CN1721502A - Liquid crystal aligning agent and liquid crystal display element - Google Patents

Liquid crystal aligning agent and liquid crystal display element Download PDF

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CN1721502A
CN1721502A CN 200510091160 CN200510091160A CN1721502A CN 1721502 A CN1721502 A CN 1721502A CN 200510091160 CN200510091160 CN 200510091160 CN 200510091160 A CN200510091160 A CN 200510091160A CN 1721502 A CN1721502 A CN 1721502A
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liquid crystal
phenyl
methyl
fluoro
styryl ketone
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CN100344731C (en
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中田正一
木村雅之
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JSR Corp
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JSR Corp
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Abstract

The present invention provides a liquid crystal aligning agent which provides a liquid crystal alignment film having surface anchoring force and pretilt angle development stability by an optical aligning method. The liquid crystal aligning agent comprises a polymer having a photo-crosslinkable structure a structure having at least one group selected from the group consisting of a fluorine-containing organic group, an alkyl group having 10 to 30 carbon atoms and alicyclic organic group having 10 to 30 carbon atoms and optionally, (C) a thermally crosslinkable structure.

Description

Liquid crystal aligning agent and liquid crystal display device
The present patent application is that application number is the dividing an application of application for a patent for invention of CN02144209.6 (applying date is on October 8th, 2002).
Technical field
The present invention relates to the formation method and the liquid crystal display device of liquid crystal aligning agent, liquid crystal orientation film.In more detail, relate to by not carrying out grinding process irradiation straight line polarising radioactive rays, thus can access the liquid crystal orientation film of orientation characteristic and pre-tilt angle performance excellent in stability liquid crystal aligning agent, use this liquid crystal aligning agent to form the method for liquid crystal orientation film and have the liquid crystal display device of this liquid crystal orientation film.
Background technology
In the past, known liquid crystal display device with TN (Twisted Nematic) type, STN (Super TwistedNematic) type liquid crystal cells, this TN type, STN type liquid crystal cells are made sandwich structure by the nematic liquid crystal that will have positive dielectric anisotropy with the substrate that band has the transparency electrode of liquid crystal orientation film, and the major axis of liquid crystal molecule is turned round continuously between substrate and turn 90 degrees above forming.
Above-mentionedly orientation takes place for liquid crystal in the liquid crystal cells method is had at substrate surface form organic membrane, then with clothes such as artificial silks along the direction surface of this organic membrane that rubs, thereby make it to have the liquid crystal aligning ability method of (carrying out grinding process); Method at substrate surface quadrature evaporation silicon oxide; Use Langmuir-Blodgett method (LB method) forms the method for the unimolecular film with chain alkyl etc.But in these methods, because the size of the substrate that both methods of back are handled is restricted, perhaps the homogeneity of liquid crystal aligning is insufficient, the liquid crystal aligning that therefore industrial general employing treatment time and the favourable employing grinding process in processing cost aspect are carried out.
On the other hand, if adopt grinding process to carry out liquid crystal aligning, then exist to be easy to produce dust in this operation, or be easy to produce the electrostatic problem.If generation static, then dust becomes bad reason takes place to show attached to alignment layer surface, in addition, occasion with substrate of TFT (thin filmtransistor) element is because the destruction that the static that produces causes the TFT element circuitry also becomes the reason that yield rate reduces.And, in the liquid crystal display device that will more and more become more meticulous from now on, owing to follow substrate surface concavo-convex of pixel densification, so the homogeneity of grinding process also becomes problem.
Make the additive method that orientation takes place for liquid crystal in the liquid crystal cells be, by to being formed at photosensitive organic films such as the poly-vinyl cinnamate irradiation straight line polarising ultraviolet ray of substrate surface, thereby in alignment films, introduce anisotropy, make it to have the liquid crystal aligning ability.Adopt this method can not produce static or dust, can realize uniform liquid crystal aligning.
As the photosensitive organic film that uses in this optical alignment method, can exemplify and resemble the material that causes photolysis the polyimide, resemble the material that causes photoisomerization the azobenzene derivatives, resemble the material that causes photo-crosslinking poly-vinyl cinnamate, poly-(4 ((2-methacryloxy) oxyethyl group) phenyl styryl ketone) etc. etc.Wherein, think at the organic film that aspect the thermostability of alignment films, electrical characteristic, preferably causes photo-crosslinking.
But, in the alignment films that obtains by this optical alignment method, can not obtain sufficient liquid crystal aligning restraint in the past, therefore, when being used for liquid crystal display device, it is bad to be easy to take place orientations such as flow orientation or disclination (デ ィ ス Network リ ネ-シ ョ Application).As the method that is used to obtain stable orientation characteristic, proposition will be heated by the liquid crystal orientation film of rayed orientation to improve the method (opening 2001-290155 number with reference to the spy) of liquid crystal aligning restraint, but usually, if heating liquid crystal orientation film, then pre-tilt angle becomes unstable, brings out the deterioration of element display quality such as inhomogeneous in the generation of generation, disclination (デ ィ ス Network リ ネ-シ ョ Application) line in pre-tilt zone or the electrooptics characteristic surface.
On the other hand, a kind of operating mode as liquid crystal display device, the known liquid crystal molecule vertical orientated vertical (homeotropic on substrate that makes with negative dielectric anisotropy, ホ メ オ ト ロ ピ ッ Network) orientation, if this operating mode impressed voltage between substrate, then liquid crystal molecule tilts to the direction that is parallel to substrate.When proposing impressed voltage, liquid crystal molecule is tilted by the direction of substrate normal direction in real estate, therefore under the state of impressed voltage not, and for substrate normal, the orientation that liquid crystal molecule is tilted a little.
But, when adopting the vergence direction of this method control liquid crystal molecule,, therefore have the problem that is easy to take place orientation disorder owing to the horizontal electric field effects that produces between ピ Network unit because the orientation limitations of direction is insufficient in the real estate of liquid crystal molecule.At this moment, the orientation limitations of direction can be improved apart from the pitch angle of substrate normal direction by increasing in the real estate of liquid crystal molecule, but, when for example having pitch angle more than 5 ° apart from the substrate normal direction, the transmitance of the light under the impressed voltage state does not increase, thereby produces the new problem that contrast gradient reduces.
Invention is described
The object of the present invention is to provide a kind of liquid crystal aligning agent, it can access and have both orientation limitations power and the stable liquid crystal orientation film of pre-tilt angle performance that carries out the liquid crystal orientation film of orientation process by optical alignment method.
Another object of the present invention is to provide the formation method of the liquid crystal orientation film that uses above-mentioned liquid crystal aligning agent of the present invention.
Another object of the present invention is to provide the display characteristic liquid crystal display device with excellent of the above-mentioned liquid crystal orientation film of a kind of the present invention of having.
Another purpose of the present invention is to provide a kind of liquid crystal aligning agent of vertical orientating type, even do not show the pitch angle apart from substrate normal, makes liquid crystal molecule have the liquid crystal orientation film of the orientation limitations power of direction in the real estate in the time of also can forming impressed voltage.
Other purposes of the present invention and advantage are by following explanation as can be known.
Adopt the present invention, the first, realize above-mentioned purpose of the present invention and advantage by a kind of liquid crystal aligning agent (below be also referred to as " liquid crystal aligning agent is 1. "), this liquid crystal aligning agent is characterised in that, contains polymkeric substance, this polymkeric substance has:
(A) can carry out the structure (below be also referred to as " structure (A) ") of crosslinking reaction by light, and
(B) has the structure (below be also referred to as " structure (B) ") of at least a kind of group of the ester ring type organic group of the alkyl that is selected from fluorine-containing organic group, carbonatoms 10～30 and carbonatoms 10～30.
Adopt the present invention, second, realize above-mentioned purpose of the present invention and advantage by a kind of liquid crystal aligning agent (below be also referred to as " liquid crystal aligning agent 2. "), this liquid crystal aligning agent comprises: the polymkeric substance that has structure (A), structure (B) and (C) carry out crosslinked structure (below be also referred to as " structure (C) ") by heat, perhaps have be selected from said structure (A), (B) and (C) at least a kind of structure mixture of polymers and have said structure (A), (B) and (C) whole polymeric blends.
The 3rd, by a kind of liquid crystal aligning agent (below be also referred to as " liquid crystal aligning agent 3. ".In addition, sometimes also with liquid crystal aligning agent 1., 3. 2. liquid crystal aligning agent be generically and collectively referred to as " liquid crystal aligning agent of the present invention " with liquid crystal aligning agent) realize above-mentioned purpose of the present invention and advantage, this liquid crystal aligning agent is characterised in that, contains:
Polymkeric substance with structure (A) and structure (B), perhaps have be selected from said structure (A) and (B) at least a kind of structure mixture of polymers and contain structure (A) and polymeric blends (B) simultaneously, and
(C ') has the compound (below be also referred to as " compound (C ') ") that carries out crosslinked structure by heat.
The 4th, the formation method by a kind of liquid crystal orientation film realizes above-mentioned purpose of the present invention and advantage, and the formation method of this liquid crystal orientation film is characterised in that, the film that is obtained by liquid crystal aligning agent of the present invention is heated to more than the room temperature, shines polarized UV rays simultaneously.
The 5th, realize above-mentioned purpose of the present invention and advantage by a kind of liquid crystal display device, this liquid crystal display device has the liquid crystal orientation film that is obtained by liquid crystal aligning agent of the present invention.
Description of drawings
Fig. 1 is the graphic representation of the stable evaluation result of the pre-tilt angle performance of expression embodiment 4 and comparative example 2.
The working of an invention mode
Describe the present invention below in detail.
Liquid crystal aligning agent 1.
1. liquid crystal aligning agent be characterised in that, contains have structure (A) and structure (B) and do not have the polymkeric substance (below be also referred to as " particular polymers ") of following structure (C).
