groups may be independently replaced by -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, Oxygen atoms do not directly bond to each other), or R ⁵ and R ⁶ bond together to form an alicyclic ring having 5 to 8 atoms], or oxygen which bonds to ring E at the ortho position to form a coumarin unit &Lt; / RTI &gt;
X and Y are each independently of the other hydrogen, fluorine, chlorine, cyano or alkyl of 1 to 12 carbon atoms optionally substituted with fluorine, wherein one or more non-adjacent CH ₂ groups are replaced by -O-, -CO- O-CO- and / or -CH = CH-,
R ³ is a hydrogen atom, a straight or branched alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by cyano or halogeno, wherein one or more CH ₂ groups are independently - O-, -CO-, -CO-O-, -O-CO-, -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ -, -NR ² -, -NR ² -CO-, -CO-NR ² -, -NR ² -CO-O-, -O-CO-NR ² -, -NR ² -CO-NR ² -, -CH = CH-, -C≡C- or -O-CO -O-, with the proviso that the oxygen atoms do not directly bond to each other and R ² represents a hydrogen atom or a lower alkyl.
[3" claim-type="Currently amended] The polymer according to claim 2, wherein the group P is a group of the formula (IV) and the formula (V).
Formula IV

Formula V

In the above formulas IV and V,
The broken line represents the binding site for S ¹ ,
R &lt; ³ &gt; is as defined for formula (II) and (III) in claim 2,
F is -OR ⁴ or -NR ⁵ R ⁶ wherein R ⁴ and R ⁵ are cyclic, linear or branched alkyl residues of 1 to 18 carbon atoms which are unsubstituted or mono- or polysubstituted by halogeno, Wherein one or more CH ₂ groups may be independently replaced with -O- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other, and R ⁶ is a hydrogen atom, Straight or branched chain alkyl residues of 1 to 18 carbon atoms, wherein one or more CH ₂ groups may be independently replaced by -O- or -CH = CH- And R &lt; ⁵ &gt; and R &lt; ⁶ &gt; together form an alicyclic ring having 5 to 8 atoms,
E is a cyclic, linear or branched alkyl residue of 1 to 12 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, wherein one or more CH ₂ groups are independently -O-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other Pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene .
[4" claim-type="Currently amended] A compound according to claim 3, wherein the group P is a straight or branched alkyl residue of 1 to 6 carbon atoms in which E is unsubstituted or mono- or polysubstituted by fluorine, wherein one or more CH ₂ groups are independently -O-, CO-, -CO-O-, -O-CO- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other, Pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-furanylene, 1,4- or 2,6-naphthylene,
Wherein F is -OR ⁴ or -NHR ⁵ wherein R ⁴ and R ⁵ are unsubstituted or mono- or polysubstituted C 1 -C 18 cyclic, linear or branched alkyl residues, wherein one or more CH ₂ Group may be independently replaced by -O-, with the proviso that the oxygen atoms are not directly bonded to each other.
[5" claim-type="Currently amended] The polymer according to any one of claims 1 to 4, wherein B represents an aromatic or alicyclic group, and n ¹ + n ² is 0 or 1.
[6" claim-type="Currently amended] The polymer according to any one of claims 1 to 4, wherein B represents a group -CR ² - and 0 <n ¹ + n ² 2.
[7" claim-type="Currently amended] 5. The polymer according to any one of claims 1 to 4, which is optically inactive.
