CN104136976B - The manufacture method of transverse electric field driving liquid crystal display cells - Google Patents
The manufacture method of transverse electric field driving liquid crystal display cells Download PDFInfo
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- CN104136976B CN104136976B CN201280070337.9A CN201280070337A CN104136976B CN 104136976 B CN104136976 B CN 104136976B CN 201280070337 A CN201280070337 A CN 201280070337A CN 104136976 B CN104136976 B CN 104136976B
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- liquid crystal
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- 229940100630 metacresol Drugs 0.000 description 1
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 1
- XXGJRAFLOAKNCC-UHFFFAOYSA-N methane;molecular hydrogen Chemical group C.[H][H] XXGJRAFLOAKNCC-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N methoxyethyl Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000000116 mitigating Effects 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N oxolan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 229960005335 propanol Drugs 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- ZXDUPDQEFOYLOM-UHFFFAOYSA-O propylideneazanium Chemical group [CH2-]CC=[NH2+] ZXDUPDQEFOYLOM-UHFFFAOYSA-O 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940086735 succinate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ODGCEQLVLXJUCC-UHFFFAOYSA-N tetrafluoroborate Chemical compound F[B-](F)(F)F ODGCEQLVLXJUCC-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The present invention is the manufacture method of a kind of transverse electric field driving liquid crystal display cells, it is characterized in that, it is included on substrate after coating of liquid crystalline alignment agent forms liquid crystal orientation film and implement orientation process, a pair substrate of this liquid crystal orientation film will be defined according to making the condition that above-mentioned liquid crystal orientation film is relative oppositely disposed via liquid crystal, make liquid crystal cell, then this liquid crystal cell is carried out light irradiation, make the optical polymerism group in liquid crystal and/or in liquid crystal orientation film carry out the operation reacted.
Description
Technical field
The present invention relates to the manufacture method of transverse electric field driving liquid crystal display cells.
Background technology
Liquid crystal display cells for LCD TV, liquid crystal display etc. is generally provided with for controlling liquid crystal in element
The liquid crystal orientation film of state of orientation.
At present, according to industrial most common method, this liquid crystal orientation film be by with cloth such as cotton, nylon, polyester towards one
The film table formed by polyamic acid and/or the polyimides by its imidizate that direction wiping is formed on electrode base board
Face, the most so-called friction treatment make.
In the orientation process of liquid crystal orientation film, the method that face carries out friction treatment is easy and highly productive
Industrial useful method.But, the high performance of liquid crystal display cells, high-definition, the requirement of maximization are improved day by day,
In the impact of the damage on liquid crystal orientation film surface, airborne dust, mechanical force or the electrostatic that are caused by friction treatment and then orientation process face
The various problems such as inhomogeneities the most obvious.
The instead method of friction treatment, it is known that the light giving liquid crystal aligning ability by irradiating polarized UV rays takes
Xiang Fa.To liquid crystal aligning based on optical alignment method process, propose according to mechanism utilize photoisomerization to react process, utilize light
The process of dimerization, utilize the process etc. (with reference to non-patent literature 1) of photolysis reactions.
Such as, in patent documentation 1, it is proposed that the polyimide film on main chain with alicyclic structures such as Tetramethylene. rings is used
Method in optical alignment method.In the case of using the polyimide film that have employed this optical alignment method as liquid crystal orientation film, with
Additive method is compared has high-fire resistance, therefore can expect its serviceability.
Such polyimide film with alicyclic structures such as Tetramethylene. rings, by irradiating the ultraviolet of short wavelength, especially
It is the polarized UV rays near 254nm, presents high anisotropy, obtain the liquid crystal orientation film that liquid crystal aligning is excellent.But,
Owing to the ultraviolet energy near 254nm is high, irradiating and need a large amount of electric power, the cost being applied not only to light orientation process is high, to ring
The load in border is the biggest.Additionally, for the ultraviolet using the higher short wavelength of energy, it is believed that also have to the electrode formed on substrate
Or thin film transistor (TFT) (being the most also denoted as TFT) brings the probability of damage.
On the other hand, the optical alignment method utilizing photoisomerization or photodimerization can pass through the inclined of more than illumination wavelength 300nm
Shake ultraviolet, gives anisotropy.But, utilize the liquid crystal orientation film obtained by the optical alignment method of photoisomerization or photodimerization
Orientation restraint weak, in the case of liquid crystal display cells, have the problem producing ghost.
Here, it is known that substrate (laterally) is above applied electric field in the horizontal direction and drives the transverse electric field of liquid crystal molecule to drive
The liquid crystal display cells of mode (IPS:In-Plane Switching).The liquid crystal display cells of this transverse electric field type of drive by
Useful in visual angle width, but owing to being easily subject to the impact of the state of orientation of liquid crystal, have be particularly easy to produce the most residual
The problem of shadow.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 9-297313 publication
Non-patent literature
Non-patent literature 1: " liquid crystal photo-alignment film " wood family rib, village of city functional material in November, 1997 Vol.17
No.1113-22 page
Summary of the invention
Invent technical problem to be solved
It is an object of the invention to provide the horizontal electricity of a kind of generation strengthening the orientation restraint of liquid crystal, suppression ghost
The manufacture method of field driving liquid crystal display cells.
Solve the technical scheme that technical problem is used
Present inventor to achieve these goals, finds when conscientiously studying, by the following method obtained by horizontal electricity
The liquid crystal display cells that field drives can realize above-mentioned purpose, thus completes the present invention；The method is to use to the addition of tool
There is a liquid crystal of the polymerizable compound of optical polymerism group, or use by having obtained by the aligning agent for liquid crystal of optical polymerism group
Liquid crystal orientation film, utilizes friction or optical alignment method to implement orientation process, after making liquid crystal cell, makes to be present in liquid by irradiating light
The optical polymerism group of brilliant alignment films and liquid crystal contact portion reacts, the liquid of part that thereby will contact with liquid crystal orientation film
The method of brilliant solidification.In sum, the technology contents of the present invention is as described below.
1. the manufacture method of a transverse electric field driving liquid crystal display cells, it is characterised in that be included on substrate painting
After cloth aligning agent for liquid crystal forms liquid crystal orientation film and implements orientation process, will define a pair of this liquid crystal orientation film via liquid crystal
Substrate, according to making the condition that described liquid crystal orientation film is relative oppositely disposed, makes liquid crystal cell, then carries out this liquid crystal cell
Light irradiates, and makes the optical polymerism group in liquid crystal and/or in liquid crystal orientation film carry out the operation reacted.
2. the manufacture method of the transverse electric field driving liquid crystal display cells as described in 1, it is characterised in that described liquid crystal contains
There is the polymerizable compound with described optical polymerism group.
3. the manufacture method of the transverse electric field driving liquid crystal display cells as described in 1 or 2, it is characterised in that described liquid
Brilliant alignment agent contains described optical polymerism group.
4. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～3, its feature exists
In, described aligning agent for liquid crystal contains the polymer on side chain with described optical polymerism group.
5. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～4, its feature exists
In, described aligning agent for liquid crystal contains the polymerizable compound with described optical polymerism group.
6. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 3～5, its feature exists
In, described optical polymerism group is the group in optical polymerism group shown below.
[changing 1]
(in formula, Me represents methyl.)
7. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～6, its feature exists
In, described orientation process is carried out by the irradiation of polarized UV rays.
8. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～7, its feature exists
In, in described orientation process, there is the photoreactive group selected from following formula (A-1)～the structure of (A-7) and react.
[changing 2]
9. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～8, its feature exists
In, the polymer contained by described aligning agent for liquid crystal comprises selected from polyimide precursor with by polyamides Asia obtained by its imidizate
At least one of amine.
10. the manufacture method of the transverse electric field driving liquid crystal display cells as according to any one of 1～9, its feature exists
In, the polymer contained by described aligning agent for liquid crystal comprises polysiloxanes.
The manufacture method of the 11. transverse electric field driving liquid crystal display cells as according to any one of 1～10, its feature exists
In, the polymer contained by described aligning agent for liquid crystal comprises poly-(methyl) acrylate.
The effect of invention
If the employing present invention, can obtain possessing and implement orientation process by friction or optical alignment method, especially by light
Orientation implements the liquid crystal orientation film of orientation process, can strengthen the transverse electric field of the generation of the orientation restraint of liquid crystal, suppression ghost
The liquid crystal display cells driven.
Detailed description of the invention
The present invention is the manufacture method of a kind of transverse electric field driving liquid crystal display cells, it is characterised in that be included in base
After coating of liquid crystalline alignment agent forms liquid crystal orientation film and implements orientation process on plate, this liquid crystal orientation film will be defined via liquid crystal
A pair substrate according to making the condition that above-mentioned liquid crystal orientation film is relative oppositely disposed, make liquid crystal cell, then brilliant to this liquid crystal
Born of the same parents carry out light irradiation, make the optical polymerism group in liquid crystal and/or in liquid crystal orientation film carry out the operation reacted.Hereinafter, respectively
Constitutive requirements are described in detail.
<optical polymerism group>
Aligning agent for liquid crystal and/or liquid crystal that the manufacture method of the present invention is used contain optical polymerism group.Gather containing light
The liquid crystal of conjunction property group is by adding compound (the hereinafter also referred to polymerism chemical combination containing optical polymerism group in liquid crystal
Thing) obtained by.Additionally, in order to obtain the aligning agent for liquid crystal containing optical polymerism group, can add poly-in aligning agent for liquid crystal
Conjunction property compound, it is also possible to import optical polymerism group on the side chain of the polymer contained by aligning agent for liquid crystal, it is also possible to be
Both.Liquid crystal orientation film obtained by such aligning agent for liquid crystal is used to contain optical polymerism group.Polymerization is added in liquid crystal
In the case of property compound, its adding proportion, relative to liquid crystal, such as can make polymerizable compound is 0.1～30 (matter
Amount) %.Additionally, in the case of adding polymerizable compound in aligning agent for liquid crystal, its adding proportion, relative to liquid crystal aligning
Agent, such as can make polymerizable compound is 0.1～30 (quality) %.
If the liquid crystal display cells containing optical polymerism group in liquid crystal orientation film and/or in liquid crystal is irradiated ultraviolet
The light such as line, then the optical polymerism group being positioned at the face contacted with liquid crystal orientation film and liquid crystal reacts, and is positioned at liquid crystal orientation film
The orientation of liquid crystal on surface be cured.Thus, shown in embodiment as be described hereinafter, obtaining the same of good liquid crystal aligning
Time, the orientation restraint of strengthening liquid crystal, as a result of which it is, the electrical characteristics of the ghost phenomena etc. caused by liquid crystal aligning confusion obtain
Improve.