Skeleton to particular polymers is not particularly limited.For example polyamic acid, polyimide, poly maleimide, polystyrene, maleimide/styrol copolymer, polyester, polymeric amide, poly-(methyl) acrylate, polysiloxane and their multipolymer.Particularly from the angle of thermotolerance, good electric performance, preferred polyimide, polyamic acid, polystyrene and maleimide/styrol copolymer.
Proportional as containing of structure in the particular polymers (A) and structure (B), for whole repeating units, it is preferred 10～95% to have a repeating unit of structure (A), and more preferably 50～90%, it is preferred 5～50% to have the repeating unit of structure (B), and more preferably 10～25%.
For liquid crystal aligning agent each constituent 1., will narrate in the back.
Liquid crystal aligning agent 2.
2. liquid crystal aligning agent be characterised in that, comprises the polymkeric substance or the polymeric blends of have structure (A), structure (B) and structure (C).Wherein said polymkeric substance is the multipolymer with structure (A), structure (B) and structure (C), polymeric blends is to use a plurality of polymkeric substance with at least a structure in structure of being selected from (A), structure (B) and the structure (C), and as the polymeric blends that all has structure (A), structure (B) and structure (C).
As preferred component of polymer, for example following 1～3.
1, above-mentioned particular polymers and have the mixture of polymers of structure (C).
2, the multipolymer that has structure (A), structure (B) and structure (C).
3, has the polymkeric substance of structure (A) and have structure (B) and do not have the polymkeric substance of structure (A) and have structure (C) and do not have the mixture of polymers of structure (A), (B).
The skeleton of the polymkeric substance that uses among the present invention is not particularly limited, as polymkeric substance with structure (A), have structure (B) and do not have the polymkeric substance of structure (A), perhaps particular polymers (also it being generically and collectively referred to as " polymkeric substance I " sometimes), for example polyamic acid, polyimide, poly maleimide, polystyrene, maleimide/styrol copolymer, polyester, polymeric amide, poly-(methyl) acrylate, polysiloxane and their multipolymer.Particularly from the angle of thermotolerance, good electric performance, preferred polyimide, polyamic acid, polystyrene and maleimide/styrol copolymer.In addition, as having structure (C) and not having the polymkeric substance of structure (A), (B), as preferred material for example Resins, epoxy, have (methyl) acrylic polymer of epoxy construction etc. at side chain, as multipolymer, as preferred material for example polystyrene and maleimide/styrol copolymer with structure (A), structure (B) and structure (C).
Proportional as containing of the structure in whole component of polymer (A)～(C), for the whole repeating units in the component of polymer, repeating unit preferred 10～95% with structure (A), more preferably 50～90%, repeating unit preferred 5～50% with structure (B), more preferably 10～25%, it is preferred 0.1～5% to have a repeating unit of structure (C), and more preferably 1～4%.
To narrate in the back for liquid crystal aligning agent each constituent 2..
Liquid crystal aligning agent 3.
3. liquid crystal aligning agent be characterised in that, contains the polymkeric substance of have structure (A) and structure (B) or polymeric blends and compound (C ').Wherein said polymkeric substance is a particular polymers, polymeric blends be have structure (A) polymkeric substance and have structure (B) and do not have the mixture of polymers of structure (A).
The skeleton of polymkeric substance is not particularly limited, and can exemplify the structure of above-mentioned polymkeric substance I as preferred material.Particularly, preferably use polyimide and/or polyamic acid, use compound as compound (C ') with epoxy construction as component of polymer.
Proportional as containing of structure in polymkeric substance or the polymeric blends (A) and structure (B), for the whole repeating units in polymkeric substance or the polymeric blends, repeating unit preferred 10～95% with structure (A), more preferably 50～90%, it is preferred 5～50% to have the repeating unit of structure (B), and more preferably 10～25%.
In addition, proportional as containing of compound (C '), for polymkeric substance or polymeric blends 100 weight parts, preferred 0.1～30 weight part, more preferably 1～10 weight part.
To narrate in the back for liquid crystal aligning agent each constituent 3..
Structure (A)
Structure (A) is not particularly limited so long as can get final product by the structure that light carries out crosslinking reaction, as preferred material, for example is selected from following formula (I), (II), (III) and at least a conjugation ketenes structure (IV).
-P 1-CR 1＝CR 2-CO-Q 1-····(I)
P 2-CR 3＝CR 4-CO-Q 2-····(II)
P 3-CR 5＝CR 6-CO-Q 3-····(III)
-P 4-CR 7＝CR 8-CO-Q 4····(IV)
In the formula, P 1, P 2, P 3, P 4, Q 1, Q 2, Q 3And Q 4Expression contains the organic group of aromatic nucleus, P 1, P 4, Q 1And Q 3For having the divalent organic group of aromatic nucleus, P 2, P 3And Q 4For having 1 valency organic group of aromatic nucleus, Q 2For having 3 valency organic groups of aromatic nucleus, R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Expression hydrogen atom or alkyl.
As P 1, P 2, P 3, P 4, Q 1, Q 2, Q 3And Q 4The organic group that contains aromatic nucleus, preferably as the organic group of carbonatoms 6～20.
In these organic groups, also can contain halogen atom.Specifically, as P 2, P 3And Q 4For example 4-amyl group phenyl, 4-fluorophenyl, 3,4-difluorophenyl, 3,4,5-trifluorophenyl, 4-octyl phenyl, 4-pentylbiphenyl base, 4-octyl group xenyl, 4-fluorine xenyl, 3,4-difluoro biphenyl, 3,4,5-trifluoro-biphenyl base, 4-octyl group-1-naphthyl, 5-amyl group-1-naphthyl, 6-octyl group-2-naphthyl, 9-anthryl, 10-amyl group-9-anthryl etc.
In addition, as P 1, P 4, Q 1And Q 3, for example 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 4,4 '-biphenylene etc.
And, as Q 2, be the skeleton of any one 3 valency, for example benzene skeleton, biphenyl backbone, naphthalene skeleton, anthracene skeleton etc.
These groups mutually can be identical, also can be different.
In addition, in the formula, R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Be hydrogen atom or alkyl, the alkyl of preferred hydrogen atom or carbonatoms 1～6.These alkyl can be the straight chain shape, also can be the side chain shape, each other can be identical, and also can be different.
As other examples of structure (A), can exemplify stilbene derivatives structure, benzophenone derivative structure, cinnyl structure etc.These structures can be the straight chain shape, also can be in tonka bean camphor structure, be the part of ring texture.These structures (A) may be used alone, can also be combi in component of polymer.
Structure (B)
Structure (B) is at least a kind of group that is selected from the ester ring type organic group of the alkyl of fluorine-containing organic group, carbonatoms 10～30 and carbonatoms 10～30, the effect that the liquid crystal orientation film that is obtained by liquid crystal aligning agent of the present invention is had the pre-tilt angle of giving.
As fluorine-containing organic group, for example trifluoromethyl, pentafluoroethyl group, 4-fluorine cyclohexyl, five fluorine cyclohexyl, 4-fluorophenyl, pentafluorophenyl group etc.As the alkyl of carbonatoms 10～30, groups such as for example positive decyl, dodecyl, n-tetradecane base, Pentadecane base, n-hexadecyl, Octadecane base, NSC 62789 base.In addition, as the ester ring type organic group of carbonatoms 10～30, for example cholesteryl, cholestane base etc.Above-mentioned fluorine-containing organic group and alkyl in structure (B), also can by-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-or-conjugated group combinations such as S-.
Structure (C)
Structure (C) is not particularly limited so long as carry out crosslinked structure by heat and get final product.As preferred material epoxy group(ing) for example.
Polymkeric substance I
As the above-mentioned polyamic acid and the polyimide of the object lesson of polymkeric substance I, by making (a) tetracarboxylic dianhydride and (b) diamine compound reaction, the preparation polyamic acid obtains by making it be dehydrated into ring preparation polyimide.At this moment, in the preparation of polyamic acid and polyimide, at least one side uses the compound that has the compound of structure (A) and/or have structure (B) in the above-mentioned (a) and (b) composition.
As tetracarboxylic dianhydride with structure (A), 2,2 '-two (4-phenyl styryl ketone base oxygen bases)-3 for example, 3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 '-two (4-phenyl styryl ketone base oxygen bases)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (4-phenyl styryl ketone base oxygen bases)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 4,4 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 6,6 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 5,5 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (4-phenyl styryl ketone base oxygen bases)-3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 '-two (4-phenyl styryl ketone base oxygen bases)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (4-phenyl styryl ketone base oxygen bases)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 4,4 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 6,6 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 5,5 '-two (4-phenyl styryl ketone base oxygen bases)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 3,3 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 3,3 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 4,4 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 4,4 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 6,6 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 6,6 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 5,5 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 5,5 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 4,4 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 4,4 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 6,6 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 6,6 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 5,5 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 5,5 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-benzophenone tetracarboxylic dianhydride, 3,3 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-benzophenone tetracarboxylic dianhydride, 2,2 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-benzophenone tetracarboxylic dianhydride, 2,2 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-4,4 ', 5,5 '-benzophenone tetracarboxylic dianhydride, 4,4 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 4,4 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 6,6 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 6,6 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 5,5 '-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 5,5 '-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3 (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-pyromellitic acid dianhydrides, 3 (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-pyromellitic acid dianhydrides, 3,6-two (6 (4-phenyl styryl ketone base oxygen base) hexyloxy)-pyromellitic acid dianhydride, 3,6-two (6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy)-pyromellitic acid dianhydride, the compound of following formula (1)～(22) expression;
Figure A20051009116000121
Figure A20051009116000131
2,2 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-3,3 ', 4,4 '-bibenzene tetracarboxylic
Dianhydride, 3 ' 3 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-4,4 ', 5,5 '-biphenyl, 5 tetracarboxylic acid dianhydrides, 2,2 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-4,4 ', 5,5 '-bibenzene tetracarboxylic dianhydride, 4,4 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 6,6 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 5,5 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 2,2 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 2,2 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-4,4 ', 5,5 '-diphenyl ether tetracarboxylic acid dianhydride, 4,4 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 6,6 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride, 5,5 '-two (4 (4-phenyl styryl ketone base) phenoxy groups)-2,2 ', 3,3 '-diphenyl ether tetracarboxylic acid dianhydride etc.These may be used alone, two or more kinds can also be used in combination.