[8" claim-type="Currently amended] 6. The compound according to any one of claims 1 to 5, wherein the group B is unsubstituted or mono-substituted by fluorine, chlorine or cyano, unsubstituted or by cyano or halogeno, or by halogeno A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, wherein at least one CH ₂ group is independently -O-, -CO-, -CO-O-, -O-CO- or -CH = CH- It can be optionally substituted with, with the proviso that oxygen atoms are not directly bonded to each other), or an aromatic substituted by, adding to the -CR ^2-polymer showing a (wherein, R ² represents a hydrogen atom or a lower alkyl).
[9" claim-type="Currently amended] The method of claim 8, wherein the group B is an unsubstituted or substituted by fluorine 1,2,5-benzenetricarboxylic or 1,3,5-benzenetricarboxylic one day group, the polymer to the spacer group S ⁵ present in the first position .
[10" claim-type="Currently amended] 10. A compound according to any one of claims 1 to 9, wherein the groups A, C and D are unsubstituted or substituted by fluorine, chlorine or cyano, unsubstituted or monosubstituted by cyano or halogeno, in the substituted number of carbon atoms of from 1 to 12 cyclic, straight or branched chain alkyl moiety by (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -CH = CH-, -C [identical to] C-, or -O-CO-O-, with the proviso that the oxygen atoms are not directly bonded to each other), or additionally cyclohexane- Diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4- or 2,6-naphthylene.
[11" claim-type="Currently amended] 11. A compound according to claim 10, wherein the groups A, C and D are straight or branched alkyl residues of 1 to 8 carbon atoms which are unsubstituted, fluorine-, unsubstituted or mono- or polysubstituted by fluorine, ₂ group may be independently substituted with -O-, -CO-, -CO-O-, -O-CO- or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other Or a cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl or 2,6-naphthylene.
[12" claim-type="Currently amended] 12. The compound according to any one of claims 1 to 11, wherein S ¹ , S ² , S ³ , S ⁴ and S ⁵ are a single covalent bond, unsubstituted or mono- or poly- substituted by fluorine, chlorine or cyano the formula - (CH _{2) r} - a linear or branched alkylene group, or formula _{^{-L 1 - (CH 2) r}} -L 2 - or _{^{-L 1 - (CH 2) r}} -L 2 - (CH 2) _s -L ³ - wherein L ¹ , L ² and L ³ are each independently a single bond or a linking functional group, R ² is a hydrogen atom or a lower alkyl, and r and s are each an integer of 1 to 20 , Provided that r + s is not more than 24 and L &lt; ¹ &gt; represents a single bond when the repeating monomer unit M is bonded to S &lt; ⁵ &gt; through a nitrogen atom or an oxygen atom defined as a part of M.
[13" claim-type="Currently amended] 13. The method of claim ^{12, S 1, S 2, S} 3, S 4 and S ⁵ is _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO-, - (CH ₂ ) _r -CO-O-, - (CH ₂ ) _r -O-CO-, - (CH ₂ ) _r -CO-NR ² -, - (CH ₂ ) _r -NR ² -CO-, ^{_{(CH 2) r -NR 2 -}} , -O- (CH 2) r -, -CO-O- (CH 2) r -, -O-CO- (CH 2) r -, -NR 2 -CO- (CH ₂ ) _r -, -CO-NR ² - (CH ₂ ) _r -, -NR ² - (CH ₂ ) _r -, -O- (CH ₂ ) _r -CO-O-, _{2) r -O-CO-, -O-} (CH 2) r -CO-NR 2 -, -O- (CH 2) r -NR 2 -, -O- (CH 2) r -O-, - ^{_{O- (CH 2) r -NR 2}} -CO-, -NR 