Optical polymerism group is the group by light generation polyreactions such as ultraviolet, such as, as long as pass through ultraviolet
Group (the hereinafter also referred to group of photopolymerization) or group (the hereinafter also referred to base of photo-crosslinking of photo-crosslinking being polymerized is carried out Deng light
Group) then it is not particularly limited, but structure as shown below is preferably used.
[changing 3]
(in formula, Me represents methyl.)
As the concrete example of polymerizable compound, represented by lower formula (I) 2 ends can be enumerated and be respectively provided with photopolymerization
The end of the compound of group, the end comprising the group with photopolymerization represented by lower formula (II) and the group with photo-crosslinking
The compound of end, 2 ends represented by lower formula (III) are respectively provided with the compound of the group of photo-crosslinking.It addition, lower formula (I)
～in (III), R12For H or the alkyl of carbon number 1～4, Z1For being taken by the alkoxyl of the alkyl of carbon number 1～12 or carbon number 1～12
The bivalence aromatic ring in generation or heterocycle, Z2For the monovalence aromatic ring that can be replaced by the alkoxyl of the alkyl of carbon number 1～12 or carbon number 1～12
Or heterocycle, Q1For divalent organic group.Q1Preferably there is phenylene (-C6H4-), biphenylene (-C6H4-C6H4-) or sub-hexamethylene
Base (-C6H10-) etc. ring structure.This is because easily increase with the interaction of liquid crystal.
[changing 4]
[changing 5]
As the concrete example of the polymerizable compound represented by formula (I), can enumerate represented by following formula (I-1)～(I-5)
Polymerizable compound.In following formula, V is singly-bound or with-R1O-represents, wherein R1Alkylene for the carbon number 1～10 of straight or branched
Base, preferably with-R1O-represents, wherein R1Alkylidene for the carbon number 2～6 of straight or branched.Additionally, W is singly-bound or with-OR2-
Expression, wherein R2For the alkylidene of the carbon number 1～10 of straight or branched, preferably with-OR2-expression, wherein R2For straight or branched
The alkylidene of carbon number 2～6.It addition, V with W can be identical structure can also be different structures, the most easily
Synthesis.
[changing 7]
It addition, even as the group of photopolymerization or the group of photo-crosslinking, not there is alpha-methylene-gamma-butyrolactone base and
There is the acrylate-based or polymerizable compound of methacrylic acid ester group, as long as have this acrylate-based or metering system
The polymerizable compound of the structure that perester radical is combined with phenylene via oxyalkylene group group at equal intervals, then with above-mentioned at two ends
The polymerizable compound being respectively provided with alpha-methylene-gamma-butyrolactone base on end is identical, can make AC stress ghost characteristic significantly carry
High, i.e. can significantly to suppress the ghost produced because of the applying of alternating current (AC).Additionally, if having acrylate-based or
The polymerizable compound of the structure that methacrylic acid ester group is combined with phenylene via oxyalkylene group group at equal intervals, then may be by
In improve the stability to heat, so can be substantially resistant to the firing temperature by high temperature such as more than 200 DEG C.
Additionally, as the concrete example of the polymerizable compound represented by formula (I), the polymerism chemical combination of following formula also can be enumerated
Thing.
[changing 8]
(in formula, R12, V, W definition same as described above.)
The manufacture method of this polymerizable compound is not particularly limited, such as, can manufacture according to synthesis example described later.
Such as, the polymerizable compound represented by above formula (I-1) can be carried out by the technology in Synthetic Organic Chemistry being combined
Synthesis.Such as, can by P.Talaga, M.Schaeffer such as the tower glugs (Talaga) that represents with following reaction equation,
C.Benezra and J.L.Stampf, in Synthesis (" synthesis " magazine), the method proposed in 530 (1990), uses SnCl2
Make 2-(bromomethyl) acrylic acid (2-(bromomethyl) propenoic acid) react with aldehydes or ketones to synthesize.It addition,
Amberlyst15 is the strong-acid ion exchange resin that Rhom and Hass's (ロ system ア ンドハ ス society) makes, and THF is four
Hydrogen furan.
[changing 9]
(in formula, R ' represents monovalent organic group.)
Additionally, 2-(bromomethyl) acrylic acid can be by the La Malaen (Ramarajan) etc. represented with following reaction equation
K.Ramarajan, K.Kamalingam, D.J.O'Donnell and K.D.Berlin are in Organic Synthesis (" organic conjunction
Become " magazine), the method proposed in vol.61,56-59 (1983) synthesizes.
[changing 10]
As concrete synthesis example, it is-R at synthesis V1O-, W are-OR2-、R1And R2Represented by identical above formula (I-1)
In the case of polymerizable compound, 2 methods represented by following reaction equation can be enumerated.
[changing 11]
[changing 12]
Additionally, at synthesis R1And R2In the case of the different polymerizable compounds represented by above formula (1), can enumerate following
Method represented by reaction equation.
[changing 13]
Additionally, in the case of the polymerizable compound represented by the above formula (I-1) that synthesis V and W is singly-bound, can enumerate down
State the method represented by reaction equation.
[changing 14]
In the case of the side chain of the polymer contained by aligning agent for liquid crystal imports optical polymerism group, even if at liquid crystal
In or aligning agent for liquid crystal in polymerizable compound few or in the case of not having, it is also possible to obtain the effect of the present invention.Certainly, liquid
Polymerizable compound can also be there is, in such a case it is possible to expect effect further in crystalline substance or in aligning agent for liquid crystal.Import
The side chain (the hereinafter also referred to side chain of optical polymerism) of optical polymerism group refers to, containing selected from methylacryloyl, acryloyl group,
The side chain of at least one of vinyl, pi-allyl, styryl and alpha-methylene-gamma-butyrolactone base.Like this, liquid crystal aligning
Polyimide precursor contained by agent and by least one in polyimides obtained by this polyimide precursor imidizate etc.
Polymer become and have containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and α-methylene
The polymer of the side chain of the optical polymerism of at least one of base-gamma-butyrolacton base, by using with above-mentioned polymerizable compound simultaneously
In aligning agent for liquid crystal, shown in embodiment as be described hereinafter, it is remarkably improved the ghost characteristic that AC stress wait.
The side chain of optical polymerism can be directly incorporated on the main chain of the polymer such as polyimide precursor or polyimides, or
Person can also be combined via suitable conjugated group.As the side chain of optical polymerism, such as, can enumerate with following formula (b) institute table
The side chain shown.
[changing 15]
-R8-R9-R10 (b)
(in formula (b), R8Represent singly-bound or-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-
N(CH3)-、-CON(CH3)-、-N(CH3) any one in CO-；R9Represent singly-bound or non-substituted or be replaced by fluorine atoms
The alkylidene of carbon number 1～20 ,-the CH of alkylidene2-can be by-CF2-or-CH=CH-arbitrarily replace, any base below enumerated
Group the most non-conterminous in the case of, it is also possible to replaced by these groups :-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-,
The carbocyclic ring of bivalence, the heterocycle of bivalence.R10Represent methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and α-
Methylene-y-butyrolactone base.)
Although it addition, can be formed by conventional organic synthesis technology, but from the viewpoint of the easiness of synthesis, on
R in formula (b)8Preferably-CH2-、-O-、-COO-、-NHCO-、-NH-、-CH2O-。
Additionally, as may replace R9Arbitrary-CH2-the carbocyclic ring of bivalence or the carbocyclic ring of heterocycle of bivalence or heterocycle, tool
Body can enumerate following structure, but is not limited thereto.
[changing 16]
R10From the viewpoint of optical polymerism, preferably methylacryloyl, acryloyl group, vinyl or alpha-methylene-γ-
Butyrolactone base.
The amount of the side chain of optical polymerism, preferably can form covalency by being carried out reaction by the irradiation of ultraviolet
In the range of orientation is solidified by key, in order to improve AC ghost characteristic further, excellent in the range of other characteristics are not affected
Select the most.
So, to manufacturing selected from having containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styrene
The polyimide precursor of the side chain of the optical polymerism of at least one of base and alpha-methylene-gamma-butyrolactone base, and by this polyamides
There is no particular limitation for the method for at least one polymer in polyimides obtained by imines precursor imidizate, such as,
Obtained by the reaction of diamidogen and tetracarboxylic dianhydride in the method for polyamic acid, diamidogen or tetracarboxylic dianhydride can be carried out copolymerization,
Described diamidogen or tetracarboxylic dianhydride have containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl
Side chain with the optical polymerism of at least one of alpha-methylene-gamma-butyrolactone base.
<polymer>
The polymer that aligning agent for liquid crystal used in the present invention contains, at polyimide precursor, obtains its imidizate
Polyimides outside, polysiloxanes or poly-(methyl) acrylate are preferably used.Herein, polyimide precursor refers to polyamic acid
(Ployamic acid, also referred to as Polyamide acid) or poly amic acid ester.Additionally, in aligning agent for liquid crystal, can contain simultaneously
Having the polymer that these are different, their content ratio can carry out various selection according to the characteristic of liquid crystal display cells.Liquid crystal takes
To total amount preferably 0.1～20 (quality) % of the polymer that agent contains.It addition, the polyamides that the aligning agent for liquid crystal of the present invention contains is sub-
The polymer such as amine precursor, polyimides, polysiloxanes or poly-(methyl) acrylate, it is desirable to be able to be dissolved in aligning agent for liquid crystal institute
In the solvent contained.
<photoreactive group>
In the operation of the orientation process in the manufacture method of the present invention, in the case of using polarized UV rays, at liquid crystal
In the polymer that alignment agent contains, the utilization being directed through polarized UV rays is needed to present the photoreactivity base of liquid crystal aligning ability
Group.Such photoreactive group can import on the main chain of polymer, it is also possible to imports on side chain.
By shining by liquid crystal orientation film obtained by the aligning agent for liquid crystal containing the polymer having imported photoreactive group
Penetrate polarized UV rays to carry out photoreaction, give with in the vertical direction of same direction, polarization direction or polarization direction each to
The opposite sex, is orientated liquid crystal.Photoreaction has photolysis, photodimerization, photoisomerization.If lifting its concrete example, as carrying out
The structure of photodimerizationization reaction, can enumerate the structure represented by following formula (A-3), (A-4), (A-5).As carrying out, photoisomerization is anti-
The structure answered, can enumerate the structure represented by following formula (A-6), (A-7).As carrying out the structure of photolysis reactions, can enumerate down
Structure represented by formula (A-1), (A-2).It addition, have selected from following formula (A-1)～the photoreactive group of the structure of (A-7)
Refer to, the structure of these formulas (A-1)～(A-7) takes group that N in the group after the H of Arbitrary Digit, formula (A-1)～(A-2) is key,
The group that in formula (A-3), O is the group of key or these structures combine with other structures (such as alkylidene etc.).