As diamine compound with structure (A); for example 4 (3; the 5-diamino phenoxy)-4 '-sec.-propyl phenyl styryl ketone; 4 (3; the 5-diamino phenoxy)-4 '-amyl group phenyl styryl ketone; 4 (3; the 5-diamino phenoxy)-4 '-octyl group phenyl styryl ketone; 4 (2; the 4-diamino phenoxy)-4 '-amyl group phenyl styryl ketone; 4 (2; the 4-diamino phenoxy)-4 '-octyl group phenyl styryl ketone; 4 (3; 5-diaminobenzene methanoyl)-4 '-amyl group phenyl styryl ketone; 4 ' (4-amyl group phenyl)-4 (3; the 5-diamino phenoxy) phenyl styryl ketone; 6 (4-phenyl styryl ketone base oxygen base) hexyloxy (2; the 4-diaminobenzene); 6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy (2; the 4-diaminobenzene); 8 (4-phenyl styryl ketone base oxygen base) octyloxy (2; the 4-diaminobenzene); 8 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyloxy (2; the 4-diaminobenzene); 10 (4-phenyl styryl ketone base oxygen base) oxygen base in the last of the ten Heavenly stems (2; the 4-diaminobenzene); 10 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxygen base in the last of the ten Heavenly stems (2; the 4-diaminobenzene); 2 (2 (4-phenyl styryl ketone base oxygen base) oxyethyl group) ethyl (3; 5-diaminobenzoic acid ester); 2 (2 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group) ethyl (3; 5-diaminobenzoic acid ester); 2 (2 (4-phenyl styryl ketone base oxygen base) oxyethyl group) oxyethyl group (2; the 4-diaminobenzene); 2 (2 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group) oxyethyl group (2; the 4-diaminobenzene); 1 ((4-phenyl styryl ketone base oxygen base) oxyethyl group)-2 ((2; the 4-diamino phenoxy) ethane oxyethyl group); 1 ((4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group)-2 ((2; the 4-diamino phenoxy) ethane oxyethyl group); 1-((4-phenyl styryl ketone base oxygen base) oxyethyl group)-2-((3; 5-diaminobenzene methanoyl) ethane oxyethyl group); 1-((4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group)-2-((3; 5-diaminobenzene methanoyl) ethane oxyethyl group); 6 (4-phenyl styryl ketone base oxygen base) hexyloxy (3; 5-diaminobenzene formyl radical); 6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy (3; 5-diaminobenzene formyl radical); 8 (4-phenyl styryl ketone base oxygen base) octyloxies (3,5-diaminobenzene formyl radical); 8 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyloxy (3,5-diaminobenzene formyl radical); 10 (4-phenyl styryl ketone base oxygen base) oxygen base in the last of the ten Heavenly stems (3; 5-diaminobenzene formyl radical); 10 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxygen base in the last of the ten Heavenly stems (3; 5-diaminobenzene formyl radical); 6 (4-phenyl styryl ketone base oxygen base) caproic acid (2, the 4-diamino-phenyl) ester; 6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) caproic acid (2, the 4-diamino-phenyl) ester; 8 (4-phenyl styryl ketone base oxygen bases)-sad-(2; the 4-diamino-phenyl) ester; 8 (4 '-fluoro-4-phenyl styryl ketone base oxygen bases)-sad-(2; the 4-diamino-phenyl) ester; 10 (4-phenyl styryl ketone base oxygen base)-capric acid-(2, the 4-diamino-phenyl) esters; 10 (4 '-fluoro-4-phenyl styryl ketone base oxygen base)-capric acid-(2, the 4-diamino-phenyl) esters; hexanodioic acid list (4-phenyl styryl ketone base) single (2; the 4-diamino-phenyl) ester; hexanodioic acid list (4 '-fluoro-4-phenyl styryl ketone base) single (2; the 4-diamino-phenyl) ester; single (2, the 4-diamino-phenyl) ester of suberic acid list (4-phenyl styryl ketone base); single (2, the 4-diamino-phenyl) ester of suberic acid list (4 '-fluoro-4-phenyl styryl ketone base oxygen base); sebacic acid list (4-phenyl styryl ketone base) single (2; the 4-diamino-phenyl) ester; sebacic acid list (4 '-fluoro-4-phenyl styryl ketone base oxygen base) single (2; the 4-diamino-phenyl) ester; two-1,1 (4-aminophenyl)-6 (4-phenyl styryl ketone base oxygen base) hexane; two-1,1 (4-aminophenyl)-6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexane; two-1; 1 (4-aminophenyl)-8 (4-phenyl styryl ketone base oxygen base) octane; two-1; 1 (4-aminophenyl)-8 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) octane; two-1,1 (4-aminophenyl)-10 (4-phenyl styryl ketone base oxygen base) decane; two-1,1 (4-aminophenyl)-10 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) decane; two-N; N-(4-aminophenyl)-N-(6 (4-phenyl styryl ketone base oxygen base) hexyloxy phenyl) amine; two-N; N-(4-aminophenyl)-N-(6 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy phenyl) amine; two-N, N-(4-aminophenyl)-N-(8 (4-phenyl styryl ketone base oxygen base) octyloxyphenyl) amine; two-N, N-(4-aminophenyl)-N-(8 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyloxyphenyl) amine; two-N; N-(4-aminophenyl)-N-(10 (4-phenyl styryl ketone base oxygen base) oxygen base phenyl in the last of the ten Heavenly stems) amine; two-N; N-(4-aminophenyl)-N-(10 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxygen base phenyl in the last of the ten Heavenly stems) amine; two-N, N-(4-aminophenyl)-N-(2 (2 (4-phenyl styryl ketone base oxygen base) oxyethyl group) ethoxyl phenenyl) amine; two-N, N-(4-aminophenyl)-N-(4 (2 (2 (4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group) oxyethyl group) phenyl) amine; 4 (4 (2; the 4-diamino phenoxy) phenyl styryl ketone phenyl); 4 (4 (2 (2; the 4-diamino phenoxy) phenyl styryl ketone phenyl oxyethyl group)); 4 (4 (6 (2, the 4-diamino phenoxy) hexyloxy) phenyl) phenyl styryl ketone; 4 (2 (2, the 4-diamino phenoxy) ethyl) phenyl styryl ketone manthanoate; 4 (6 (2; the 4-diamino phenoxy) phenyl styryl ketone manthanoate hexyl); 4 (4 (2; the 4-diamino phenoxy) phenyl styryl ketone benzoyloxy); 4 (4 (2, the 4-diamino phenoxy) phenyl) phenyl styryl ketone manthanoate; 4 (4 (2 (2, the 4-diamino phenoxy) oxyethyl group) benzoyloxy) phenyl styryl ketone; 4 (4 (2 (2; the 4-diamino phenoxy) phenyl styryl ketone manthanoate phenyl oxyethyl group)); 4 (4 (6 (2; the 4-diamino phenoxy) phenyl styryl ketone benzoyloxy hexyloxy)); 4 (4 (6 (2, the 4-diamino phenoxy) hexyloxy) phenyl) phenyl styryl ketone manthanoate; 4 (4 (3,5-diaminobenzene methanoyl) phenyl) phenyl styryl ketone; 4 (4 (2 (3; 5-diaminobenzene methanoyl) phenyl styryl ketone phenyl oxyethyl group)); 4 (4 (6 (3; 5-diaminobenzene methanoyl) phenyl styryl ketone phenyl hexyloxy)); 4 (2 (3,5-diaminobenzene methanoyl) ethyl) phenyl styryl ketone manthanoate; 4 (6 (3,5-diaminobenzene methanoyl) hexyl) phenyl styryl ketone manthanoate; 4 (4 (3; 5-diaminobenzene methanoyl) phenyl styryl ketone benzoyloxy); 4 (4 (3; 5-diaminobenzene methanoyl) phenyl styryl ketone manthanoate phenyl); 4 (4 (2 (3,5-diaminobenzene methanoyl) oxyethyl group) benzoyloxy) phenyl styryl ketone; 4 (4 (2 (3,5-diaminobenzene methanoyl) oxyethyl group) phenyl) phenyl styryl ketone manthanoate; 4 (4 (6 (3; 5-diaminobenzene methanoyl) phenyl styryl ketone benzoyloxy hexyloxy)); 4 (4 (6 (3,5-diaminobenzene methanoyl) hexyloxy) phenyl) phenyl styryl ketone manthanoate etc.They may be used alone, two or more kinds can also be used in combination.
In addition, as tetracarboxylic dianhydride, can exemplify compound as following chemical formula (23)～(36) expression with structure (B).They may be used alone, two or more kinds can also be used in combination.
Figure A20051009116000171
As diamine compound with structure (B); can exemplify as; 1-dodecyloxy-2; the 4-diaminobenzene; 1-tetradecyloxyaniline-2; the 4-diaminobenzene; 1-pentadecane oxygen base-2; the 4-diaminobenzene; 1-n-Hexadecane oxygen base-2; the 4-diaminobenzene; 1-octadecane oxygen base-2; the 4-diaminobenzene; 1-cholesteryl oxygen base-2; the 4-diaminobenzene; 1-cholestane base oxygen base-2; the 4-diaminobenzene; dodecyloxy (3,5-diaminobenzene formyl radical); tetradecyloxyaniline (3,5-diaminobenzene formyl radical); pentadecane oxygen base (3; 5-diaminobenzene formyl radical); n-Hexadecane oxygen base (3; 5-diaminobenzene formyl radical); octadecane oxygen base (3,5-diaminobenzene formyl radical); cholesteryl oxygen base (3,5-diaminobenzene formyl radical); cholestane base oxygen base (3; 5-diaminobenzene formyl radical); (2; the 4-diamino phenoxy) cetylate; (2, the 4-diamino phenoxy) stearate; (2, the 4-diamino phenoxy)-4-trifluoro methyl benzoate; the compound of following formula (37) expression.
