CN104136976A - Method for manufacturing liquid-crystal display element for use with in-plane switching - Google Patents

Method for manufacturing liquid-crystal display element for use with in-plane switching Download PDF

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Publication number
CN104136976A
CN104136976A CN201280070337.9A CN201280070337A CN104136976A CN 104136976 A CN104136976 A CN 104136976A CN 201280070337 A CN201280070337 A CN 201280070337A CN 104136976 A CN104136976 A CN 104136976A
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Prior art keywords
liquid crystal
aligning agent
crystal display
display cells
electric field
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CN201280070337.9A
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CN104136976B (en
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万代淳彦
芦泽亮一
山之内洋一
南悟志
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

Abstract

A method for manufacturing an in-plane switching liquid-crystal display element, said method being characterized by including a step wherein, after an alignment process in which a liquid-crystal aligning agent is applied to substrates to form liquid-crystal alignment films, liquid-crystal cells are created by arranging a pair of substrates with the aforementioned liquid-crystal alignment films formed thereon opposite each other such that said liquid-crystal alignment films face each other with liquid crystal interposed therebetween, and said liquid-crystal cells are then exposed to light, causing photopolymerizable groups in the liquid crystal and/or in the liquid-crystal alignment films to react.

Description

Transverse electric field drives the manufacture method with liquid crystal display cells
Technical field
The present invention relates to transverse electric field and drive the manufacture method with liquid crystal display cells.
Background technology
Liquid crystal display cells for LCD TV, liquid crystal display etc. is provided with conventionally for controlling the liquid crystal orientation film of the state of orientation of liquid crystal in element.
At present, according to the most general industrial method, this liquid crystal orientation film be by with the cloth such as cotton, nylon, polyester towards a direction wiping be formed on electrode base board by polyamic acid and/or by its imidizate the film surface that forms of polyimide, be that so-called friction treatment is made.
In the orientation process of liquid crystal orientation film, the method for face being carried out to friction treatment is easy and the industrial useful method of highly productive.But, requirement to the high performance of liquid crystal display cells, high-definition, maximization improves day by day, and impact and then the variety of issues such as unevenness in orientation process face of damage, airborne dust, mechanical force or the static on the liquid crystal orientation film surface being caused by friction treatment are day by day obvious.
The method of friction treatment instead, knownly gives the optical alignment method of liquid crystal aligning ability by irradiating polarized UV rays.Liquid crystal aligning based on optical alignment method is processed, according to mechanism, proposed processing, the processing that utilizes photodimerization that utilizes photoisomerization to react, (with reference to the non-patent literatures 1) such as processing that utilizes photolysis reactions.
For example, in patent documentation 1, proposed that the method for the polyimide film of the alicyclic structures such as cyclo-butane ring for optical alignment method will be there is on main chain.In the situation that use has adopted the polyimide film of this optical alignment method as liquid crystal orientation film, compare and there is high-fire resistance with additive method, therefore can expect its serviceability.
The polyimide film with alicyclic structures such as cyclo-butane rings like this, by irradiating near short wavelength's the polarized UV rays of ultraviolet ray, especially 254nm, presents high anisotropy, obtains the good liquid crystal orientation film of liquid crystal aligning.But, because near ultraviolet energy 254nm is high, irradiate and need a large amount of electric power, not only high for the cost of light orientation process, also large to the load of environment.In addition,, in order to use the short wavelength's that energy is stronger ultraviolet ray, think also to have to the electrode forming on substrate or thin film transistor (TFT) (being also denoted as below TFT) and bring the possibility of damage.
On the other hand, utilize the optical alignment method of photoisomerization or photodimerization can pass through polarized UV rays more than illumination wavelength 300nm, give anisotropy.But, a little less than utilizing the orientation limitations power of the resulting liquid crystal orientation film of optical alignment method of photoisomerization or photodimerization, for liquid crystal display cells in the situation that, have the problem that produces ghost.
Here, the known liquid crystal display cells that drives the transverse electric field type of drive (IPS:In-Plane Switching) of liquid crystal molecule to applying electric field on substrate (laterally) in the horizontal direction.The liquid crystal display cells of this transverse electric field type of drive is because visual angle is wide and useful, but owing to being easily subject to the impact of the state of orientation of liquid crystal, has the problem that especially easily produces ghost as above.
Prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-297313 communique
Non-patent literature
Non-patent literature 1: " liquid crystal photo-alignment film " wooden family rib, city village functional material in November, 1997 Vol.17 No.1113-22 page
Summary of the invention
Invent technical matters to be solved