[changing 17]
<polyimide precursor and by polyimides obtained by its imidizate>
Polyimide precursor contained by aligning agent for liquid crystal used in the present invention, such as, have represented by following formula (1)
Repetitive (construction unit).
[changing 18]
In formula (1), R1For hydrogen atom or the alkyl of carbon number 1～4.From the complexity being carried out imidizate by heating
From the point of view of viewpoint, particularly preferred hydrogen atom or methyl.X2Being 4 valency organic groups, its structure is not particularly limited.If tool to be enumerated
Style, then can enumerate following formula (X-1)～(X-43).From the viewpoint of liquid crystal aligning, X2Preferably (X-1)～(X-10), (X-
26)～(X-28), (X-31)～(X-37).Additionally, from obtaining the mitigation of the residual charge of accumulation under the effect of DC voltage
From the viewpoint of fast liquid crystal orientation film, preferably using there is aromatic ring structure tetracarboxylic dianhydride as raw material, as formula (1)
X2Structure, more preferably (X-26), (X-27), (X-28), (X-32), (X-35) or (X-37).
[changing 19]
(in formula (X-1), R2、R3、R4And R5It is separately hydrogen atom, halogen atom, the alkyl of carbon number 1～6, carbon number
Alkenyl, alkenyl or the phenyl of 2～6.From the viewpoint of liquid crystal aligning, R2、R3、R4And R5Preferably hydrogen atom, halogen is former
Son, methyl or ethyl, more preferably hydrogen atom or methyl, further preferably selected from the structure represented by following formula (X1-1)～(X1-2)
At least one.)
[changing 20]
[changing 22]
[changing 23]
In the operation of the orientation process in the manufacture method of the present invention, in the case of using polarized UV rays, as X2
Preferred structure, (X1-1), (X1-2), (X-2), (X-3), (X-5), (X-7), (X-8), (X-9), (X-10) can be enumerated, special
Not preferably (X1-1), (X1-2) and (X-6).
In above-mentioned formula (1), Y2For divalent organic group, its structure is not particularly limited.If Y to be enumerated2Concrete example, then
Following formula (Y-1)～(Y-73) can be enumerated.
[changing 24]
[changing 25]
[changing 26]
[changing 27]
[changing 28]
[changing 29]
[changing 30]
[changing 31]
(in formula, Me represents methyl.)
In order to expect the deliquescent raising to organic solvent such as polyimide precursor or polyimides, preferably comprise
There is the construction unit of the structure of (Y-8), (Y-20), (Y-21), (Y-22), (Y-28), (Y-29) or (Y-30).
Polyimide precursor contained by aligning agent for liquid crystal used in the present invention passes through diamine component (tool the most described later
The diamidogen such as the diamidogen having the side chain of optical polymerism or the diamidogen with photoreactive group) and tetracarboxylic dianhydride's composition (after such as
Tetracarboxylic dianhydride, tetrabasic carboxylic acid diester diacid chloride or the tetrabasic carboxylic acid diester etc. stated) reaction and obtain.Specifically, polyamic acid is
Obtained by the reaction of diamine component with tetracarboxylic dianhydride.Poly amic acid ester is by by diamine component and tetrabasic carboxylic acid diester two
Acyl chlorides carries out reacting or being entered in the presence of suitable condensing agent, alkali with diamine component by tetrabasic carboxylic acid diester in the presence of a base
Row reaction obtains.Additionally, polyimides can carry out dehydration closed-loop by making this polyamic acid or carry out poly amic acid ester
Heating is so that its closed loop obtains.As for obtaining the polymer of liquid crystal orientation film, described polyamic acid, poly amic acid ester and
Any one in polyimides is the most useful.
<there is the diamidogen of the side chain of optical polymerism>
As having containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and α-methylene
The diamidogen of the side chain of the optical polymerism of at least one of base-gamma-butyrolacton base, such as, can enumerate and have represented by above formula (b)
The diamidogen of side chain.More specifically, such as can enumerate the diamidogen represented with following formula (2), but be not limited thereto.
[changing 32]
(the R in formula (2)8、R9And R10Definition identical with above formula (b).)
To two amino (-NH in formula (2)2) binding site do not limit.Specifically, can enumerate relative to side chain
Conjugated group phenyl ring on 2,3,2,4,2,5,2,6,3,4,3,5.Wherein, when synthesizing polyamides acid
Reactivity from the viewpoint of, preferably 2,4,2,5 or 3,5.If further contemplating easiness during synthesis diamidogen, the most excellent
Select 2,4 or 3,5.
As having containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and α-methylene
The diamidogen of the side chain of the optical polymerism of at least one of base-gamma-butyrolacton base, specifically can enumerate following compound, but also
It is not limited to this.
[changing 33]
(in formula, X represents singly-bound, or selected from-O-,-COO-,-NHCO-, the conjugated group of-NH-, Y represents singly-bound, or non-
The alkylidene of the carbon number 1～20 replaced or be replaced by fluorine atoms.)
Above-mentioned have comprise selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and α-methylene
The diamidogen of the photoreactive side chain of at least one of base-gamma-butyrolacton base can be according to the liquid made when liquid crystal orientation film
The characteristics such as brilliant orientation, tilt angle, voltage retention performance, accumulated charge, liquid crystal response speed when making liquid crystal display cells
Deng, it is used alone, or mixing two or more.
Additionally, such have containing selected from methylacryloyl, acryloyl group, vinyl, pi-allyl, styryl and
The diamidogen of the side chain of the optical polymerism of at least one of alpha-methylene-gamma-butyrolactone base, is preferably used and reaches at polyamic acid
The amount of 10～70 moles of % of the total amount of the diamine component used during synthesis, more preferably 20～60 moles %, particularly preferred 30
～50 moles of %.
<there is the diamidogen of photoreactive group>
In the operation of the orientation process in the manufacture method of the present invention, in the case of using polarized UV rays, at liquid crystal
In the polymer that alignment agent contains, need to import photoreactive group.
Using the orientation process side carrying out photolysis reactions by the irradiation of polarized UV rays and make anisotropy produce
In the case of method, the structure of above formula (A-1), (A-2) can be imported polyimide precursor and the main chain of polyimides.
Carry out photodimerization or photoisomerization reaction in use by the irradiation of polarized UV rays and make anisotropy produce
Method for orientation treatment in the case of, the structure of above formula (A-3), (A-7) can be imported main chain or the side chain of polymer.
As polymer contained in aligning agent for liquid crystal, using polyimide precursor and by obtained by its imidizate
In the case of polyimides, there is the tetracarboxylic dianhydride used in the structure containing above formula (A-3)～(A-7) in main chain or side chain
Or the method for diamidogen, but from the viewpoint of the easiness of synthesis, it is preferably used in side chain containing above formula (A-3)～(A-7)
The diamidogen of structure.It addition, the side chain of diamidogen refers to the structure being branched off from the structure of 2 amino connecting diamidogen.As
The concrete example of such diamidogen, can enumerate the compound represented by following formula, but not limited to by these.
[changing 34]
(in formula, X represents singly-bound, or selected from-O-,-COO-,-NHCO-, the conjugated group of-NH-, Y represents singly-bound, or non-
The alkylidene of the carbon number 1～20 replaced or be replaced by fluorine atoms.R represents hydrogen atom, or carbon that is non-substituted or that be replaced by fluorine atoms
The alkyl of several 1～5 or alkylether radicals.)
<tetracarboxylic dianhydride's composition>
In order to obtain polyamic acid contained in aligning agent for liquid crystal used in the present invention, for reacting with diamine component
Tetracarboxylic dianhydride be not particularly limited.Enumerate its concrete example below.
As having the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure, 1,2,3,4-Tetramethylene. tetrabasic carboxylic acids can be enumerated
Dianhydride, 1,2-dimethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride,
1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 2,3,4,5-tetrahydrochysene
Furan tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, 3,4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3,4-bis-
Carboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, bicyclo-[3,3,0] octane-2,4,
6,8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, cis-3,
7-dibutyl ring octyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, three ring [4.2.1.02,5] nonane-3,4,7,8-tetrabasic carboxylic acid-
3,4:7,8-dianhydride, six ring [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-
Dianhydride, 4-(2,5-dioxotetrahydro furan-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic anhydride etc..
Further, if also using aromatic series four outside the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure
Carboxylic acid dianhydride, then liquid crystal aligning improves, and can reduce the accumulated charge of liquid crystal cell, thus preferably.As aromatic series
Tetracarboxylic dianhydride, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid
Dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetrabasic carboxylic acid
Dianhydride, double (3,4-dicarboxyphenyi) ether dianhydride, double (3,4-dicarboxyphenyi) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride,
2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc..
Tetracarboxylic dianhydride can be according to liquid crystal aligning during formation liquid crystal orientation film, voltage retentivity, accumulated charge etc.
Characteristic, uses a kind or be two kinds or more.
In order to obtain poly amic acid ester contained in aligning agent for liquid crystal used in the present invention, for anti-with diamine component
The tetrabasic carboxylic acid dialkyl answered is not particularly limited.Enumerate its concrete example below.
As the object lesson of aliphatic tetrabasic carboxylic acid diester, can enumerate 1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyls, 1,
2-dimethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl, 1,3-dimethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl group
Ester, 1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl, 1,2,3,4-Pentamethylene. tetrabasic carboxylic acid dialkyl,
2,3,4,5-oxolane tetrabasic carboxylic acid dialkyl, 1,2,4,5-cyclopentanetetracarboxylic's dialkyl, 3,4-dicarboxyl-1-hexamethylene
Base dialkyl succinate, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1,2,3,4-butane tetracarboxylic
Acid dialkyl ester, bicyclo-[3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid dialkyl, 3,3 ', 4,4 ' dicyclohexyl tetrabasic carboxylic acid dioxanes
Base ester, 2,3,5-tricarboxylic cyclopentyl dialkyl acetates, cis-3,7-dibutyl ring octyl-1,5-diene-1,2,5,6-tetrabasic carboxylic acid
Dialkyl, three ring [4.2.1.02,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.12, 7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxotetrahydro
Furan-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc..
As aromatic tetracarboxylic acid's dialkyl, can enumerate Pyromellitic Acid dialkyl, 3,3 ', 4,4 '-biphenyl tetracarboxylic acid
Acid dialkyl ester, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3,3 ', 4,
4 '-benzophenone tetrabasic carboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetrabasic carboxylic acid dialkyl, double (3,4-dicarboxyphenyi) ether two
Arrcostab, double (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid
Dialkyl etc..
<manufacture method of polyamic acid>
Poly amic acid ester as polyimide precursor can be synthesized by method shown below.