Figure A20051009116000181
In the present invention in the polyimide of Shi Yonging, under the degree of not damaging effect of the present invention can and with other tetracarboxylic dianhydrides and/or diamine compound.These other compositions are for example with respect to above-mentioned compound with structure (A) with have the total amount of the compound of structure (B), preferably at 60 moles below the %, more preferably use below the % at 20 moles.
As other tetracarboxylic dianhydrides, can exemplify as 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, the ethylene-dimalonic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,2,3, the 4-cyclopentane tetracarboxylic acid dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1,2-dioctyl phthalate dianhydride, two ring [2.2.2]-Xin-7-alkene-2,3,5, aliphatics and ester ring type tetracarboxylic dianhydrides such as 6-tetracarboxylic acid dianhydride; Pyromellitic acid dianhydride, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic acid dianhydride, 1,2,3,4-furans tetracarboxylic acid dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, two (phthalic acid) phenylphosphine oxide dianhydride, right-phenylene-two (triphenyl phthalic acid) dianhydride, between-phenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4, aromatic tetracarboxylic acid's dianhydrides such as 4 '-ditan dianhydride.
Wherein, preferred 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, ethylene-dimalonic acid dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic acid dianhydride.They may be used alone, two or more kinds can also be used in combination.
As other diamine compounds, can exemplify as Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino benzanilide, 4,4 '-diamino-diphenyl ether, 1, the 5-diaminonaphthalene, 3,3-dimethyl-4,4 '-benzidine, 5-amino-1 (4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1 (4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 2,2-two (4-amino-benzene oxygen) propane, 2,2-two [4 (4-amino-benzene oxygen) phenyl] propane, 2,2-two [4 (4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4 (4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogenation anthracene, 2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 ' (to the phenylene isopropylidene) pentanoic, 4,4 ' (metaphenylene isopropylidene) pentanoic, 2,2 '-two [4 (4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl; Diamino 4-phenyl-thiophene etc. has heteroatomic aromatic diamine; 1,1-m-xylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 4,4-diaminostilbene, 7-heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4, the inferior indanyl dimethylene of 7-endo-methylene group diamines, three ring [6.2.1.0 2.7]-Ya undecyl dimethyl diamines, 4,4 '-methylene radical two aliphatics and ester ring type diamines such as (cyclo-hexylamine); Diamino organo-siloxanes such as diamino hexamethyldisiloxane.
Wherein, preferred Ursol D, 4,4 '-diaminodiphenyl-methane, 1,5-diaminonaphthalene, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 4,4 ' (to the phenylene isopropylidene) pentanoic, 2,2-two [4 (4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2 '-two [4 (4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl.They may be used alone, two or more kinds can also be used in combination.
The polyimide that uses among the present invention can above-mentioned by making (a) tetracarboxylic dianhydride composition and (b) two amine component polycondensations obtain polyamic acid, then under the condition that dewatering agent and imidization catalyst exist, heat as required, make it imidization and obtain.Temperature of reaction when making it imidization by heating is generally 60～300 ℃, preferred 100～170 ℃.When temperature of reaction was lower than 60 ℃, reaction was carried out slowly, and in addition, when surpassing 300 ℃, the molecular weight of polyamic acid significantly reduces sometimes.Reaction when in addition, making it imidization under the condition of dewatering agent and imidization catalyst existence can be carried out in organic solvent.Temperature of reaction is generally 0～180 ℃, preferred 60～150 ℃.As above-mentioned dewatering agent, can use as acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydrides.In addition, as imidization catalyst, can use as tertiary amines such as pyridine, trimethylpyridine, lutidine, triethylamines.The consumption of dewatering agent for 1 mole of the repeating unit of polyamic acid, preferred 1.6～20 moles.In addition, the consumption of imidization catalyst for 1 mole of the dewatering agent that uses, preferred 0.5～10 mole.By the consumption of this imidization catalyst, dewatering agent, can adjust the containing ratio of amido acid residue in the polyimide.
Polystyrene and vinylbenzene/maleimide copolymer as polymkeric substance I specific examples can obtain by making styrene derivatives or styrene derivatives and phenyl maleimide derivative carry out radical polymerization under the condition that exists at initiator.The polystyrene that uses among the present invention and vinylbenzene/maleimide copolymer have structure (A) by use compound obtains as at least a composition in styrene derivatives and the phenyl maleimide derivative composition with the compound with structure (B).
Having the structure (A), a styrene derivative, can be exemplified such as 4 - (4 - Chalcone Yloxy) styrene, 4 - (4 - chalcone yloxy) α-methyl styrene, 4 - (2 - (4 - chalcone-yloxy) ethoxy) styrene, 4 - (2 - (4 - yloxy chalcone Yl) ethoxy) α-methyl styrene, 4 - (4 - (4 - chalcone group) butoxy) Styrene, 4 - (4 - (4 - chalcone yl) butoxy) α-methyl styrene, 4 - (6 - (4 - chalcone group) hexyloxy) styrene, 4 - (6 - (4 - Chalcone Yl) hexyloxy) α-methyl styrene, 4 - (8-( 4 - chalcone-yloxy) octyl Oxy) styrene, 4 - (8-( 4 - chalcone yloxy) octyloxy) α-methyl styrene Ene, 4 - (4 - carboxy chalcone) styrene, 4 - (4 - carboxy chalcone) α-methyl Group styrene, 4 - (2 - (4 - chalcone group carboxy) ethoxy) styrene, 4 - (2 - (4 - chalcone group carboxy) ethoxy) α-methyl styrene, 4 - (4 - (4 - Chalcone Carboxy) butoxy) styrene, 4 - (4 - (4 - carboxy chalcone) butoxy) α - Methyl styrene, 4 - (6 - (4 - carboxy chalcone) hexyloxy) styrene, 4 - (6 - (4 - carboxy chalcone) hexyloxy) α-methyl styrene, 4 - (8-( 4 - Chalcone carboxy) octyloxy) styrene, 4 - (8-( 4 - carboxy chalcone) octyloxy Yl) α-methyl styrene, 4 - (2 - (4 - chalcone yl) ethoxy) styrene, 4 - (2 - (4 - chalcone yl) ethoxy) α-methyl styrene, 4 - (4 - (4 - Cha Chalcone yl) butoxy) styrene, 4 - (4 - (4 - chalcone group) butoxy) α-methyl Group styrene, 4 - (6 - (4 - chalcone) hexyloxy) styrene, 4 - (6 - (4 - Chalcone) hexyloxy) α-methyl styrene, 4 - (8-( 4 - chalcone group) octyl Oxy) styrene, 4 - (8-( 4 - chalcone group) octyloxy) α-methyl styrene, 4 - (2 - (4 - chalcone-yloxy) ethyl) styrene, 4 - (2 - (4 - chalcone group Yloxy)-ethyl) α-methyl styrene, 4 - (4 - (4 - chalcone-yloxy) butyl) Styrene, 4 - (4 - (4 - chalcone-yloxy) butyl) α-methyl styrene, 4 - (6 - (4 - chalcone-yloxy) hexyl) styrene, 4 - (6 - (4 - chalcone-yloxy) Hexyl) α-methyl styrene, 4 - (8-( 4 - chalcone-yloxy) octyl) styrene, 4 - (8-( 4 - chalcone-yloxy) octyl) α-methyl styrene, 4 - (2 - (4 - Chalcone carboxy) ethyl) styrene, 4 - (2 - (4 - chalcone group carboxy) ethyl) α-methyl styrene, 4 - (4 - (4 - carboxy chalcone) butyl) styrene, 4 - (4 - (4 - carboxy chalcone) butyl) α-methyl styrene, 4 - (6 - (4 - Chalcone Carboxy) hexyl) styrene, 4 - (6 - (4 - carboxy chalcone) hexyl) α-methyl Group styrene, 4 - (8-( 4 - carboxy chalcone) octyl) styrene, 4 - (8-( 4 - Chalcone group carboxy) octyl) α-methyl styrene, 4 - (2 - (4 - chalcone group) Ethyl) styrene, 4 - (2 - (4 - chalcone yl)-ethyl) α-methyl styrene, 4 - (4 - (4 - chalcone yl) butyl) styrene, 4 - (4 - (4 - chalcone yl) butyric Yl) α-methyl