2 - (CH 2) r -CO-O-, -NR 2 - (CH 2) r -O-, -NR 2 - (CH 2) ^{_{r -NR 2 -, -NR 2 -}} (CH 2) r -O-CO-, -CO-NR 2 - (CH 2) r -O-, -CO-NR 2 - (CH 2) r -NR 2 ^{-, -CO-NR 2 - (} CH 2) r -O-CO-, -O-CO- (CH 2) r -CO-, -O-CO- (CH 2) r -O-, -O- ^{_{CO- (CH 2) r -NR 2}} -, -O-CO- (CH 2) r -CO-O-, -O-CO- (CH 2) r -CO-NR 2 -, -O-CO- ^{_{(CH 2) r -NR 2 -CO-}} , - (CH 2) r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - (CH 2 _{) r -O-CO- (CH 2} ) s -, - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH 2 _{) s -, - (CH 2} ) r -O- (CH 2) s -O-, - (CH 2) r -CO-O- (CH 2) _{s -O-, (CH 2) r} -O-CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO- (CH 2) s -O-, - (CH 2) ^{_{r -NR 2 -CO-O- (CH}} 2) s -O-, -O- (CH 2) r -O- (CH 2) s -, -O- (CH 2) r -CO-O- ( _{CH 2) s -, -O- (} CH 2) r -NR 2 -CO- (CH 2) s -, -O- (CH 2) r -NR 2 -CO-O- (CH 2) s -, _{-O- (CH 2) r -CO-} O- (CH 2) s -O-, -O- (CH 2) r -O- (CH 2) s -O-, -O- (CH 2) r _{^{-NR 2 -CO- (CH 2) s}} -O-, -O- (CH 2) r -NR 2 -CO-O- (CH 2) s -O-, -CO-O- (CH 2) r -O- (CH ₂ ) _s - or -CO- O- (CH ₂ ) _r -O- (CH ₂ ) _s -O- wherein r and s are each from 1 to 20 With the proviso that r + s is not more than 21 and R ² is hydrogen or lower alkyl.
[14" claim-type="Currently amended] 14. The method of claim ^{13, S 1, S 2, S} 3, S 4 and S ⁵ is _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO-O- _{, - (CH 2) r -O} -CO-, - (CH 2) r -CO-NH-, - (CH 2) r -NH-CO-, -O- (CH 2) r -, -CO- _{O- (CH 2) r -,} -CO-NH- (CH 2) r -, -O-CO- (CH 2) r -, -O-CO- (CH 2) r -CO-O-, - _{0- (CH 2) r -O-} CO-, -O- (CH 2) r -CO-NH-, -O- (CH 2) r -NH-CO-, -CO-O- (CH 2) _{r -O-, -CO-NH- (CH} 2) r -O-, -O- (CH 2) r -O-, - (CH 2) r -NH-CO- (CH 2) s -, - _{(CH 2) r -NH-CO} -O- (CH 2) s -, - (CH 2) r -O- (CH 2) s -O-, - (CH 2) r -NH-CO- (CH _{2) s -O-, - (CH} 2) r -NH-CO-O- (CH 2) s -O-, -O- (CH 2) r -NH-CO- (CH 2) s -, - _{O- (CH 2) r -O- (} CH 2) s -O-, -O-CO- (CH 2) r -O- (CH 2) s -O-, -CO-O- (CH 2) _{r -O- (CH 2) s -O-} , -O- (CH 2) r -NH-CO- (CH 2) s -O- , or _{-O-CO- (CH 2) r} -NH-CO- (CH ₂ ) _s -O-, wherein r and s are each an integer of 2 to 12, and the sum of r and s is 15 or less.
[15" claim-type="Currently amended] 15. A compound according to any one of claims 1 to 14, wherein R &lt; ¹ &gt; is a hydrogen atom, a linear or branched alkyl residue of 1 to 12 carbon atoms which is unsubstituted or substituted by halogeno or polyhalogeno, CH ₂ groups may be independently substituted with -O-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, Lt; / RTI &gt;
[16" claim-type="Currently amended] 16. The method of claim 15 wherein, R ¹ is C 1 -C 8 straight or branched chain alkyl moiety of (wherein one or more CH ₂ groups are each independently -O-, -CO-, -CO-O-, -O -CO- Or -CH = CH-, with the proviso that the oxygen atoms are not directly bonded to each other.
[17" claim-type="Currently amended] 17. The polymer according to any one of claims 1 to 16, wherein the repeating monomer unit M is an acrylate, a methacrylate, a styrene derivative, an imide, an amic acid and an ester or an amide imide thereof.
[18" claim-type="Currently amended] 18. The process according to any one of claims 1 to 17, wherein the imide unit M synthesizing the main chain comprises at least one group of the formulas IIIa, Va and VII and / or a homologous group of the formula IVa, VI and VIII, Polymer.
&Lt; RTI ID =