Specifically, can by making tetracarboxylic dianhydride and diamidogen in presence of organic solvent, in-20 DEG C～150 DEG C, excellent
0 DEG C～50 DEG C reaction is selected to synthesize for 30 minutes～24 hours, preferably 1～12 hour.
Organic solvent used in above-mentioned reaction, considers from the dissolubility of monomer and polymer, preferably N, N-dimethyl
Methanamide, METHYLPYRROLIDONE, gamma-butyrolacton, these can use one kind or two or more being used in mixed way.Polymer
Concentration, from the viewpoint of being not susceptible to the precipitation of polymer and being readily available high molecular body, preferably 1～30 mass %, more
Preferably 5～20 mass %.
Polyamic acid obtained as described above can be injected into poor solvent according to while being sufficiently stirred for reaction solution
In mode make polymer separate out and reclaim.Additionally, after separating out for several times and cleaning with poor solvent, by room temperature or add
Heated drying can obtain the powder of sublimed polyamic acid.Poor solvent is not particularly limited, can enumerate water, methanol, ethanol,
Hexane, butyl cellosolve, acetone, toluene etc..
<manufacture method of poly amic acid ester>
As the poly amic acid ester of polyimide precursor, can be synthesized by the method for (1)～(3) described below.
(1) situation about synthesizing is carried out by polyamic acid
Poly amic acid ester can be by carrying out being esterified synthesizing by the polyamic acid obtained by tetracarboxylic dianhydride and diamidogen.
Specifically, can by making polyamic acid and esterifying agent in presence of organic solvent, in-20 DEG C～150 DEG C, excellent
0 DEG C～50 DEG C reaction is selected to synthesize for 30 minutes～24 hours, preferably 1～4 hour.
As esterifying agent, the esterifying agent that preferably easily can be removed by purification, DMF two can be enumerated
Methyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N, N-dimethyl formyl
Amine di neo-pentyl butyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-second
Base-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, chlorination 4-(4,6-dimethoxy-1,3,5-triazine-2-
Base)-4-methyl morpholineSalt etc..The addition of esterifying agent, relative to the repetitive of 1 mole of polyamic acid, preferably 2～6 rub
That equivalent.
Solvent used in above-mentioned reaction, from the point of view of the dissolubility of polymer, preferably DMF, N-first
Base-2-Pyrrolidone or gamma-butyrolacton, these solvents can use a kind or two or more are used in mixed way.Gather from being not susceptible to
The precipitation of compound and from the viewpoint of being readily available high molecular body, concentration during synthesis preferably 1～30 mass %, more preferably 5
～20 mass %.
(2) situation about synthesizing is carried out by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamidogen
Poly amic acid ester can be synthesized by tetrabasic carboxylic acid diester diacid chloride and diamidogen.
Specifically, can by make tetrabasic carboxylic acid diester diacid chloride and diamidogen in the presence of alkali and organic solvent, in-20～
150 DEG C, preferably 0～50 DEG C reaction synthesizes for 30 minutes～24 hours, preferably 1～4 hour.
Above-mentioned alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., in order to make reaction leniently carry out, preferably
Pyridine.The addition of alkali is from the amount easily removed and from the viewpoint of being readily available high molecular body, relative to tetrabasic carboxylic acid diester
Diacid chloride, preferably 2～4 times moles.
Solvent used in above-mentioned reaction, considers from the dissolubility of monomer and polymer, preferably N-methyl-2-pyrroles
Alkanone, gamma-butyrolacton, these can one kind or two or more be used in mixed way.From being not susceptible to the precipitation of polymer and being readily available
From the viewpoint of high molecular body, polymer concentration preferably 1～30 mass % during synthesis, more preferably 5～20 mass %.Additionally,
In order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the solvent used in the synthesis of poly amic acid ester is dehydrated the most as far as possible
State, is preferably carried out in nitrogen atmosphere, to prevent being mixed into of foreign gas.
(3) situation of synthesizing polyamides acid is carried out by tetrabasic carboxylic acid diester and diamidogen
Poly amic acid ester can synthesize by making tetrabasic carboxylic acid diester and diamidogen polycondensation.
Specifically, can by make tetrabasic carboxylic acid diester and diamidogen in the presence of condensing agent, alkali, organic solvent, in 0 DEG C～
150 DEG C, preferably 0 DEG C～100 DEG C of reactions synthesize for 30 minutes～24 hours, preferably 3～15 hours.
As above-mentioned condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethyl can be used
Aminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzo three
Azoles-1-base)-N, N, N ', N '-tetramethylureaTetrafluoroborate, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylureaHexafluorophosphate, (2,3-dihydro-2-sulfur generation-3-benzoOxazolyl) phosphonic acid diphenyl ester etc..The addition of condensing agent relative to
Tetrabasic carboxylic acid diester, preferably 2～3 times moles.
Above-mentioned alkali can use the tertiary amine such as pyridine, triethylamine.From the amount easily removed and the sight being readily available high molecular body
From the point of view of Dian, the addition of alkali relative to diamine component, preferably 2～4 times moles.
Additionally, in above-mentioned reaction, add lewis acid and reaction can be made to carry out efficiently as additive.As Louis
Acid, the preferably lithium halide such as lithium chloride, lithium bromide.Lewis acidic addition rubs relative to diamine component preferably 0～1.0 times
You.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, particularly preferably
Above-mentioned (1) or the synthetic method of above-mentioned (2).
The solution of poly amic acid ester obtained as described above can be injected into according to while being sufficiently stirred for reaction solution
Mode in poor solvent makes polymer separate out.Separate out for several times and with poor solvent clean after, at normal temperatures or heating
It is dried, it is possible to obtain the powder of sublimed poly amic acid ester.Poor solvent is not particularly limited, water, methanol, second can be enumerated
Alcohol, hexane, butyl cellosolve, acetone, toluene etc..
<manufacture method of soluble polyimide>
Above-mentioned polyimides can be by manufacturing above-mentioned polyamic acid or poly amic acid ester imidizate.By polyamides
In the case of amino acid ester manufactures polyimides, easy is chemical imidization, and this chemical imidization is to make above-mentioned polyamide
Acid esters solution or poly amic acid ester powder are dissolved in organic solvent, add base catalyst in the polyamic acid solution of gained.
Chemical imidization carries out imidization reaction at a lower temperature, and is not susceptible to polymerization during imidizate
The reduction of thing molecular weight, thus preferably.
Chemical imidization can by be intended to the poly amic acid ester of imidizate in organic solvent, at base catalyst
In the presence of stirring carry out.As organic solvent, solvent used when can use above-mentioned polyreaction.As base catalyst,
Pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein triethylamine is owing to having make reaction carry out enough
Alkalescence and preferred.
Temperature when carrying out imidization reaction can be-20 DEG C～140 DEG C, and preferably 0 DEG C～100 DEG C, the response time can
Think 1～100 hour.The amount of base catalyst is 0.5～30 mole times of amic acid ester group, preferably 2～20 moles times.Obtain
The acid imide rate of the polymer obtained can be controlled by regulation catalytic amount, temperature, response time.After imidization reaction
Solution remains the catalyst etc. of interpolation, the most preferably reclaims the imide amination polymer prepared and with having by following method
After machine solvent re-dissolved, it is used as aligning agent for liquid crystal.
In the case of being manufactured polyimides by polyamic acid, easy is chemical imidization, and this chemical imidization is
Catalyst is added in the solution of the above-mentioned polyamic acid prepared by the reaction of diamine component and tetracarboxylic dianhydride.Chemistry acid imide
Change is to carry out imidization reaction at a lower temperature, and is not susceptible to polymer molecular weight during imidizate
Reduction, thus preferably.
Chemical imidization can pass through in organic solvent, stirring desire acid imide in the presence of base catalyst and anhydride
The polymer changed is carried out.As organic solvent, solvent used when can use above-mentioned polyreaction.As base catalyst,
Pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated.Wherein pyridine is because having the suitable alkali making reaction carry out
Property and preferred.Additionally, as anhydride, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, uses acetic anhydride
Time be prone to the purification that carries out reacting after terminating, thus preferably.
Temperature when carrying out imidization reaction can be-20 DEG C～140 DEG C, and preferably 0 DEG C～100 DEG C, the response time can
Think 1～100 hour.The amount of base catalyst is 0.5～30 mole times of amide acidic group, preferably 2～20 moles times, anhydride
1～50 mole times that amount is amide acidic group, preferably 3～30 moles times.The acid imide rate of the polymer obtained can be by regulation
Catalytic amount, temperature, response time control.
Solution after the imidization reaction of poly amic acid ester or polyamic acid remains the catalyst etc. of interpolation, therefore
Preferably by following method, reclaim the imide amination polymer prepared and with after organic solvent re-dissolved, be used as the present invention's
Aligning agent for liquid crystal.
The solution of polyimides obtained as described above can be by being simultaneously injected into poor solvent well-beaten
Polymer is made to separate out.After separating out for several times and cleaning with poor solvent, at normal temperatures or heat drying, it is possible to obtain purification
The powder of poly amic acid ester.
Aforementioned poor solvent is not particularly limited, methanol, acetone, hexane, butyl cellosolve, heptane, methyl second can be enumerated
Base ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene etc..
<manufacture method of polysiloxanes>
Obtain the method for the polysiloxanes of use in the present invention to be not particularly limited, such as by alkoxy silane organic molten
Agent is carried out be condensed and obtain.Generally, polysiloxanes can be as organic molten by being dissolved in equably after above-mentioned alkoxy silane polycondensation
Solution in agent obtains.
As the method by alkoxy silane polycondensation, such as, can enumerate alkoxy silane water in alcohol or solvents such as glycols
The method solving, being condensed.
Now, any one during hydrolysis-condensation reaction can be partial hydrolysis and complete hydrolysis.During complete hydrolysis, in theory
The water of 0.5 times mole of the whole alkoxyls in addition alkoxy silane, but be generally preferred to add more than 0.5 times mole
The water of amount.
In the present invention, the amount of the water used by above-mentioned reaction can the most suitably select, but generally preferably alkoxyl
0.5 of whole alkoxyls in silane～2.5 times moles.
Additionally, generally under the purpose promoting hydrolysis, condensation reaction, use hydrochloric acid, sulphuric acid, nitric acid, acetic acid, formic acid, grass
The acid such as acid, maleic acid, fumaric acid, the alkali such as ammonia, methylamine, ethamine, ethanolamine, triethylamine, the slaine of hydrochloric acid, sulphuric acid, nitric acid etc.
Deng catalyst.Additionally, typically heat also by by the solution having dissolved alkoxy silane, promote hydrolysis, condensation further
Reaction.Now, can the most suitably select heating-up temperature and heat time heating time.Such as can enumerate and heat at 50 DEG C, stir
The method of 24 hours, heats, stirs the method etc. of 1 hour under reflux.