styrene, 4 - (6 - (4 - chalcone) hexyl) styrene, 4 - (6 - (4 - chalcone) hexyl) α-methyl styrene, 4 - (8-( 4 - chalcone group) Octyl) styrene, 4 - (8-( 4 - chalcone group) octyl) α-methyl styrene, 4 - (4 - methyl chalcone yloxy) styrene, 4 - (4 - methyl chalcone yloxy) α - Methyl styrene, 4 - (2 - (4 - chalcone yloxy) ethoxy methyl) styrene, 4 - (2 - (4 - chalcone yloxy) ethoxy methyl) α-methyl styrene, 4 - (4 - (4 - chalcone yl) butoxy methyl) styrene, 4 - (4 - (4 - Chalcone Yl) butoxy methyl) α-methyl styrene, 4 - (6 - (4 - chalcone-yloxy) Hexyloxy methyl) styrene, 4 - (6 - (4 - chalcone group) hexyloxy meth) α - Methyl styrene, 4 - (8-( 4 - chalcone-yloxy)-octyl methyl) styrene, 4 - (8-( 4 - chalcone-yloxy) methyl octyloxy) α-methyl styrene, 4 - (4 - Carboxy methyl chalcone group) styrene, 4 - (4 - carboxy methyl chalcone group) α-methyl- Styrene, 4 - (2 - (4 - carboxy chalcone) ethoxymethyl) styrene, 4 - (2 - (4 - carboxy chalcone) ethoxymethyl) α-methyl styrene, 4 - (4 - (4 - Chalcone carboxy) butoxy methyl) styrene, 4 - (4 - (4 - carboxy chalcone) Butoxymethyl) α-methyl styrene, 4 - (6 - (4 - carboxy chalcone) hexyloxy Methyl) styrene, 4 - (6 - (4 - carboxy chalcone) hexyloxy methyl) α-methyl- Styrene, 4 - (8-( 4 - carboxy chalcone) octyloxy methyl) styrene, 4 - (8 - (4 - carboxy chalcone) octyloxy methyl) α-methyl styrene, 4 - (2 - (4 - Chalcone group) ethoxymethyl) styrene, 4 - (2 - (4 - chalcone-yl) ethoxy Methyl) α-methyl styrene, 4 - (4 - (4 - chalcone yl) butoxy methyl) phenyl Ene, 4 - (4 - (4 - chalcone yl) butoxy methyl) α-methyl styrene, 4 - (6 - (4 - chalcone yl) hexyl methyl) styrene, 4 - (6 - (4 - chalcone group) Hexyloxymethyl) α-methyl styrene, 4 - (8-( 4 - chalcone group) octyl methyl) Styrene, 4 - (8-( 4 - chalcone group) octyloxy methyl) α-methyl styrene, 4 - (4'-fluoro-4 - chalcone yloxy) styrene, 4 - (4'-fluoro-4 - chalcone group Oxy) α-methyl styrene, 4 - (2 - (4'-fluoro-4 - chalcone yloxy) ethoxy Yl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone-yloxy) ethoxy) α-methyl Group styrene, 4 - (4 - (4'-fluoro-4 - chalcone group) butoxy) styrene, 4 - (4 - (4'_ fluoro-4 - chalcone yl) butoxy) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone group) hexyloxy) styrene, 4 - (6 - (4 ' - Fluoro-4 - chalcone group) hexyloxy) α-methyl styrene, 4 - (8-( 4'- Fluoro-4 - chalcone yloxy) octyloxy) styrene, 4 - (8-( 4'-fluoro-4 - Cha Chalcone yloxy) octyloxy) α-methyl styrene, 4 - (4'-fluoro-4 - carboxylic chalcone group Yl) styrene, 4 - (4 - '- fluoro-4 - carboxy chalcone) α-methyl styrene, 4 - (2 - (4'-fluoro-4 - chalcone group carboxy) ethoxy) styrene, 4 - (2 - (4 ' - Fluoro-4 - chalcone group carboxy) ethoxy) α-methyl styrene, 4 - (4 - (4'- Fluoro-4 - carboxy chalcone) butoxy) styrene, 4 - (4 - (4'-fluoro-4 - Cha Chalcones carboxy) butoxy) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone Keto carboxyl) hexyloxy) styrene, 4 - (6 - (4'-fluoro-4 - carboxy chalcone) Hexyloxy) α-methyl styrene, 4 - (8-( 4'-fluoro-4 - carboxy chalcone) octyl Oxy) styrene, 4 - (8-( 4'-fluoro-4 - carboxy chalcone) octyloxy) α- Methyl styrene, 4 - (2 - (4'-fluoro-4 - chalcone yl) ethoxy) styrene, 4 - (2 - (4'-fluoro-4 - chalcone yl) ethoxy) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - chalcone yl) butoxy) styrene, 4 - (4 - (4'-fluoro-4 - Cha Chalcone yl) butoxy) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone group) Hexyloxy) styrene, 4 - (6 - (4'-fluoro-4 - chalcone) hexyloxy) α-methyl Group styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyloxy) styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyloxy) α-methyl styrene, 4 - (2 - (4 ' - Fluoro-4 - chalcone-yloxy) ethyl) styrene, 4 - (2 - (4'-fluoro-4 - Cha Chalcone-yloxy) ethyl) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - chalcone Yloxy) butyl) styrene, 4 - (4 - (4'-fluoro-4 - chalcone-yloxy) butyl) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone-yloxy) hexyl)-phenylethyl Ene, 4 - (6 - (4'-fluoro-4 - chalcone-yloxy) hexyl) α-methyl styrene, 4 - (8-( 4'-fluoro-4 - chalcone-yloxy)-octyl) styrene, 4 - (8-( 4 ' - Fluoro-4 - chalcone-yloxy) octyl) α-methyl styrene, 4 - (2 - (4'-fluoro -4 - Chalcone carboxy) ethyl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone Carboxy)-ethyl) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - carboxylic chalcone group Yl) butyl) styrene, 4 - (4 - (4'-fluoro-4 - carboxy chalcone) butyl) α - Methyl styrene, 4 - (6 - (4'-fluoro-4 - carboxy chalcone) hexyl) styrene, 4 - (6 - (4'-fluoro-4 - carboxy chalcone) hexyl) α-methyl styrene, 4 - (8 - (4'-fluoro-4 - carboxy chalcone) octyl) styrene, 4 - (8-( 4'-fluoro- - Chalcone group carboxy) octyl) α-methyl styrene, 4 - (2 - (4'-fluoro-4 - Cha Chalcone yl) ethyl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone yl)-ethyl) α - Methyl styrene, 4 - (4 - (4'-fluoro-4 - chalcone yl) butyl) styrene, 4 - (4 - (4'-fluoro-4 - chalcone yl) butyl) α-methyl styrene, 4 - (6 - (4 ' - Fluoro-4 - chalcone) hexyl) styrene, 4 - (6 - (4'-fluoro-4 - chalcone Yl) hexyl) α-methyl styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyl) Styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyl) α-methyl styrene, 4 - (4'-fluoro-4 - methyl chalcone yloxy) styrene, 4 - (4'-fluoro-4 - chalcone Methyl ketone yloxy) α-methyl styrene, 4 - (2 - (4'-fluoro-4 - yloxy chalcone Yl) ethoxy methyl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone-yloxy) ethyl Oxymethyl) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - chalcone-yloxy) Butoxy methyl) styrene, 4 - (4 - (4'-fluoro-4 - chalcone group) butoxy Methyl) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone yloxy) hexyloxycarbonyl Yl methyl) styrene, 4 - (6 - (4'-fluoro-4 - chalcone group) hexyloxy methyl) α-methyl styrene, 4 - (8-( 4'-fluoro-4 - chalcone-yloxy) methyl octyloxy) Styrene, 4 - (8-( 4'-fluoro-4 - chalcone-yloxy) methyl octyloxy) α-methyl Group styrene, 4 - (2 - (4'-fluoro-4 - chalcone group) ethoxymethyl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone group) ethoxymethyl) α-methyl styrene, 4 - (4'-fluoro-4 - carboxy methyl chalcone group) styrene, 4 - (4'-fluoro-4 - chalcone Carboxy methyl) α-methyl styrene, 4 - (2 - (4'-fluoro-4 - carboxy chalcone) Ethoxy-methyl) styrene, 4 - (2 - (4'-fluoro-4 - carboxy chalcone) ethoxy Methyl) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - carboxy chalcone) butoxy Yl methyl) styrene, 4 - (4 - (4'-fluoro-4 - carboxy chalcone) butoxymethyl) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - chalcone group carboxy) methyl-hexyloxy) Styrene, 4 - (6 - (4'-fluoro-4 - carboxy chalcone) hexyloxy methyl) α-methyl Group styrene, 4 - (8-( 4'-fluoro-4 - carboxy chalcone) octyl methyl) phenyl Ene, 4 - (8-( 4'-fluoro-4 - carboxy chalcone) octyloxy methyl) α-methyl benzyl Ethylene, 4 - (2 - (4'-fluoro-4 - chalcone group) ethoxy methyl) styrene, 4 - (2 - (4'-fluoro-4 - chalcone group) ethoxymethyl) α-methyl styrene, 4 - (4 - (4'-fluoro-4 - chalcone yl) butoxy methyl) styrene, 4 - (4 - (4'-fluoro -4 - Chalcone yl) butoxy methyl) α-methyl styrene, 4 - (6 - (4'-fluoro-4 - Chalcone yl) hexyl methyl) styrene, 4 - (6 - (4'-fluoro-4 - chalcone group) Hexyloxymethyl) α-methyl styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyl Methyl) styrene, 4 - (8-( 4'-fluoro-4 - chalcone group) octyl methyl) α-methyl styrene, 4 - (3 - (4 - vinyl-phenyl)) propoxy)-4'-fluoro investigation Chalcone, 4 - (3 - (4 - vinyl-phenyl)) propoxy) chalcone by the following formula (38) - (45) a compound represented. ...
Figure A20051009116000251
Wherein, the compound of preferred 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) vinylbenzene, 4-(6-(4-phenyl styryl ketone base oxygen base) octyloxy) vinylbenzene and above-mentioned formula (38)～(45) expression.They may be used alone, two or more kinds can also be used in combination.