The object of the present invention is to provide a kind of orientation limitations power of strengthening liquid crystal and drive the manufacture method with liquid crystal display cells, suppress the transverse electric field of the generation of ghost.
The technical scheme that technical solution problem adopts
Present inventor to achieve these goals, finds while conscientiously studying, by the following method and transverse electric field drive the liquid crystal display cells of use can realize above-mentioned purpose, thereby completed the present invention; The method is to use the liquid crystal that has added the polymerizable compound with optical polymerism group, or use by have optical polymerism group aligning agent for liquid crystal and liquid crystal orientation film, utilize friction or optical alignment method implementation orientation to process, make after liquid crystal structure cell, by irradiating light, the optical polymerism group that is present in liquid crystal orientation film and liquid crystal contact portion is reacted, by this by the curing method of the liquid crystal of the part contacting with liquid crystal orientation film.In sum, technology contents of the present invention is as described below.
1. a transverse electric field drives the manufacture method with liquid crystal display cells, it is characterized in that, being included in coating of liquid crystalline alignment agent on substrate forms after liquid crystal orientation film implementation orientation processing, Jie by liquid crystal by a pair of substrate that has formed this liquid crystal orientation film according to the condition subtend that described liquid crystal orientation film is relative is configured, make liquid crystal structure cell, then this liquid crystal structure cell is carried out to irradiation, the operation that the optical polymerism group in liquid crystal and/or in liquid crystal orientation film is reacted.
2. the transverse electric field as described in 1 drives the manufacture method with liquid crystal display cells, it is characterized in that, described liquid crystal contains the polymerizable compound with described optical polymerism group.
3. the transverse electric field as described in 1 or 2 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains described optical polymerism group.
4. the transverse electric field as described in any one in 1～3 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains the polymkeric substance on side chain with described optical polymerism group.
5. the transverse electric field as described in any one in 1～4 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains the polymerizable compound with described optical polymerism group.
6. the transverse electric field as described in any one in 3～5 drives the manufacture method with liquid crystal display cells, it is characterized in that, described optical polymerism group is the group being selected from optical polymerism group shown below.
[changing 1]
(in formula, Me represents methyl.)
7. the transverse electric field as described in any one in 1～6 drives the manufacture method with liquid crystal display cells, it is characterized in that, described orientation process is undertaken by the irradiation of polarized UV rays.
8. the transverse electric field as described in any one in 1～7 drives the manufacture method with liquid crystal display cells, it is characterized in that, in described orientation process, the photoreactive group with the structure that is selected from following formula (A-1)～(A-7) reacts.
[changing 2]
9. the transverse electric field as described in any one in 1～8 drives the manufacture method with liquid crystal display cells, it is characterized in that, the contained polymkeric substance of described aligning agent for liquid crystal comprise be selected from polyimide precursor and by its imidizate and at least a kind of polyimide.
10. the transverse electric field as described in any one in 1～9 drives the manufacture method with liquid crystal display cells, it is characterized in that, the contained polymkeric substance of described aligning agent for liquid crystal comprises polysiloxane.
11. transverse electric fields as described in any one in 1～10 drive the manufacture method with liquid crystal display cells, it is characterized in that, the contained polymkeric substance of described aligning agent for liquid crystal comprises poly-(methyl) acrylate.
The effect of invention
If employing the present invention, can obtain possessing by friction or optical alignment method implementation orientation and process, particularly by light, be orientated the liquid crystal orientation film that implementation orientation is processed, can strengthen the orientation limitations power of liquid crystal, the transverse electric field of the generation of inhibition ghost drives the liquid crystal display cells of use.
Embodiment
The present invention is that a kind of transverse electric field drives the manufacture method with liquid crystal display cells, it is characterized in that, being included in coating of liquid crystalline alignment agent on substrate forms after liquid crystal orientation film implementation orientation processing, Jie by liquid crystal by a pair of substrate that has formed this liquid crystal orientation film according to the condition subtend that above-mentioned liquid crystal orientation film is relative is configured, make liquid crystal structure cell, then this liquid crystal structure cell is carried out to irradiation, the operation that the optical polymerism group in liquid crystal and/or in liquid crystal orientation film is reacted.Below, respectively constitutive requirements are described in detail.
< optical polymerism group G reatT.GreaT.GT