Additionally, as other method, such as the mixture that can enumerate heating alkoxy silane, solvent and oxalic acid is carried out
The method of polycondensation.Specifically, for adding oxalic acid in advance in alcohol, after forming the alcoholic solution of oxalic acid, heated by this solution
The method being mixed into alkoxy silane under state.Now, the consumption of oxalic acid is relative to the whole alkoxyls 1 contained by alkoxy silane
Mole, preferably 0.2～2 mole.Heating in the method, can be carried out at liquid temperature 50～180 DEG C.In order to avoid there is liquid
Evaporation, be vaporized, heating dozens of minutes～the method for tens hours the most under reflux.
In the case of using multiple alkoxy silane when manufacturing polysiloxanes, can be by alkoxy silane to be pre-mixed
Obtained by the form of mixture mix, it is also possible to mix multiple alkoxy silane successively.
As in order to obtain the alkoxy silane that polysiloxanes is used, illustrate following compound.
As having the alkoxysilane compound containing trialkylsilyl group in molecular structure of optical polymerism group on side chain, 3-methacryloxy can be enumerated
Propyl trimethoxy silicane, 3-methacryloxypropyl, methacryloxymethyl trimethoxy
Silane, methacryloxymethyl triethoxysilane, 3-acryloxypropyl trimethoxy silane, 3-acryloxy
Propyl-triethoxysilicane, acryloyl-oxyethyl trimethoxy silane, acryloyl-oxyethyl triethoxysilane, styrene
Ethyl trimethoxy silane, styrene ethyl triethoxysilane, 3-(N-styrene methyl-2-aminoethylamino) propyl group three
Methoxy silane, ethenylphenyl ethyl trimethoxy silane, ethenylphenyl ethyl triethoxysilane, vinyl trimethoxy
Base silane etc..
As other alkoxysilane compound containing trialkylsilyl group in molecular structure, MTMS, MTES, ethyl can be enumerated
Trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy
Silane, 3-TSL 8330, APTES, N-2 (amino-ethyl) 3-aminopropyl three
Ethoxysilane, N-2 (amino-ethyl) 3-TSL 8330,3-(2-aminoethylaminopropyl) trimethoxy
Silane, 3-(2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyl trimethoxy silane, 2-(2-
Aminoethylthio ethyl) triethoxysilane, 3-Mercaptopropyltriethoxysilane, mercapto methyl trimethoxy silane, second
Thiazolinyl triethoxysilane, 3-NCO propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, chloropropyl three second
TMOS, bromopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, dimethyldiethoxysilane, dimethyl
Dimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, dimethoxydiphenylsilane, diphenyl
Diethoxy silane, 3-amino propyl methyl diethoxy silane, 3-dimethyl Ethoxysilane, trimethyl ethoxy
Base silane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureido-propyl trimethoxy silane and
γ-ureido-propyl tripropoxy silane etc..
Solvent (hereinafter also referred to polymer solvent) used during alkoxy silane polycondensation is as long as dissolve alkoxy silane
Solvent, there is no particular limitation.Even if additionally, in the case of alkoxy silane is undissolved, as long as at alkoxyl silicone
The solvent that the polycondensation reaction of alkane is dissolved while carrying out.Generally, due to it is raw by the polycondensation reaction of alkoxy silane
Become alcohol, therefore use alcohols, di-alcohols, dihydroxylic alcohols ethers or the organic solvent good with alcohols intermiscibility.
As the concrete example of above-mentioned polymer solvent, the alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol can be enumerated；Second
Glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,3-propylene glycol, 1,2-butanediol, 1,3 butylene glycol, 1,4-fourth two
Alcohol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-PD, 2,3-penta 2
The glycols such as alcohol, 1,6-HD；Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one propyl ether, ethylene glycol one fourth
Base ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate butyl ether, diethylene glycol monomethyl
Ether, diethylene glycol monoethyl ether, diethylene glycol one propyl ether, diethylene glycol-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl base
Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, Glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol one propyl group
Ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol dipropyl ether, propylene glycol dibutyl ethers
Deng glycol ethers；METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, gamma-butyrolacton, diformazan
Sulfoxide, tetramethylurea, HMPA, metacresol etc..
In the present invention, above-mentioned polymer solvent can will use after multiple mixing.
<manufacture method of poly-(methyl) acrylate>
To the method obtaining poly-(methyl) used in the present invention acrylate, there is no particular limitation.Can be by making third
The monomer of enoic acid ester compounds or methacrylate compound etc., and use as required there is optical polymerism group or light
The monomer of reactive group, and the polymerization initiator etc. used as required carries out with the temperature of 50 DEG C～110 DEG C in a solvent
Polyreaction and obtain.As long as the solvent at this moment used dissolves monomer and the solvent of the polymer obtained, the most especially
Limit.
As acrylate compounds, such as, can enumerate acrylic acid methyl ester., ethyl acrylate, isopropyl acrylate, propylene
Acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2-trifluoro ethyl ester,
Tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2-methoxy acrylate, methoxyethyl three second
Diol ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid tetrahydro furfuryl ester, acrylic acid 3-methoxybutyl, acrylic acid 2-methyl-2-
Adamantane esters, acrylic acid 2-propyl group-2-adamantane esters, acrylic acid 8-methyl-8-tricyclodecyl and acrylic acid 8-ethyl-8-
Tricyclodecyl etc..
As methacrylate compound, such as, can enumerate methyl methacrylate, ethyl methacrylate, methyl-prop
Isopropyl gadoleate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, first
Base phenyl acrylate, methacrylic acid 2,2,2-trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, methyl
Isobornyl acrylate, methacrylic acid 2-methoxy acrylate, methacrylic acid methoxyl group triglycol ester, methacrylic acid 2-
Ethoxy ethyl ester, methacrylic acid tetrahydro furfuryl ester, methacrylic acid 3-methoxybutyl, methacrylic acid 2-methyl-2-gold
Just Arrcostab, methacrylic acid 2-propyl group-2-adamantane esters, methacrylic acid 8-methyl-8-tricyclodecyl and metering system
Acid 8-ethyl-8-tricyclodecyl etc..
As the concrete example of solvent, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, methyl cellosolve acetic acid can be enumerated
Ester, ethyl cellosolve acetate, diethylene glycol monomethyl ether, TC, propylene glycol, propylene glycol monomethyl ether,
Propylene glycol monomethyl ether, propylene glycol propyl ether acetas, toluene, dimethylbenzene, methyl ethyl ketone, Ketocyclopentane, Ketohexamethylene,
2 pentanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl
Ethyl, 2-hydroxy-3-methyl methyl butyrate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-second
Epoxide ethyl propionate, 3-ethoxypropanoate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, lactic acid second
Ester, butyl lactate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone etc..
The solution of polymer obtained by as above is put in the lower methanol of stirring, ethanol, water etc. and carries out reprecipitation, will generation
Precipitate filter clean after, under normal or reduced pressure, be can be made into the powder body of desired polymer by room temperature or heat drying.
By such operation, can remove the polymerization initiator or unreacted monomer coexisted with polymer, its result is available purification
The powder body of polymer.Fully in the case of purification, the powder body obtained can not can be dissolved in solvent again in once-through operation
In, repeat aforesaid operations.
<aligning agent for liquid crystal>
In the case of using polyimide precursor or polyimides as the polymer contained by aligning agent for liquid crystal, polyamides
Imines precursor or the molecular weight of polyimides, with Weight-average molecular gauge preferably 2000～500000, more preferably 5000～300000,
Further preferred 10000～100000.It addition, number-average molecular weight preferably 1000～250000, more preferably 2500～150000, enter
One step preferably 5000～50000.
In the case of using polysiloxanes as the polymer contained by aligning agent for liquid crystal, the molecular weight of polysiloxanes,
With Weight-average molecular gauge preferably 2000～500000, more preferably 5000～300000, further preferred 10000～100000.This
Outward, number-average molecular weight preferably 1000～250000, more preferably 2500～150000, further preferred 5000～50000.
In the case of using poly-(methyl) acrylate as the polymer contained by aligning agent for liquid crystal, poly-(methyl) third
The molecular weight of olefin(e) acid ester, with Weight-average molecular gauge preferably 2000～500000, more preferably 5000～300000, further preferably
10000～100000.Additionally, number-average molecular weight preferably 1000～250000, more preferably 2500～150000, further preferably
5000～50000.
The organic solvent contained in aligning agent for liquid crystal used in the present invention, as long as can uniform dissolution aligning agent for liquid crystal institute
The above-mentioned polymer contained or the solvent of polymerizable compound, there is no particular limitation.If enumerating its concrete example,
In the case of using polyimide precursor or polyimides as polymer, DMF, N, N-diethyl can be enumerated
Base Methanamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam,
2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethylsulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone,
3-methoxyl group-N, N-dimethylpropionamide etc..Additionally, in the case of using polysiloxanes as polymer, such as can enumerate
The polyol compound such as ethylene glycol, 1,2-PD, the amide compound such as N-METHYLFORMAMIDE, DMF etc..
Additionally, in the case of using poly-(methyl) acrylate as polymer, such as alcoholic compound, ketonic compound, acyl can be enumerated
Amines or ester compounds or other aprotic compound etc..These solvents can use a kind or two or more be mixed
Close and use.Even additionally, the solvent of polymer or polymerizable compound can not be dissolved the most equably, as long as at polymer
Or in the range of polymerizable compound do not separates out, it is possible to mix with above-mentioned organic solvent.
The aligning agent for liquid crystal of the present invention is except comprising the organic solvent for the purpose of dissolving polymer or polymerizable compound
Outside, it is also possible to comprise the solvent for the purpose of improving painting film uniformity when aligning agent for liquid crystal is coated substrate.This solvent
Generally use the solvent of low surface tension compared with above-mentioned organic solvent.If enumerating its concrete example, then can enumerate ethyl cellosolve,
Butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-second
Epoxide-2-propanol, 1-butoxy-2-propanol, 1-phenoxy group-2-propanol, single propylene glycol acetate, propylene glycol diacetate, third
Glycol-1-monomethyl ether-2-acetas, propylene glycol-1-list ether-2-acetas, butyl cellosolve acetate, dipropylene glycol, 2-
(2-ethoxy-c epoxide) propanol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..This
A little solvents and can use two or more.
In aligning agent for liquid crystal used in the present invention, in addition to mentioned component, as long as not damaging the effect of the present invention
In the range of, it is also possible to add the polymer beyond above-mentioned polymer, to change dielectric constant or the electric conductivity etc. of liquid crystal orientation film
Electrolyte for the purpose of electrical characteristics or conductive materials, silane coupled for the purpose of improving liquid crystal orientation film and the adaptation of substrate
Agent, to improve the hardness of film when making liquid crystal orientation film or the cross-linked compound for the purpose of consistency and to burn till
The imidizate making polyimide precursor during film carry out efficiently for the purpose of imidizate accelerator etc..