IVa

The formula Va

VI

Formula VII

VIII

In formulas (IIIa) to (VIII) above,
The dashed line represents the bond to S ⁵ ,
T ¹ represents a tetravalent organic radical of tetracarboxylic dianhydride after removal of the two -CO-O-CO- groups, the four valences being distributed among the four different carbon atoms of the radical,
T ² and T ³ are each independently an aromatic or cycloaliphatic trivalent group wherein the three valences are distributed among the three different carbon atoms of the group and the group is unsubstituted or substituted by fluorine, chlorine or cyano, Or a cyclic, straight or branched chain alkyl residue of 1 to 18 carbon atoms which is unsubstituted or mono- or polysubstituted by halogeno, wherein one or more CH ₂ groups are independently -O-, -CO-, - CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other,
S ⁶ , S ⁷ , S ⁸ , S ⁹ and S ¹⁰ are independently a single covalent bond or a straight-chain or branched alkylene of 1 to 24 carbon atoms which is unsubstituted, mono- or polysubstituted by cyano or halogeno, moiety (wherein one or more CH ₂ groups are independently selected from -O-, -CO-, -CO-O-, -O-CO-, -Si (CH 3) 2 -O-Si (CH 3) 2 -, ^{-NR 2 -, -NR 2 -CO-,} -CO-NR 2 -, -NR 2 -CO-O-, -O-CO-NR 2 -, -NR 2 -CO-NR 2 -, -CH = -, -CO-O-, with the proviso that oxygen atoms are not directly bonded to each other and R ² represents a hydrogen atom or a lower alkyl. And,
J is a divalent, trivalent or tetravalent aromatic or alicyclic group, wherein the valencies are distributed among the different atoms of these groups, these groups being unsubstituted or substituted by fluorine, chlorine or cyano, , Cyclic, straight or branched chain alkyl residues having from 1 to 18 carbon atoms, wherein one or more CH ₂ groups are independently replaced by -O-, CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, with the proviso that the oxygen atoms are not directly bonded to each other Or further represents a nitrogen atom or -CR ² -, wherein R ² is a hydrogen atom or lower alkyl,
K represents a radical of an aliphatic, alicyclic or aromatic diamine after removing two amino groups,
G represents a monovalent organic group derived from an alcohol after removal of a hydrogen atom or a hydroxy group.
[19" claim-type="Currently amended] 19. The compound of claim 18, wherein the groups T ² and T ³ are trivalent aromatic or carbocyclic groups wherein the three valences are distributed between three different carbon atoms, two of which are located at adjacent carbon atoms ).
[20" claim-type="Currently amended] 20. The compound of claim 19, wherein the groups T ² and T ³ are trivalent benzene derivatives wherein the three valences are distributed among three different carbon atoms, polymer.
[21" claim-type="Currently amended] 19. The method of claim 18 to any one of Claim 20, S ⁶ is _{- (CH 2) r -,} - (CH 2) r -O-, - (CH 2) r -CO-, - (CH 2) _{r -CO-O-, - (CH} 2) r -O-CO-, - (CH 2) r -CO-NR 2 -, - (CH 2) r -NR 2 -CO-, - (CH 2) ^{_{r -NR 2 -, - (CH}} 2) r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - (CH 2) r -O-CO _{- (CH 2) s -,} - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH 2) s -, - ( _{CH 2) r -O- (CH 2} ) s -O-, - (CH 2) r -CO-O- (CH 2) s -O-, - (CH 2) r -O-CO- (CH 2 _{) s -O-, - (CH 2} ) r -NR 2 -CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO-O- (CH 2) s -O-, Chain or branched alkylene group of the formula - (CH ₂ ) _r -O- (CH ₂ ) _s -CO-O- or - (CH ₂ ) _r -O- (CH ₂ ) _s -O- And s are each an integer from 1 to 20, with the proviso that r + s is not more than 21 and R ² is hydrogen or lower alkyl.
[22" claim-type="Currently amended] 19. The method of claim 18 to any one of Claim 21, S ⁷ and S ¹⁰ are _{- (CH 2) r -,} -O- (CH 2) r -, -CO- (CH 2) r -, -CO _{-O- (CH 2) r -,} -O-CO- (CH 2) r -, -NR 2 -CO- (CH 2) r -, -NR 2 - (CH 2) r -, -CO-NR _{^{2 - (CH 2) r -}} , -NR 2 -CO- (CH 2) r -, -O- (CH 2) r -O- (CH 2) s -, - (CH 2) r -CO-O _{- (CH 2) s -,} - (CH 2) r -O-CO- (CH 2) s -, - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) ^{_{r -NR 2 -CO-O- (CH}} 2) s -, -O- (CH 2) r -O- (CH 2) s -, -O- (CH 2) r -CO-O- (CH 2 _{) s -, -O- (CH 2} ) r -O-CO- (CH 2) s -, -O- (CH 2) r -NR 2 -CO- (CH 2) s -, -O- (CH ^{_{2) r -NR 2 -CO-O-}} (CH 2) s -, -O-CO- (CH 2) r -O- (CH 2) s - or _{-CO-O- (CH 2) r} -O - (CH ₂ ) _s -, wherein r and s are each from 1 to 20, with the proviso that r + s is not more than 21 and R ² is hydrogen or lower alkyl.