As maleimide derivatives, can exemplify phenyl maleimide as 4-(4-phenyl styryl ketone base oxygen base) with structure (A), 4-(2-(4-phenyl styryl ketone base oxygen base) oxyethyl group) phenyl maleimide, 4-(4-(4-phenyl styryl ketone base oxygen base) butoxy) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base oxygen base) octyloxy) phenyl maleimide, 4-(4-phenyl styryl ketone base carboxyl) phenyl maleimide, 4-(2-(4-phenyl styryl ketone base carboxyl) oxyethyl group) phenyl maleimide, 4-(4-(4-phenyl styryl ketone base carboxyl) butoxy) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base carboxyl) hexyloxy) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base carboxyl) octyloxy) phenyl maleimide, 4-(2-(4-phenyl styryl ketone base) oxyethyl group) phenyl maleimide, 4-(4-(4-phenyl styryl ketone base) butoxy) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base) hexyloxy) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base) octyloxy) phenyl maleimide, 4-(2-(4-phenyl styryl ketone base oxygen base) ethyl) phenyl maleimide, 4-(4-(4-phenyl styryl ketone base oxygen base) butyl) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base oxygen base) hexyl) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base oxygen base) octyl group) phenyl maleimide, 4-(2-(4-phenyl styryl ketone base carboxyl) ethyl) phenyl maleimide, 4-(4-phenyl styryl ketone base carboxyl) butyl) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base carboxyl) hexyl) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base carboxyl) octyl group) phenyl maleimide, 4-(2-(4-phenyl styryl ketone base) ethyl) phenyl maleimide, 4-(4-(4-phenyl styryl ketone base) butyl) phenyl maleimide, 4-(6-(4-phenyl styryl ketone base) hexyl) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base) octyl group) phenyl maleimide, 4-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) oxyethyl group) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) butoxy) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyloxy) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyloxy) phenyl maleimide, 4-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) oxyethyl group) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) butoxy) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) hexyloxy) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) octyloxy) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base) oxyethyl group) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base) butoxy) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base) hexyloxy) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base) octyloxy) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) ethyl) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) butyl) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyl group) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) ethyl) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) butyl) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) hexyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) octyl group) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base) ethyl) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base) butyl) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base) hexyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base) octyl group) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyloxy methyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base carboxyl) octyloxy methyl) phenyl maleimide, 4-(2-(4 '-fluoro-4-phenyl styryl ketone base) ethoxyl methyl) phenyl maleimide, 4-(4-(4 '-fluoro-4-phenyl styryl ketone base) butoxymethyl) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base) hexyloxy methyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base) octyloxy methyl) phenyl maleimide, the compound of following formula (46)～(49) expression etc.
Wherein, the compound of preferred 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) phenyl maleimide, 4-(8-(4-phenyl styryl ketone base oxygen base) octyloxy) phenyl maleimide, 4-(6-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) hexyl) phenyl maleimide, 4-(8-(4 '-fluoro-4-phenyl styryl ketone base oxygen base) octyl group) phenyl maleimide, above-mentioned formula (46)～(49) expression.They may be used alone, two or more kinds can also be used in combination.
As styrene derivatives with structure (B), can exemplify as to trifluoromethyl styrene, to trifluoromethyl-alpha-methyl styrene, to trifluoromethoxy vinylbenzene, to trifluoromethoxy-alpha-methyl styrene, 4-(2,2, the 2-trifluoro ethoxy) vinylbenzene, 4-(2,2, the 2-trifluoro ethoxy)-alpha-methyl styrene, to n-Hexadecane oxygen base vinylbenzene, to n-Hexadecane oxygen base-alpha-methyl styrene, to the palm acetoxystyrene, to palm acyloxy-alpha-methyl styrene, to octadecane oxygen base vinylbenzene, to octadecane oxygen base-alpha-methyl styrene, to stearoyl-oxy vinylbenzene, to stearoyl-oxy-alpha-methyl styrene, to cholesteryl oxygen base vinylbenzene, to cholesteryl oxygen base-alpha-methyl styrene, to cholestane base oxygen base vinylbenzene, to cholestane base oxygen base-alpha-methyl styrene.
In addition, as maleimide derivatives with structure (B), can exemplify as 4-trifluoromethyl maleimide, 4-Trifluoromethoxyphen-l maleimide, 4-(2,2,2-trifluoro ethoxy) phenyl maleimide, 4-n-Hexadecane oxygen base phenyl maleimide, 4-palm acyloxy phenyl maleimide, 4-octadecane oxygen base phenyl maleimide, 4-stearoyl-oxy phenyl maleimide, 4-cholesteryl oxygen base phenyl maleimide, 4-cholestane base oxygen base phenyl maleimide etc.
The polystyrene that uses among the present invention and vinylbenzene/maleimide copolymer also can make the monomer copolymerization with structure (C), make the multipolymer of have structure (A), structure (B) and structure (C).
As monomer with structure (C), glycidyl acrylate for example, glycidyl methacrylate, the α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, vinylformic acid-6,7-epoxy heptyl ester, methacrylic acid-6,7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, adjacent vinyl benzene methyl glycidyl ether, between the vinyl benzene methyl glycidyl ether, to vinyl benzene methyl glycidyl ether etc.These monomers may be used alone, can also be used in combination.
In the polystyrene of Shi Yonging and the vinylbenzene/maleimide copolymer, under the degree of not damaging effect of the present invention, can and use other free radical polymerization monomers in the present invention.Other free radical polymerization monomers, p-poly-phenyl ethene for vinylbenzene, to vinylbenzene/maleimide copolymer, for the total amount of vinylbenzene and maleimide, preferably uses with 50 moles of %.
As other free radical polymerization monomers, can exemplify as aliphatics (methyl) acrylic compound such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-ethylhexyl (methyl) acrylate, polyethyleneglycol (methyl) acrylate, trimethylolpropane tris (methyl) acrylate; Ester ring type (methyl) acrylic compound such as (methyl) vinylformic acid tetrahydrofuran (THF) methyl esters, (methyl) cyclohexyl acrylate, (methyl) acrylate glycidyl ester, Dicyclopentadiene (DCPD) (methyl) acrylate, two cyclopentyl (methyl) acrylate, three ring decyl (methyl) acrylate, isobornyl (methyl) acrylate;
Aromatic series (methyl) acrylic compound such as 4-(methyl) acryloxy phenyl styryl ketone, 4-(methyl) acryloxy-4 '-phenyl phenyl styryl ketone, 4-(methyl) acryloxy-4 '-amyl group phenyl styryl ketone, 4-(methyl) acryloxy-4 '-(4-amyl group phenyl) phenyl styryl ketone, (methyl) vinylformic acid benzene methyl, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate; Ethene, propylene, butylene, vinylbenzene, p-methylstyrene, to trifluoromethyl styrene, alpha-methyl styrene, to trifluoromethyl-alpha-methyl styrene, 4 (4-trifluoromethyl benzoyloxy) vinylbenzene, to n-Hexadecane oxygen base vinylbenzene, to the palm acetoxystyrene, 4-trifluoromethyl-3 (4-ethenylphenyl) propionic ester, 4-hexadecyl-3 (4-ethenylphenyl) propionic ester, 4-octadecyl-3 (4-ethenylphenyl) propionic ester, vinylchlorid, vinyl-acetic ester, vinyl compounds such as vinyl cyanide;
Maleic acid derivatives such as maleic anhydride, phenyl maleimide;
Dienes such as divinyl, isoprene, chloroprene etc.
Wherein, optimization styrene, p-methylstyrene, alpha-methyl styrene.They may be used alone, two or more kinds can also be used in combination.
The polystyrene that uses among the present invention and vinylbenzene/maleimide copolymer are according to circumstances, can be in the presence of catalyzer such as superoxide such as azo-compounds such as Diisopropyl azodicarboxylate, benzoyl peroxide, with above-mentioned styrene derivatives and/or maleimide derivatives polymerization and obtain.This polymkeric substance may be used alone, two or more kinds can also be used in combination.
The polystyrene that obtains using among the present invention and the additive method of vinylbenzene/maleimide copolymer have phenyl maleimide derivative and the monomer with structure (B) that styrene derivatives that acetoxyl replaces and/or acetoxyl are replaced, the monomer with structure (C) etc. to carry out radical polymerization, replace above-mentioned ethanoyl with the functional group with structure (A) then.
Polymkeric substance with structure (C)
As the polymkeric substance with structure (C), preferred material can exemplify polymkeric substance or the Resins, epoxy that above-mentioned monomer with structure (C) is according to circumstances obtained with above-mentioned other free radical polymerization monomer copolymerization.
As Resins, epoxy, can use Resins, epoxy as the expression of following formulas (i) such as bisphenol A type epoxy resin, bisphenol f type epoxy resin; The Resins, epoxy that following formulas such as phenol novolac type Resins, epoxy, cresols novolac type Resins, epoxy are (ii) represented; The Resins, epoxy that following formula such as multifunctional type Resins, epoxy is (iii) represented etc.
Figure A20051009116000301
In the formula, X be methylene radical, carbonatoms 2～6 alkylidene group, carbonatoms 2～6 the fluoro alkylidene group or have the divalent organic group of ester ring type skeleton, R is the alkyl of carbonatoms 1～3, Y is the organic group of p valency, m is 0～4 integer, and m ' is 0～3 integer, and n and p are the number more than 2.
They can be used as commercially available product and obtain.For example, as bisphenol A type epoxy resin, can exemplify Epikote828, Epikote1001, Epikote1002, Epikote1003, Epikote1004, Epikote1007, Epikote1009, Epikote1010 (above oiling シ エ Le epoxy (strain) system) etc., as bisphenol f type epoxy resin, can exemplify Epikote807, Epikote834 (above oiling シ エ Le epoxy (strain) system) etc., as phenol novolak type epoxy resin, can exemplify Epikote152, Epikote154, Epikote157H65 (above oiling シ エ Le epoxy (strain) system), EPPN201, EPPN202 (above Japanese chemical drug (strain) system) etc., as the cresols phenolic resin varnish type epoxy resin, can exemplify EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above Japanese chemical drug (strain) system), Epikote180S75 (oiling シ エ Le epoxy (strain) system) etc., in addition, as the ring type aliphatic epoxy resin, can exemplify Araldite CY175, Araldite CY177, Araldite CY179 (above CibaSpeciality Chemicals (strain) system), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above U.C.B society system), シ ョ one ダ ィ Application 509 (clear and electrician's (strain) system), Araldite CY-182, Araldite CY-192, AralditeCY-184 (above Ciba Speciality Chemicals (strain) system), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (above big Japanese ink industry (strain) system), Epikote871, Epikote872, EP1032H60 (above oiling シ エ Le epoxy (strain) system), ED-5661, ED-5662 (above Celanese Coating (strain) system) etc., as the aliphatic poly glycidyl ether, can exemplify Epikote190P, Epikote191P (above oiling シ エ Le epoxy (strain) system), Epolite100MF (common prosperity society chemistry (strain) system), エ ピ ォ-Le TMP (Japanese grease (strain) system) etc.
Compound (C ')
As the compound that uses among the present invention (C '), preferred substance is epoxy compounds for example.As epoxy compounds, preferred substance can exemplify as ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.