<manufacture of liquid crystal orientation film>
The liquid crystal orientation film that the manufacture method of the present invention is used is to coat on substrate by above-mentioned aligning agent for liquid crystal, according to
Needs burn till after being dried, and carry out the coated surface of gained obtained by orientation process.
As the substrate of coating of liquid crystalline alignment agent, as long as the high substrate of the transparency is then not particularly limited, it is possible to use glass
The plastic bases etc. such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate, from the viewpoint making production technology simplify
Set out, the substrate that be formed with ITO (Indium Tin Oxide) electrode etc. for liquid crystal drive is preferably used.Additionally, reflection
In type liquid crystal display cells, it is possible to use the opaque material such as silicon wafer, but being only limitted to the substrate of side, electrode now is also
The reflectorized materials such as aluminum can be used.As the coating process of the aligning agent for liquid crystal described in the present invention, spin-coating method, printing can be enumerated
Method, ink-jet method etc..
Dry, firing process after coating of liquid crystalline alignment agent may select arbitrary temp and time.Generally, in order to fully remove
The organic solvent contained, preferably preferably makes it be dried 1 minute～10 minutes at 50 DEG C～120 DEG C, the most preferably at 150 DEG C～
5 minutes～120 minutes are preferably burnt till at 300 DEG C.The thickness of the film after burning till is not particularly limited, if but the thinnest, then have
Time liquid crystal display cells reliability can reduce, the most preferably 5～300nm, more preferably 10～200nm.
<orientation process>
Orientation process used in the manufacture method of the present invention, is the orientation process by friction, and by irradiating partially
The what is called of ultraviolet of shaking utilizes the orientation process of optical alignment method.
As the preferred concrete example of the orientation process utilizing optical alignment method, can enumerate to irradiate in above-mentioned film coated surface and contain
Above below the 400nm of wavelength 200nm, the ultraviolet of above below the 350nm of preferred more than 210nm below 380nm, such as 300nm
The ultraviolet to certain orientation polarization, according to circumstances, carry out heat treated with the temperature of 150～250 DEG C further, give liquid
The method of brilliant alignment capability.Additionally, in order to improve liquid crystal aligning, shine while film substrate can be heated at 50～250 DEG C
Penetrate ultraviolet.Aforementioned ultraviolet irradiation amount preferably 1～10000mJ/cm2Scope, particularly preferred 1～2000mJ/cm2Model
Enclose.
Further, the film of above-mentioned illuminated polarized UV rays also can enter with water or the solution containing specific organic solvent subsequently
Row contact processes.To above-mentioned organic solvent, there is no particular limitation, can enumerate water, methanol, ethanol, 2-propanol, acetone, methyl
Ethyl ketone, 1-methoxyl group-2-acetone, 1-methoxy-2-propanol acetas, butyl cellosolve, ethyl lactate, methyl lactate, double
Pyruvic alcohol, 3-methoxy methyl propionate, 3-ethoxyl ethyl propionate, propyl acetate, butyl acetate, and cyclohexyl acetate etc..On
State in solvent, from be readily available anisotropy high, without uneven liquid crystal orientation film in terms of from the point of view of, be preferably selected from 1-methoxyl group-
2-propanol, 1-methoxy-2-propanol acetas, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-methoxy propyl
Acid methyl ester, 3-ethoxyl ethyl propionate, propyl acetate, butyl acetate and at least one of cyclohexyl acetate.Particularly preferably selected from 1-
Methoxy-2-propanol and at least one of ethyl lactate.
The film of illuminated polarized UV rays contacts process preferably by impregnation process, spray with the solution comprising organic solvent
The process that mist process etc. makes film and liquid be fully contacted is carried out.Wherein, preferably film is impregnated in the solution containing organic solvent
Process 10 seconds～1 hour, the method for more preferably 1～30 minute.Contact process can be carried out at normal temperatures can also be under heating
Carry out, implement at preferably 10～80 DEG C, more preferably 20～50 DEG C.Furthermore it is possible to implement the contact-enhancings such as ultrasound wave as required
Method.
After above-mentioned contact processes, in order to remove the organic solvent in used solution, water, methanol, ethanol, 2-can be used
The low boiling point solvents such as propanol, acetone, methyl ethyl ketone carry out the either one or both in washing (flushing) and being dried.As being dried
Time temperature, preferably 80～250 DEG C, more preferably 80～150 DEG C.
The liquid crystal orientation film obtained as mentioned above can make liquid crystal molecule stably be orientated towards certain orientation.
<manufacture method of transverse electric field driving liquid crystal display cells>
Transverse electric field driving liquid crystal display cells manufactured by the manufacture method of the present invention is to obtain above-mentioned band liquid crystal
After the substrate of alignment films, manufacture, by known method, the liquid crystal cell that transverse electric field drives, use this transverse electric field to drive and use
Liquid crystal cell make transverse electric field driving liquid crystal display cells.It addition, transverse electric field type of drive (IPS:In-Plane
Switching) liquid crystal display cells refers to, drives liquid crystal molecule for substrate (transverse direction) in the horizontal direction upper applying electric field
The liquid crystal display cells of mode.
As an example of the manufacture method of transverse electric field driving liquid crystal display cells, with the liquid crystal of passive-matrix structure
Illustrate as a example by showing element.Alternatively, it is also possible to be pie graph as shown in each pixel portion be provided with TFT (thin film transistor (TFT)
(Thin Film Transistor)) etc. the transverse electric field driving liquid crystal display cells of active matrix structure of switch element.
As for manufactured by the present invention the substrate of transverse electric field driving liquid crystal display cells, as long as transparent
High substrate, is not particularly limited, it is common that be formed with the substrate of transparency electrode for driving liquid crystal on substrate.Make
For concrete example, the substrate as substrate described in the manufacture of above-mentioned liquid crystal orientation film can be enumerated.
Additionally, liquid crystal orientation film be coated with above-mentioned aligning agent for liquid crystal on the substrate after burn till, as desired by friction
Process or irradiate the lonizing radiation such as polarized UV rays and formed.Then, with liquid crystal aligning face each other on the substrate of a side
The substrate of mode overlap the opposing party in opposite directions, engages periphery encapsulant.In order to control substrate gap, in encapsulant
Generally it is mixed into sept in advance.It addition, preferably in the face being not provided with encapsulant, part spreads the most in advance for controlling base
The sept of sheet separation.A part at encapsulant pre-sets can be from the peristome of outside filling liquid crystal.
Then, by being arranged at the peristome of encapsulant, note in the space surrounded by two pieces of substrates and encapsulant
Enter liquid crystal material.As liquid crystal material, such as, can enumerate liquid crystal MLC-2041 (Merck joint-stock company (メ ルク Co., Ltd.)
System) etc..Then, this peristome cement is sealed.Injection can use vacuum impregnation, it is possible to use profit in an atmosphere
By the method for capillarity.Thereby make the liquid crystal cell that transverse electric field drives.
Then, the light such as the liquid crystal cell irradiation ultraviolet radiation driven to this transverse electric field.Here, ultraviolet irradiation amount example
As for 1～60J, preferably below 40J, ultraviolet irradiation amount can suppress less because of the destruction of the component of composition liquid crystal display cells
The reliability decrease produced, and reduce ultraviolet irradiation time and can improve manufacture efficiency, thus properly.The ultraviolet irradiated
Wavelength for example, 200nm～400nm.
If to light such as liquid crystal cell irradiation ultraviolet radiations produced above, i.e., liquid crystal orientation film or liquid crystal are irradiated ultraviolet
The light such as line, then the optical polymerism group being positioned on the face connected with liquid crystal orientation film and liquid crystal reacts, and is positioned at liquid crystal aligning
The orientation of the liquid crystal on the surface of film is cured.Thus, shown in embodiment as be described hereinafter, the orientation restraint of liquid crystal is reinforced, its
Result is, has obtained the electrical characteristics improved transverse electric field driving of the ghost phenomena etc. caused by liquid crystal aligning confusion
Use liquid crystal display cells.
Then, the setting of polaroid is carried out.Specifically, viscous on the face of the side contrary with liquid crystal layer of 2 pieces of substrates
Paste a pair polaroid.Through above operation, transverse electric field driving liquid crystal display cells can be obtained.
By the manufacture method of the transverse electric field driving liquid crystal display cells of the present invention as above manufacture horizontal
Electric field driven liquid crystal display cells, due to the element that the orientation restraint being liquid crystal is strong, inhibit ghost to produce, therefore can be very
Well for big picture and the LCD TV etc. of high-resolution.
Embodiment
Hereinafter, the present invention will be described in more detail to enumerate embodiment, but the present invention is not limited to this.
<preparation of aligning agent for liquid crystal>
The abbreviation used in the preparation of following aligning agent for liquid crystal is as follows.
(tetracarboxylic dianhydride)
BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
CBDA:1,2,3,4-Tetramethylene. tetracarboxylic dianhydride
(diamidogen)
P-PDA: p-phenylenediamine
DA-1: (E)-2,4 diaminobenzene ethyl 3-(4-cyclohexyl phenyl) acrylate represented by following formula
[changing 35]
DA-2: the diamine compound represented by following formula
[changing 36]
DA-3: the diamine compound represented by following formula
[changing 37]
BEM-S: 2-(methacryloxy) the ethyl 3,5-diaminobenzoic acid ester represented by following formula
[changing 38]
(methacrylic acid monomer)
MA1: the methacrylic acid monomer represented by following formula
[changing 39]
MA1 synthesizes with the synthetic method described in Japanese Patent Laid-Open 2010-18807 publication.
(radical polymerization initiator)
AIBN:2,2 '-azodiisobutyronitrile
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N
BCS: butyl cellosolve
(polymerizable compound)
RM1: 5,5 ' (4,4 '-(double phenyl-4,4 '-diyl double (epoxide)) double (butane-4,1-two represented by following formula
Base)) double (3-methylene dihydrofuran-2 (3H)-one)
[changing 40]
RM2: the polymerizable compound represented by following formula
[changing 41]
RM3: the polymerizable compound represented by following formula
[changing 42]
Additionally, the molecule measuring fixed condition of polymer (polyamic acid, polyimides) is as follows.