[23" claim-type="Currently amended] 22. A compound according to any one of claims 18 to 22, wherein S ⁸ and S ⁹ are selected from the group consisting of - (CH ₂ ) _r -, - (CH ₂ ) _r --O--, - (CH ₂ ) _r --CO--, - CH ₂ ) _r -CO-O-, - (CH ₂ ) _r -O-CO-, - (CH ₂ ) _r -CO-NR ² -, - (CH ₂ ) _r -NR ² -CO-, CH ₂ ) _r -NR ² -, -O- (CH ₂ ) _r -, -CO-O- (CH ₂ ) _r -, -O-CO- (CH ₂ ) _r -, -NR ² -CO- _{CH 2) r -, -CO-} NR 2 - (CH 2) r -, -NR 2 - (CH 2) r -, -O- (CH 2) r -CO-O-, -O- (CH 2 _{) r -O-CO-, -O- (} CH 2) r -CO-NR 2 -, -O- (CH 2) r -NR 2 -, -O- (CH 2) r -O-, -O ^{_{- (CH 2) r -NR 2}} -CO-, -NR 2 - (CH 2) r -CO-O-, -NR 2 - (CH 2) r -O-, -NR 2 - (CH 2) r ^{-NR 2 -, -NR 2 - (} CH 2) r -O-CO-, -CO-NR 2 - (CH 2) r -O-, -CO-NR 2 - (CH 2) r -NR 2 - ^{, -CO-NR 2 - (CH} 2) r -O-CO-, -O-CO- (CH 2) r -CO-, -O-CO- (CH 2) r -O-, -O-CO ^{_{- (CH 2) r -NR 2}} -, -O-CO- (CH 2) r -CO-O-, -O-CO- (CH 2) r -CO-NR 2 -, -O-CO- ( ^{_{CH 2) r -NR 2 -CO-,}} - (CH 2) r -O- (CH 2) s -, - (CH 2) r -CO-O- (CH 2) s -, - (CH 2) _{r -O-CO - (CH 2} ) s -, - (CH 2) r -NR 2 -CO- (CH 2) s -, - (CH 2) r -NR 2 -CO-O- (CH 2 ) _s- , - (CH ₂ ) _r -O- (CH ₂ ) _s -O-, - (CH _{2) r -CO-O- (CH} 2) s -O-, - (CH 2) r -O-CO- (CH 2) s -O-, - (CH 2) r -NR 2 -CO- ( _{CH 2) s -O-, - (} CH 2) r -NR 2 -CO-O- (CH 2) s -O-, -O- (CH 2) r -O- (CH 2) s -, - _{O- (CH 2) r -CO-} O- (CH 2) s -, -O- (CH 2) r -NR 2 -CO- (CH 2) s -, -O- (CH 2) r -NR _{^{2 -CO-O- (CH 2)}} s -, -O- (CH 2) r -CO-O- (CH 2) s -O-, -O- (CH 2) r -O- (CH 2) _{s -O-, -O- (CH 2)} r -NR 2 -CO- (CH 2) s -O-, -O- (CH 2) r -NR 2 -CO-O- (CH 2) s - _{O-, -CO-O- (CH 2} ) r -O- (CH 2) s - or _{-CO-O- (CH 2) r} -O- (CH 2) s -O- is straight chain or branched alkylene Group, wherein r and s are each an integer from 1 to 20, with the proviso that r + s is not more than 21 and R ² is hydrogen or lower alkyl.
[24" claim-type="Currently amended] 24. Polymer according to any one of claims 1 to 23, characterized in that it is a copolymer.
[25" claim-type="Currently amended] 24. The polymer according to any one of claims 18 to 23, wherein at least 50% of the monomer building blocks forming the main chain are connected to one or two side chains comprising the entire of formula (I) except M.
[26" claim-type="Currently amended] The polymer according to claim 25, wherein at least 70% of the monomer building blocks forming the main chain are connected to one or two side chains.
[27" claim-type="Currently amended] 24. The polymer according to any one of claims 18 to 23, wherein the monomer building blocks carrying side chains are each connected to only one side chain.
[28" claim-type="Currently amended] 27. A polymer according to any one of claims 18 to 27, wherein G is hydrogen, the polymer comprising at least one group of the formula (IV), (VI) or (VIII).
[29" claim-type="Currently amended] 29. The polymer according to any one of claims 1 to 28, which contains as an additive a silane-containing compound and / or an epoxy-containing crosslinking agent.
[30" claim-type="Currently amended] 30. The polymer according to any one of claims 1 to 29, comprising as an additive a photosensitizer, a photoradical generator and / or a cationic photoinitiator.
[31" claim-type="Currently amended] 31. The polymer of any one of claims 1 to 30, wherein the polymer is a mixture of one or more other polymers, oligomers, monomers, photoactive polymers, photoactive oligomers and / or photoactive monomers.
[32" claim-type="Currently amended] 32. The polymer according to any one of claims 1 to 31, which is applied to a support and optionally crosslinked by irradiation with linear polarized light after an imidization step.
[33" claim-type="Currently amended] The use of the polymer according to any one of claims 1 to 32 as an orientation layer for liquid crystals and in the production of optical structural elements.
[34" claim-type="Currently amended] 34. The method of claim 33, wherein a solution of the polymeric material is prepared and then applied to a support, followed by optionally irradiating an area optionally covered or oriented using electrodes in a spin coating apparatus to produce a uniform layer Use of polymers.
[35" claim-type="Currently amended] An optical or electro-optical device having at least one orientation layer, characterized in that the orientation layer contains a polymer according to any one of claims 1 to 32.
[36" claim-type="Currently amended] 32. The use of a polymer according to any one of claims 1 to 32 in the preparation of an unstructured or structured optical element or multilayer system.