Solvent
Liquid crystal aligning agent of the present invention is made of the solution of above-mentioned component of polymer.Solvent as use this moment gets final product so long as can dissolve the organic solvent of this component of polymer, is not particularly limited.For example, when using polyimide as component of polymer, can exemplify N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, dimethyl-imidazolinone, hexamethyl phosphoric triamide etc. are non-proton to be polar solvent;
Ester series solvents such as butyl cellosolve acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC;
Ketone series solvents such as methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, methylcyclohexanone;
Halogen solvents such as chlorobenzene, orthodichlorobenzene, zellon, 1; Phenol solvents such as meta-cresol, xylenol, phenol, halogenated phenol.They can use separately, can make up also that solvent uses more than 2 kinds.In addition, in the scope that polymkeric substance is not separated out, in above-mentioned solvent can and with the poor solvent of used polymkeric substance.
In addition, in order to improve the cohesiveness with substrate, liquid crystal aligning agent of the present invention can contain the compound of functional silanes.As the compound that contains functional silanes, can exemplify TSL 8330 as 3-, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-phenmethyl-3-TSL 8330, N-phenmethyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene and special clear 63-291922 communique tetracarboxylic dianhydride who puts down in writing and the reactant that contains amino silane compounds etc. opened.
Liquid crystal orientation film
As using liquid crystal aligning agent of the present invention to form the method for liquid crystal orientation film, can exemplify following method.At first, in the nesa coating side of the substrate that is provided with nesa coating, apply liquid crystal aligning agent of the present invention by roller painting, rotational method, print process etc., heating makes it to form and films under 40～200 ℃ temperature.The thickness of filming is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
As aforesaid substrate, can use by glass such as float glass, soda-lime glasss, resemble the transparency carrier that plastics film polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, the polycarbonate etc. constitutes.
As above-mentioned nesa coating, can use for example SnO 2The NESA film, the In that constitute 2O 3-SnO 2The ITO film that constitutes etc.Can use photo-engraving process when in addition, these nesa coatings form pattern, adopt the method for pre-mask etc.
When applying liquid crystal aligning agent, good for the cohesiveness that further makes substrate and nesa coating and film, also can on substrate and nesa coating, apply the compound that contains functional silanes, titanic acid ester etc. in advance.
Then, to the above-mentioned irradiates light of filming, preferred straight line polarising radioactive rays.The radioactive rays that use preferably have the ultraviolet ray and the visible light of 150nm～800nm wavelength, wherein, especially preferably have the ultraviolet ray of 240nm～450nm wavelength.
As above-mentioned light source, can use as Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, エ キ シ マ-laser etc.
2. or liquid crystal aligning agent 3. the time in addition, use liquid crystal aligning agent, preferably above-mentioned filming is heated to more than the room temperature, shine simultaneously.At this moment, preferred 30～300 ℃ of Heating temperature, more preferably 30～200 ℃.
In addition, preferred 1 second to 1 hour of the time of heat treated, preferred especially 1 second to 5 minutes.
In addition, this heat treatment step also can be in the manufacturing process of liquid crystal display device, and the sealing agent thermofixation operation with sealing agent encapsulated liquid crystals unit peripheral part the time is carried out simultaneously.
Liquid crystal display device
Liquid crystal display device of the present invention can followingly obtain.With 2 substrate face-offs that formed above-mentioned liquid crystal orientation film, make the polarization direction of the straight line polarization radioactive rays of irradiating liquid crystal alignment films become given angle, with the peripheral part between the sealing agent hermetic sealing substrate, filling liquid crystal, the sealing filling orifice forms liquid crystal cells.Then, paste polaroid on its two sides, the polarization direction that makes polaroid becomes given angle with the polarization direction of the straight line polarization radioactive rays of irradiated substrate liquid crystal orientation film respectively, makes liquid crystal display device.Formed the angle of polarization direction angulation with each substrate and the polaroid of the straight line polarization radioactive rays that shine in 2 substrates of liquid crystal orientation film by adjustment, can access liquid crystal display device with TN type or STN type liquid crystal cells.
As above-mentioned sealing agent, for example can use and contain solidifying agent and as Resins, epoxy of the alumina balls of separaant (spacer) etc.
As above-mentioned liquid crystal, can use for example nematic liquid crystal, dish-like liquid crystal etc.The occasion of TN type liquid crystal cells, be preferably formed nematic liquid crystal, can use for example Schiff bases liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, terphenyl class liquid crystal, phenylbenzene cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, the occasion of STN type liquid crystal cells also can be added in above-mentioned liquid crystal as cholesteryl liquid crystals such as cholesteryl chloride (コ レ ス チ Le Network ロ ラ ィ De), n-nonanoic acid cholesterol ester, carbonic acid cholesterol esters or as commercially available chirality agent of trade(brand)name C-15, CB-15 (メ Le Network society system) etc. again.And, also can use strong dielectricity liquid crystal such as right-removal monosilane oxygen base Ben Yajiaji-right-amino-2-methyl butyl laurate.
As the polaroid that uses in the liquid crystal cells outside, can exemplify polaroid that the polarizing coating that is called as the H film that absorbs iodine when making polyvinyl alcohol extend orientation forms with the clamping of rhodia protective membrane or the polaroid that itself constitutes by the H film etc.
The liquid crystal orientation film that forms by method of the present invention has the high liquid crystal aligning restraint of optical alignment film than in the past, has high pre-tilt angle performance stability, when therefore using it to constitute liquid crystal display device, have the effect that disclination of preventing (デ ィ ス Network リ ネ-シ ョ Application) line produced or prevented the generation of pre-tilt zone, can prevent to be orientated bad.Therefore, can constitute not show uneven, have in the face electrooptics characteristic and a high liquid crystal display device of contrast gradient uniformly.
Embodiment
Be described more specifically the present invention below by embodiment, but the present invention is not limited by these embodiment.
Synthesis example 1
With 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) vinylbenzene 0.04 mole (17.1g), n-Hexadecane oxygen base vinylbenzene 0.01 mole of (3.45g), 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) phenyl maleimide 0.05 mole (24.8g) and Diisopropyl azodicarboxylate 3.0g are dissolved among the N,N-DIMETHYLACETAMIDE 500ml, in nitrogen environment, 80 ℃ reaction 10 hours down.The heavy-gravity reaction mixture is dropped in the methyl alcohol, make polymer precipitation, drying, gathered (vinylbenzene-phenyl maleimide) multipolymer (below be called " polymkeric substance 1 ") 44.5g.
Synthesis example 2
With 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) vinylbenzene 0.1 mole (42.8g), trifluoromethyl styrene 0.01 mole (1.72g) and Diisopropyl azodicarboxylate 3.0g are dissolved among the N,N-DIMETHYLACETAMIDE 500ml, in nitrogen environment, 80 ℃ reaction 10 hours down.The heavy-gravity reaction mixture is dropped in the methyl alcohol, make polymer precipitation, drying, obtain polystyrene copolymer (below be called " polymkeric substance 2 ") 37.8g.
Synthesis example 3
The polymerization of polyamic acid
With 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 0.1 mole of (22.4g), 1-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy)-2,4-diaminobenzene 0.05 mole of (21.5g) and 1-n-Hexadecane oxygen base-2,4-diaminobenzene 0.05 mole (17.4g) is dissolved among the N-N-methyl-2-2-pyrrolidone N-300g, and 60 ℃ were reacted 6 hours down.Then, reaction mixture is injected in the excessive methyl alcohol, makes reaction product precipitation, use the methanol wash throw out, reduced pressure, 40 ℃ be drying 15 hours down, obtains polyamic acid (below be called " polymkeric substance 3a ") 60.7g.
Imidization reaction
In the polymkeric substance 3a 60.7g that obtains, add N-N-methyl-2-2-pyrrolidone N-380g, pyridine 16g and diacetyl oxide 20.5g, 120 ℃ of following imidizations 4 hours.Then, reaction mixture is injected in the excessive methyl alcohol, makes the reaction product precipitation.Use the methanol wash throw out, under the reduced pressure dry 15 hours, obtain polyimide (below be called " polymkeric substance 3b ") 54.4g.
Compare synthesis example
With 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 0.1 mole of (22.4g), Ursol D 0.05 mole of (5.4g) and 1-n-Hexadecane oxygen base-2,4-diaminobenzene 0.05 mole (17.4g) is dissolved among the N-N-methyl-2-2-pyrrolidone N-300g, and 60 ℃ were reacted 6 hours down.Then, reaction mixture is injected in the excessive methyl alcohol, makes reaction product precipitation, use the methanol wash throw out, reduced pressure, 40 ℃ be drying 15 hours down, obtains polyamic acid (below be called " polymkeric substance 3a ' ") 45.0g.
Imidization reaction
In the polymkeric substance 3a ' 45g that obtains, add N-N-methyl-2-2-pyrrolidone N-380g, pyridine 16g and diacetyl oxide 20.5g, 120 ℃ of following imidizations 4 hours.Then, reaction mixture is injected in the excessive methyl alcohol, makes the reaction product precipitation.Use the methanol wash throw out, under the reduced pressure dry 15 hours, obtain polyimide (below be called " polymkeric substance 3b ' ") 40.5g.
Embodiment 1
The polymkeric substance 1 that obtains in the synthesis example 1 is dissolved in the gamma-butyrolactone, makes the solution of solid component concentration 4 weight %, with the filter filtration of aperture 1 μ m, preparation liquid crystal aligning agent solution.This solution is coated on the glass substrate of band ito transparent electrode film with turner, and making thickness is 0.1 μ m, and drying is 1 hour under 180 ℃, forms film.Then, use the Hg-Xe lamp, by the light of パ ィ レ ッ Network ス (registered trade mark) glass polaroid SPF-50C-32 (Sigma ray machine system) the blocking-up wavelength shorter than 320nm, by the normal direction of real estate to the rectilinearly polarized light 1.0J/cm of this film surface irradiation based on the 365nm wavelength 2
For the above-mentioned a pair of substrate that has carried out radiation treatment, silk screen printing contains the epoxy adhesive of diameter 17 μ m alumina balls on the face that forms liquid crystal orientation film, overlaps then, and the direction of the polarization plane of irradiation ultraviolet radiation is parallel to each other, carry out crimping, make adhesive cures.Then, by inlet inject nematic liquid crystal (メ Le Network society system, MLC-6608) after, with the sealing of epoxies binding agent.And, the flow orientation when injecting liquid crystal in order to remove, be heated to 120 ℃ after, slowly be cooled to room temperature.On the unit of making, paste polaroid, make the polarization direction of polaroid consistent, make liquid crystal display device with the ultraviolet polarization plane of irradiation.