Device: room temperature gel permeation chromatography (GPC) dress that Sen Xiu science Co., Ltd. (セ Application シ ュ science society) makes
Put (SSC-7200),
Post: the post (KD803, KD805) that Showa Denko K. K (Shodex society) makes
Column temperature: 50 DEG C
Eluent: N, N'-dimethylformamide is (as additive, lithium bromide hydrate (LiBr H2O) it is 30 mmoles
You/liter, phosphoric anhydride crystallization (orthophosphoric acid) be 30 mM/ls, oxolane (THF) be 10 ml l)
Flow velocity: 1.0 ml/min
Calibration trace making standard specimen: (molecular weight is about for Dong Cao company (ソ society) TSK processed standard poly(ethylene oxide)
Be 900000,150000,100000,30000) and Polymer Laboratory company (Port リ マ ラ ボ ラ ト リ society) make poly-second two
Alcohol (molecular weight is about 12000,4000,1000).
(synthesis example 1)
In DA-1 (5.10g, 14.0 mMs), add NMP (22.0g), be stirred at room temperature after making it be completely dissolved,
Adding CBDA (2.66g, 13.6 mMs) and NMP (22.0g), at room temperature reaction obtains polyamic acid solution in 10 hours.?
This polyamic acid solution (40g) adds NMP (40.0g) and BCS (20.0g), obtains liquid by being stirred at room temperature 5 hours
Brilliant alignment agent (A1).The number-average molecular weight of this polyamic acid is 6500, and weight average molecular weight is 26000.
Additionally, it (is 10 matter relative to solid composition that the above-mentioned aligning agent for liquid crystal (A1) relative to 10.0g adds 60mg
Amount %) polymerizable compound RM1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (A2).
(synthesis example 2)
NMP (20.8g) is added, in room in DA-1 (3.57g, 9.8 mMs) and BEM-S (1.11g, 4.2 mMs)
After the lower stirring of temperature makes it be completely dissolved, add CBDA (2.66g, 13.6 mMs) and NMP (20.8g), at room temperature react 10
Hour obtain polyamic acid solution.In this polyamic acid solution (40g), add NMP (40.0g) and BCS (20.0g), pass through
It is stirred at room temperature 5 hours and obtains aligning agent for liquid crystal (B1).The number-average molecular weight of this polyamic acid is 7500, and weight average molecular weight is
25000。
Additionally, it (is 10 matter relative to solid composition that the above-mentioned aligning agent for liquid crystal (B1) relative to 10.0g adds 60mg
Amount %) polymerizable compound RM1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (B2).
<making 1 of liquid crystal cell>
(comparative example 1)
Use the aligning agent for liquid crystal (A2) obtained in synthesis example 1, carry out the system of liquid crystal cell according to step as follows
Make.Substrate is 30mm × 40mm size, the glass substrate of thickness 0.7mm, use be configured with by ito film patterning and formed,
The substrate of comb-shaped pixel electrode.Pixel electrode has arrangement multiple middle bodies bending, the electrode member of " く " word shape
And the comb-shaped shape constituted.The short side direction width of each electrode member is 3 μm, is spaced apart 6 μm between electrode member.Formed
The pixel electrode of each pixel is made up of arrange the bending of multiple middle body, the electrode member of " く " word shape, so each pixel
Shape be not oblong-shaped, but have the bending of in the same manner as electrode member middle body, as the shape of thick " く " word.
Then, each pixel is split with the sweep of its central authorities up and down for boundary, has the 1st region and downside of the upside of sweep
The 2nd region.When 1st region of each pixel and the 2nd region are compared, find to constitute the electrode unit of their pixel electrode
The formation direction of part is different.I.e., using the orientation process direction of liquid crystal orientation film described later as in the case of benchmark, pixel
The 1st region in, the electrode member of pixel electrode is formed in the way of in the angle (clockwise) of+10 °, the 2nd of pixel
In region, the electrode member of pixel electrode is formed in the way of in the angle (clockwise) of-10 °.I.e., the 1st of each pixel
In region and the 2nd region, the liquid crystal evoked to be applied by the voltage between pixel electrode and opposite electrode is in real estate
The mode that direction is opposite directions of spinning movement (in-plane changes) is constituted.The liquid crystal aligning that synthesis example 1 is obtained
Agent (A2) is spun on ready above-mentioned electroded substrate.Then, after the hot plate of 90 DEG C is dried 60 seconds, at 200 DEG C
Burn till in heated air circulation type stove 30 minutes, form the liquid crystal orientation film of thickness 100nm.Then, shine to coated surface across polarization plates
Penetrate the ultraviolet 20mJ/cm of 313nm2, obtain the substrate of band liquid crystal orientation film.Additionally, being formed without as substrate in opposite directions
Also aligning agent for liquid crystal (A2) is used to be similarly formed film on the glass substrate with the column spacer that height is 4 μm of electrode,
Implement orientation process.(Xie Li KCC (vertical chemistry) system of printing and sealing agent on the liquid crystal orientation film of side substrate
XN-1500T).Then, by the substrate of opposite side so that the condition that relative orientation direction is 0 ° of liquid crystal orientation film is fitted
After, curing sealant, prepare negative crystal born of the same parents.This negative crystal born of the same parents utilize decompression injection method inject liquid crystal MLC-2041, and (Merck share is public
Department's system), seal inlet, (transverse electric field drives to obtain possessing IPS (In-Plane Switching) mode liquid crystal display element
The liquid crystal display cells of mode) liquid crystal cell of structure.
(embodiment 1)
For carrying out, with comparative example 1, the liquid crystal cell that identical operation manufactures, irradiate 365nm's from the outside of liquid crystal cell
Ultraviolet 20J/cm2(irradiating for 2 times), obtains the liquid crystal cell of embodiment 1.
(comparative example 2)
In addition to using aligning agent for liquid crystal (B2) to replace aligning agent for liquid crystal (A2), carry out the operation identical with comparative example 1,
Obtain the liquid crystal cell of comparative example 2.
(embodiment 2)
For carrying out, with comparative example 2, the liquid crystal cell that identical operation manufactures, irradiate 365nm's from the outside of liquid crystal cell
Ultraviolet 20J/cm2(irradiating for 2 times), obtains the liquid crystal cell of embodiment 2.
(comparative example 3)
In addition to using aligning agent for liquid crystal (A1) to replace aligning agent for liquid crystal (A2), carry out the operation identical with comparative example 1,
Obtain the liquid crystal cell of comparative example 3.
(ghost evaluates 1)
By each embodiment 1～2 and the IPS pattern liquid crystal cell that prepared of comparative example 1～3 be arranged on polarizing axis orthogonal
Two pieces of Polarizers configuring of mode between, make backlight luminous when no applied voltage, so that the brightness of transmission light
The condition minimized have adjusted the arrangement angles of liquid crystal cell.Then, the darkest angle being reached from the 2nd region of pixel
Anglec of rotation when making liquid crystal cell rotate reaching the darkest angle to the 1st region calculates as initial stage orientation azimuth.
Then, under room temperature environment, the 8V of 24 hours is applied with frequency 30HzPPAlternating voltage.Then, the pixel electricity of liquid crystal cell is made
It is in short-circuit condition between pole and opposite electrode, places 1 hour in room temperature in this condition.After placement, measure in the same manner
Orientation azimuth, the azimuthal difference of orientation before and after exchange being driven calculates as angle delta (deg.).
[table 1]
This result is as shown in table 1, has irradiated the embodiment 1 and 2 of UV after adding polymerizable compound or liquid crystal cell manufacture,
With do not add polymerizable compound, do not have UV to irradiate the comparative example 3 of (2 times irradiate) or brilliant at liquid crystal after liquid crystal cell makes
The comparative example 1 that born of the same parents do not have UV to irradiate after making is compared with 2, and the azimuthal difference of orientation before and after exchange drives is the least.But, can
To think that the orientation restraint of embodiment 1 and 2 is strong, ghost characteristic is the most excellent.This pass through after being considered liquid crystal cell manufacture into
Row irradiates from outside UV, and the photopolymerizable compound that with the addition of forms polymer layer at alignment layer surface, thereby makes orientation solid
The reason changed.Further, since embodiment 1 exchange with both embodiments 2 the azimuthal difference of orientation before and after driving be all zero and
It is difficult to compare, but the orientation before and after comparative example 2 exchange using the polymer having imported the BEM-S with optical polymerism drives
Azimuthal difference is less than comparative example 1 be can confirm that, the polymer having been imported the BEM-S with optical polymerism by use can be further
Improve ghost characteristic.
(synthesis example 3)
CBDA (1.94g, 10.0 mMs), DA-2 (4.49g, 10.0 mMs) are mixed in NMP (25.7g),
Under room temperature, reaction obtains polyamic acid solution in 10 hours.This polyamic acid solution (32.1g) adds NMP (32.1g) and
BCS (42.9g) after being diluted to 6 weight %, obtains aligning agent for liquid crystal (C) by being stirred at room temperature 10 hours.This polyamide
The number-average molecular weight of acid is 13000, and weight average molecular weight is 19000.
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (C) of 10.0g
Property compound R M1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (C1).
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (C) of 10.0g
Property compound R M2, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (C2).
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (C) of 10.0g
Property compound R M3, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (C3).
(synthesis example 4)
BODA (2.50g, 10.0 mMs), DA-3 (9.65g, 20.0 mMs) are mixed in NMP (42.3g), with
After 80 DEG C are reacted 5 hours, add CBDA (1.92g, 10.0 mMs) and NMP (14.1g), within 10 hours, gathered with 40 DEG C of reactions
Amic acid solution.In this polyamic acid solution (70.4g), add NMP (70.4g) and BCS (93.8g) and be diluted to 6 weights
After amount %, obtain aligning agent for liquid crystal (D) by being stirred at room temperature 10 hours.The number-average molecular weight of this polyamic acid is 12000,
Weight average molecular weight is 21000.
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (D) of 10.0g
Property compound R M1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (D1).
(synthesis example 5)
By CBDA (1.92g, 10.0 mMs), p-PDA (0.54g, 5.0 mMs), DA-2 (2.24g, 5.0 mMs)
Mixing in NMP (18.9g), at room temperature reaction obtains polyamic acid solution in 10 hours.At this polyamic acid solution (23.6g)
Middle addition NMP (23.6g) and BCS (31.5g) after being diluted to 6 weight %, obtain liquid crystal by being stirred at room temperature 10 hours
Alignment agent (E).The number-average molecular weight of this polyamic acid is 19000, and weight average molecular weight is 28000.
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (E) of 10.0g
Property compound R M1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (E1).
(synthesis example 6)
MA1 (5.54g, 16.0 mMs) is dissolved in NMP (51.1g), after carrying out degassing in 6 minutes with membrane pump, adds
Enter AIBN (0.131g, 0.8 mM) and again carry out degassing in 6 minutes.React 20 hours with 65 DEG C afterwards, obtain methacrylic acid
Ester polymer solution.In this polymer solution, add BCS (37.8g) and be diluted to 6 mass %, by being stirred at room temperature 5
Hour obtain aligning agent for liquid crystal (F).The number-average molecular weight of this polymer is 16000, and weight average molecular weight is 39000.