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同族专利:

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公开号 | 公开日

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EP1171493B1|2003-04-23|

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EP1171493A1|2002-01-16|

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KR100585044B1|2006-06-01|

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HK1039949A1|2003-08-22|

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CN1345342A|2002-04-17|

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DE60002312D1|2003-05-28|

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US6649230B1|2003-11-18|

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JP4755345B2|2011-08-24|

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WO2000059966A1|2000-10-12|

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GB9907801D0|1999-06-02|

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JP2002541277A|2002-12-03|

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DE60002312T2|2004-02-19|

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CN1157425C|2004-07-14|

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AT238361T|2003-05-15|

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AU3315400A|2000-10-23|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1999-04-06|Priority to GB9907801.6

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1999-04-06|Priority to GBGB9907801.6A

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2000-03-27|Application filed by 보러 롤란드, 롤리크 아게

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2000-03-27|Priority to PCT/IB2000/000349

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2001-12-07|Publication of KR20010108454A

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2006-06-01|Application granted

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2006-06-01|Publication of KR100585044B1

优先权:

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申请号 | 申请日 | 专利标题

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GB9907801.6|1999-04-06|

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GBGB9907801.6A|GB9907801D0|1999-04-06|1999-04-06|Photoactive polymers|

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PCT/IB2000/000349|WO2000059966A1|1999-04-06|2000-03-27|Photoactive polymers|