In this liquid crystal display device, liquid crystal carries out vertical orientated, and its orientation is good.Impressed voltage 12V observes and the parallel liquid crystal aligning of ultraviolet polarization plane that shines thereon.
Embodiment 2
The polymkeric substance 2 that in using synthesis example 2, obtains, make liquid crystal display device similarly to Example 1, can access element with good state of orientation.Impressed voltage under condition is similarly to Example 1 then observed and the parallel orientation of ultraviolet polarization plane of shining.
Embodiment 3
The polymkeric substance 3b that in using synthesis example 3, obtains, make liquid crystal display device similarly to Example 1, can access element with good state of orientation.Impressed voltage under condition is similarly to Example 1 then observed and the parallel orientation of ultraviolet polarization plane of shining.
Comparative example 1
Use and compare the polymkeric substance 3b ' that obtains in the synthesis example, form film similarly to Example 1 on substrate, irradiation straight line polarized UV rays uses it to make liquid crystal display device then.In this liquid crystal display device, identical with embodiment 1, can access good vertical orientatedly, but under condition similarly to Example 1, during impressed voltage, can not observe liquid crystal aligning.
Embodiment 4
(1) with 4-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy) vinylbenzene 0.04 mole (17.1g), (6-(4-phenyl styryl ketone base oxygen base hexyloxy) phenyl maleimide 0.05 mole (24.8g) and Diisopropyl azodicarboxylate 3.0g are dissolved among the N,N-DIMETHYLACETAMIDE 500ml, in nitrogen environment, 80 ℃ reaction 10 hours down to n-Hexadecane oxygen base vinylbenzene 0.01 mole of (3.45g), 4-.The heavy-gravity reaction mixture that obtains is dropped in the methyl alcohol, make polymer precipitation, drying, obtain maleimide/styrol copolymer 44.5g.
(2) will add bisphenol f type epoxy resin (oiling シ エ Le epoxy (strain) system with respect to the maleimide/styrol copolymer that obtains, Epikote828) substance dissolves of 2 weight % is in gamma-butyrolactone, make the solution of solid component concentration 4 weight %, filter with aperture 1 μ m filters, and prepares liquid crystal aligning agent of the present invention.
(3) the liquid crystal aligning agent rotation that obtains is coated on the glass substrate of band ITO electrode, making thickness is 80nm, and drying is 2 minutes under 130 ℃, forms film.Then, this film surface is heated to 180 ℃, use high pressure Hg lamp simultaneously, light by パ ィ レ ッ Network ス (registered trade mark) glass polaroid SPF-50C-32 (Sigma ray machine system) the blocking-up wavelength shorter than 320nm, by the normal direction of real estate from the angular illumination of 45 degree that tilt based on the rectilinearly polarized light of 365nm wavelength 240 seconds, make liquid crystal orientation film.Irradiation dose is 5.3J/cm 2
(4) for a pair of substrate that has formed above-mentioned liquid crystal orientation film, silk screen printing contains the epoxy adhesive of diameter 17 μ m alumina balls on the face that forms liquid crystal orientation film, overlaps substrate, and the ultraviolet polarization direction of irradiation is parallel to each other, carry out crimping, make adhesive cures.Then, by inlet inject nematic liquid crystal (メ Le Network society system, MLC-6608) after, with the sealing of epoxies binding agent.And, the flow orientation when injecting liquid crystal in order to remove, be heated to 120 ℃ after, slowly be cooled to room temperature.On the unit of making, paste polaroid, make the polarization direction of polaroid consistent, make liquid crystal display device with the ultraviolet polarization direction of irradiation.
During (5) to the liquid crystal display device impressed voltage that obtains, the orientation of liquid crystal is good, and external alive ON-OFF replys, and the light and shade of observing liquid crystal display device changes, and contrast gradient is good.In addition, pre-tilt angle is 3 °.
(6) liquid crystal display device that obtains after 60 minutes, is measured pre-tilt angle in heating under 70 ℃, 100 ℃, 120 ℃, 150 ℃, 170 ℃ respectively, pre-tilt angle is 3 ° ± 0.2 ° as shown in Figure 1, pre-tilt angle performance excellent in stability.
Embodiment 5
(1) with 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 0.1 mole of (22.4g), 1-(6-(4-phenyl styryl ketone base oxygen base) hexyloxy)-2,4-diaminobenzene 0.05 mole of (21.5g), 1-n-Hexadecane oxygen base-2,4-diaminobenzene 0.05 mole (17.4g) is dissolved among the N-N-methyl-2-2-pyrrolidone N-300g, and 60 ℃ were reacted 6 hours down.Then, reaction mixture is injected in the excessive methyl alcohol, makes the reaction product precipitation.Then, use methanol wash, reduced pressure, 40 ℃ dry 15 hours down obtain polyamic acid 60.7g.
In the polyamic acid that obtains, add N-N-methyl-2-2-pyrrolidone N-380g, pyridine 16g and diacetyl oxide 20.5g, under 120 ℃, carried out imidization reaction 4 hours.Reaction mixture is injected in the excessive methyl alcohol, makes the reaction product precipitation, use methanol wash then, drying is 15 hours under the reduced pressure, obtains polyimide 54.4g.
(2) will add N with respect to the polyimide that obtains, N, N ', N '-four glycidyl group-4, the substance dissolves of 4 '-diaminodiphenyl-methane, 2 weight % is in gamma-butyrolactone, make the solution of solid component concentration 4 weight %,, prepare liquid crystal aligning agent of the present invention with the filter filtration of aperture 1 μ m.
(3) except that using the liquid crystal aligning agent that obtains, carry out similarly to Example 1, make liquid crystal display device.During to the liquid crystal display device impressed voltage that obtains, the orientation of liquid crystal is good, and external alive ON-OFF replys, and the light and shade of observing liquid crystal display device changes, and contrast gradient is good.In addition, pre-tilt angle is 3 °.
(4) liquid crystal display device that obtains after 60 minutes, is measured pre-tilt angle in heating under 70 ℃, 100 ℃, 120 ℃, 150 ℃, 170 ℃ respectively, pre-tilt angle is 3 ° ± 0.3 °, pre-tilt angle performance excellent in stability.
Comparative example 2
Use the maleimide/styrene polymer that obtains among the embodiment 4 (1), except that not using bisphenol f type epoxy resin, carry out similarly to Example 4, obtain liquid crystal aligning agent and liquid crystal display device.The liquid crystal display device liquid crystal aligning and the contrast gradient that obtain are good, but with the same condition of embodiment 4 (6) under when estimating, pre-tilt angle is uneven, as shown in Figure 1, in 1.5 °～3 ° scope, pre-tilt angle performance poor stability.
As mentioned above, according to the formation method of the liquid crystal orientation film that uses liquid crystal aligning agent of the present invention, the dust that the static that produces when grinding process in the past can not take place causes adheres to, and therefore the destruction of TFT element circuitry can form liquid crystal orientation film in high yields ground.In addition, the liquid crystal aligning agent that forms by the inventive method has high liquid crystal aligning restraint and pre-tilt angle performance stability, therefore preferably be not orientated bad being difficult to generation when using as demonstration such as TN type, STN types, the high liquid crystal display device of display quality can be accessed, various devices can be effective to.For example be suitable for the display unit of desk calculator, wrist-watch, timer, coefficient display panel, word processor, PC, LCD TV etc.

Claims (3)

1, a kind of liquid crystal aligning agent, it is characterized in that, comprise: have the structure that (A) can carry out crosslinking reaction by light, (B) be selected from the ester ring type organic group of the alkyl of fluorine-containing organic group, carbonatoms 10～30 and carbonatoms 10～30 at least a kind of group and (C) as the polymkeric substance that carries out the epoxy construction of crosslinked structure by heat
Said structure (A) is to be selected from following formula (I), (II), (III) and (IV) at least a structure in the structure of expression:
-P 1-CR 1＝CR 2-CO-Q 1- ····(I)
P 2-CR 3＝CR 4-CO-Q 2- ····(II)
P 3-CR 5＝CR 6-CO-Q 3- ····(III)
-P 4-CR 7＝CR 8-CO-Q 4 ····(IV)
In the formula, P 1And P 4Identical or different, expression has the divalent organic group of aromatic nucleus, P 2, P 3And Q 4Identical or different, expression has 1 valency organic group of aromatic nucleus, Q 2Expression has 3 valency organic groups of the aromatic nucleus that is selected from benzene, biphenylene, naphthalene and anthracene, Q 1And Q 3Identical or different, be selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene and 4,4 '-biphenylene, in addition, R 1, R 2, R 3, R 4, R 5, R 6, R 7And R 8Identical or different, expression hydrogen atom or alkyl,
And, said structure (A), (B) and (C), for whole repeating units, repeating unit with structure (A) contains with the ratio of 10～95 moles of %, repeating unit with structure (B) contains with the ratio of 5～50 moles of %, and the repeating unit with structure (C) contains with the ratio of 0.1～5 mole of %.
2, a kind of formation method of liquid crystal orientation film is characterized in that, will be heated to more than the room temperature by the film that the described liquid crystal aligning agent of claim 1 obtains, and carries out the polarized UV rays irradiation simultaneously.
3, a kind of liquid crystal display device wherein contains the liquid crystal orientation film that is obtained by the described liquid crystal aligning agent of claim 1.
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