Additionally, add the polymerization of 30mg (being 5 mass % relative to solid composition) in the aligning agent for liquid crystal (F) of 10.0g
Property compound R M1, at room temperature 3 the times stirring make it dissolve, prepare aligning agent for liquid crystal (F1).
<making 2 of liquid crystal cell>
(embodiment 3)
Use the aligning agent for liquid crystal (C1) obtained in synthesis example 3, carry out the system of liquid crystal cell according to step as follows
Make.Substrate is 30mm × 40mm size, the glass substrate of thickness 0.7mm, use be configured with by ito film patterning and formed,
The substrate of comb-shaped pixel electrode.Pixel electrode has arrangement multiple middle bodies bending, the electrode member of " く " word shape
And the comb-shaped shape constituted.The short side direction width of each electrode member is 10 μm, is spaced apart 20 μm between electrode member.Shape
The pixel electrode becoming each pixel is made up of arrange the bending of multiple middle body, the electrode member of " く " word shape, so each picture
The shape of element is not oblong-shaped, but has that middle body in the same manner as electrode member bends, as the shape of thick " く " word
Shape.Then, each pixel is split with the sweep of its central authorities up and down for boundary, have sweep upside the 1st region and
2nd region of downside.When 1st region of each pixel and the 2nd region are compared, find to constitute the electricity of their pixel electrode
The formation direction of pole element is different.I.e., using the orientation process direction of liquid crystal orientation film described later as in the case of benchmark,
In 1st region of pixel, the electrode member of pixel electrode is formed in the way of in the angle (clockwise) of+15 °, pixel
In 2nd region, the electrode member of pixel electrode is formed in the way of in the angle (clockwise) of-15 °.I.e., each pixel
In 1st region and the 2nd region, the liquid crystal evoked to be applied by the voltage between pixel electrode and opposite electrode is in real estate
The mode that direction is opposite directions of spinning movement (in-plane changes) constitute.The liquid crystal that synthesis example 3 obtains is taken
It is spun on ready above-mentioned electroded substrate to agent (C1).Then, after the hot plate of 80 DEG C is dried 90 seconds, at 160 DEG C
Heated air circulation type stove in burn till 30 minutes, formed thickness 100nm liquid crystal orientation film.Then, across polarization plates to coated surface
Irradiate polarized UV rays 50mJ/cm of 313nm2(irradiating for 1 time), obtains the substrate of band liquid crystal orientation film.Additionally, as in opposite directions
Substrate be formed without electrode have height be 4 μm column spacer glass substrate on also use aligning agent for liquid crystal (C1)
It is similarly formed film, implements orientation process.Printing and sealing agent (Xie Li KCC on the liquid crystal orientation film of side substrate
XN-1500T processed).Then, by the substrate of opposite side so that the condition that relative orientation direction is 0 ° of liquid crystal orientation film is fitted
After, curing sealant, prepare negative crystal born of the same parents.This negative crystal born of the same parents utilize decompression injection method inject liquid crystal MLC-2041, and (Merck share is public
Department's system), seal inlet, (transverse electric field drives to obtain possessing IPS (In-Plane Switching) mode liquid crystal display element
The liquid crystal display cells of mode) liquid crystal cell of structure.
After manufacturing liquid crystal cell, the reorientation carried out 60 minutes with the baking ovens of 120 DEG C processes.Afterwards, liquid crystal cell is made
It is in short-circuit condition between pixel electrode and opposite electrode, irradiates the ultraviolet by 365nm band filter to liquid crystal cell
20J/cm2(irradiating for 2 times).
(ghost evaluates 2)
IPS pattern liquid crystal cell embodiment 3 prepared is arranged on two pieces configured in the way of polarizing axis is orthogonal
Between Polarizer, make backlight luminous when no applied voltage, so that the condition that the brightness of transmission light minimizes is adjusted
The whole arrangement angles of liquid crystal cell.Then, play the 1st region reach reaching the darkest angle from the 2nd region of pixel
Anglec of rotation when making liquid crystal cell rotate till dark angle calculates as initial stage orientation azimuth.Then, at 60 DEG C of baking ovens
In, the 16V of 168 hours is applied with frequency 30HzPPAlternating voltage.Then, pixel electrode and the opposite electrode of liquid crystal cell are made
Between be in short-circuit condition, in this condition in room temperature place 1 hour.After placement, measure orientation azimuth in the same manner, will
The azimuthal difference of orientation before and after exchange drives calculates as angle delta (deg.).Ghost evaluation result is shown in table 2.
(embodiment 4)
In addition to using aligning agent for liquid crystal (C2) to replace aligning agent for liquid crystal (C1), with step system same as in Example 3
After making liquid crystal cell, carry out ghost evaluation.
(embodiment 5)
In addition to using aligning agent for liquid crystal (C3) to replace aligning agent for liquid crystal (C1), with step system same as in Example 3
After making liquid crystal cell, carry out ghost evaluation.
(embodiment 6)
Except using aligning agent for liquid crystal (D1) to replace aligning agent for liquid crystal (C1), the irradiation dose of polarized UV rays is set to
500mJ/cm2In addition, after manufacturing liquid crystal cell with step same as in Example 3, ghost evaluation is carried out.
(embodiment 7)
In addition to using aligning agent for liquid crystal (E1) to replace aligning agent for liquid crystal (C1), with step system same as in Example 3
After making liquid crystal cell, carry out ghost evaluation.
(embodiment 8)
Except using aligning agent for liquid crystal (F1) to replace aligning agent for liquid crystal (C1), the irradiation dose of polarized UV rays is set to
500mJ/cm2In addition, after manufacturing liquid crystal cell with step same as in Example 3, ghost evaluation is carried out.
(embodiment 9)
In addition to using aligning agent for liquid crystal (C) to replace aligning agent for liquid crystal (C1), with step manufacture same as in Example 3
After liquid crystal cell, carry out ghost evaluation.
(comparative example 4)
Except use aligning agent for liquid crystal (C) replace aligning agent for liquid crystal (C1), do not carry out 2 times irradiate beyond, with embodiment 3
After identical step manufactures liquid crystal cell, carry out ghost evaluation.
(comparative example 5)
Except using aligning agent for liquid crystal (D) to replace aligning agent for liquid crystal (C1), the irradiation dose of polarized UV rays is set to
500mJ/cm2, do not carry out, beyond 2 irradiations, after manufacturing liquid crystal cell with step same as in Example 3, carrying out ghost evaluation.
(comparative example 6)
Except use aligning agent for liquid crystal (E) replace aligning agent for liquid crystal (C1), do not carry out 2 times irradiate beyond, with embodiment 3
After identical step manufactures liquid crystal cell, carry out ghost evaluation.
(comparative example 7)
Except using aligning agent for liquid crystal (F) to replace aligning agent for liquid crystal (C1), the irradiation dose of polarized UV rays is set to
500mJ/cm2, do not carry out, beyond 2 irradiations, after manufacturing liquid crystal cell with step same as in Example 3, carrying out ghost evaluation.
[table 2]
By the results verification of table 2, do not add any one in the comparative example 4～7 of polymerizable compound after AC drives
Orientation azimuth is significantly deviateed, but with the addition of polymerizable compound and carry out UV irradiation (2 photographs after liquid crystal cell manufacture
Penetrate) though embodiment 3～8 AC drive after compared with comparative example 4～7, its orientation azimuth also almost without deviation.This
Outward, it is known that containing there is on side chain the polymer of optical polymerism group and carrying out UV irradiation (2 times after liquid crystal cell manufacture
Irradiate) embodiment 9 with do not carry out 2 times irradiate comparative example 4 compared with, be orientated azimuthal deviation little.Its reason speculates such as
Under: embodiment 3～9 occurs by being radiated at the optical polymerism group of polymerizable compound or polymer on alignment films interface for 2 times
Polymerization, by liquid crystal orientation film surface cure, is therefore orientated azimuthal deviation the least.
Claims (11)
1. the manufacture method of a transverse electric field driving liquid crystal display cells, it is characterised in that be included in coating fluid on substrate
After brilliant alignment agent forms liquid crystal orientation film and implements orientation process, a pair substrate of this liquid crystal orientation film will be defined via liquid crystal
According to making, the condition that described liquid crystal orientation film is relative is oppositely disposed, makes liquid crystal cell, then this liquid crystal cell is carried out illumination
Penetrate, make the described optical polymerism base of the polymerizable compound with optical polymerism group in liquid crystal and/or in liquid crystal orientation film
Group carries out the operation reacted,
Described polymerizable compound is lower formula (I), lower formula (II) or the compound represented by lower formula (III),
In formula (I)～(III), R12For H or the alkyl of carbon number 1～4, Z1For can be by the alkyl of carbon number 1～12 or carbon number 1～12
Alkoxyl substituted bivalence aromatic ring or heterocycle, Z2For can be replaced by the alkoxyl of the alkyl of carbon number 1～12 or carbon number 1～12
Monovalence aromatic ring or heterocycle, Q1For divalent organic group.
2. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described liquid
Brilliant containing the polymerizable compound with described optical polymerism group.
3. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1 or 2, it is characterised in that institute
State aligning agent for liquid crystal and contain described optical polymerism group.
4. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described liquid
Brilliant alignment agent contains the polymer on side chain with described optical polymerism group.
5. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described liquid
Brilliant alignment agent contains the polymerizable compound with described optical polymerism group.
6. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 3, it is characterised in that described light
Polymerizable group is the group in optical polymerism group shown below；
In formula, Me represents methyl.
7. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described in take
Carried out by the irradiation of polarized UV rays to processing.
8. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described in take
In processing, there is the photoreactive group selected from following formula (A-1)～the structure of (A-7) and react,
9. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described liquid
The polymer that brilliant alignment agent is comprised contains selected from polyimide precursor with by least 1 of polyimides obtained by its imidizate
Kind.
10. the manufacture method of transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described
Polymer contained by aligning agent for liquid crystal comprises polysiloxanes.
The manufacture method of 11. transverse electric field driving liquid crystal display cells as claimed in claim 1, it is characterised in that described
Polymer contained by aligning agent for liquid crystal comprises poly-(methyl) acrylate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-281552 | 2011-12-22 | ||
| JP2011281552 | 2011-12-22 | ||
| PCT/JP2012/083259 WO2013094734A1 (en) | 2011-12-22 | 2012-12-21 | Method for manufacturing liquid-crystal display element for use with in-plane switching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104136976A CN104136976A (en) | 2014-11-05 |
| CN104136976B true CN104136976B (en) | 2016-11-30 |
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