The aligning agent for liquid crystal that manufacture method of the present invention is used and/or liquid crystal contain optical polymerism group.The liquid crystal that contains optical polymerism group is to obtain by add the compound (below also referred to as polymerizable compound) that contains optical polymerism group in liquid crystal.In addition, for the aligning agent for liquid crystal that obtains containing optical polymerism group, can in aligning agent for liquid crystal, add polymerizable compound, also can be on the side chain of the contained polymkeric substance of aligning agent for liquid crystal lead-in light polymerizable group, can be also the two.The liquid crystal orientation film that uses such aligning agent for liquid crystal and obtain contains optical polymerism group.The in the situation that of adding polymerizable compound in liquid crystal, its adding proportion, with respect to liquid crystal, for example can make polymerizable compound is 0.1～30 (quality) %.In addition, the in the situation that of adding polymerizable compound in aligning agent for liquid crystal, its adding proportion, with respect to aligning agent for liquid crystal, for example can make polymerizable compound is 0.1～30 (quality) %.
If to the light such as liquid crystal display cells irradiation ultraviolet radiation that contain optical polymerism group in liquid crystal orientation film and/or in liquid crystal, the optical polymerism group that is positioned at the face contacting with liquid crystal with liquid crystal orientation film reacts, and the orientation that is positioned at the surperficial liquid crystal of liquid crystal orientation film is cured.Thus, shown in embodiment, when obtaining good liquid crystal aligning, strengthen the orientation limitations power of liquid crystal as described later, consequently, the electrical characteristics of the ghost phenomena being caused by liquid crystal aligning confusion etc. are improved.
Optical polymerism group is by the group of the light polymerization reaction take places such as ultraviolet ray, for example, so long as carry out the group (below also referred to as photopolymerisable group) of polymerization or the group of the photo-crosslinking group of photo-crosslinking (below also referred to as) by light such as ultraviolet rays, be not particularly limited, but preferably use structure shown below.
[changing 3]
(in formula, Me represents methyl.)
Concrete example as polymerizable compound, can exemplify the compound that 2 represented ends of following formula (I) have respectively photopolymerisable group, represented the comprising of following formula (II) has the end of photopolymerisable group and has the compound of end of the group of photo-crosslinking, and 2 represented ends of following formula (III) have respectively the compound of the group of photo-crosslinking.In addition, in following formula (I)～(III), R 12for the alkyl of H or carbon number 1～4, Z 1for divalence aromatic ring or the heterocycle that can be replaced by the alkoxy of the alkyl of carbon number 1～12 or carbon number 1～12, Z 2for monovalence aromatic ring or the heterocycle that can be replaced by the alkoxy of the alkyl of carbon number 1～12 or carbon number 1～12, Q 1for divalent organic group.Q 1preferably there is phenylene (C 6h 4-), biphenylene (C 6h 4-C 6h 4-) or cyclohexylidene (C 6h 10-) etc. ring structure.This is because easily increase with the interaction of liquid crystal.
[changing 4]
[changing 5]
As the concrete example of the represented polymerizable compound of formula (I), can exemplify the represented polymerizable compound of following formula (I-1)～(I-5).In following formula, V is singly-bound or with-R 1o-represents, R wherein 1for the alkylidene of the carbon number 1～10 of straight or branched, preferably with-R 1o-represents, R wherein 1alkylidene for the carbon number 2～6 of straight or branched.In addition, W is singly-bound or with-OR 2-represent, R wherein 2for the alkylidene of the carbon number 1～10 of straight or branched, preferably with-OR 2-represent, R wherein 2alkylidene for the carbon number 2～6 of straight or branched.In addition, V and W can be also different structures for identical structure, if the same easily synthetic.
[changing 7]
In addition, even the group as photopolymerisable group or photo-crosslinking does not have alpha-methylene-gamma-butyrolactone base and has acrylate-based or methacrylate based polymerizable compound, so long as there is this acrylate-based or methacrylate based Jie by the polymerizable compound of the oxyalkylene group structure that uniformly-spaced group is combined with phenylene, identical with the above-mentioned polymerizable compound respectively on two ends with alpha-methylene-gamma-butyrolactone base, can make AC stress ghost characteristic significantly improve, , can significantly suppress the ghost producing that applies because of alternating current (AC).In addition, if there is acrylate-based or methacrylate based Jie by the polymerizable compound of the oxyalkylene group structure that uniformly-spaced group is combined with phenylene, may be owing to having improved hot stability, thus fully withstand high temperatures as 200 ℃ of above firing temperatures.
In addition,, as the concrete example of the represented polymerizable compound of formula (I), also can exemplify the polymerizable compound of following formula.
[changing 8]
(in formula, R 12, V, W definition same as described above.)
The manufacture method of this polymerizable compound is not particularly limited, for example, can manufacture according to synthesis example described later.For example, the represented polymerizable compound of above formula (I-1) can be by being combined the technology in Synthetic Organic Chemistry to synthesize.For example, can be by the P.Talaga such as tower glug (Talaga) that represent with following reaction equation, M.Schaeffer, C.Benezra and J.L.Stampf are at Synthesis (< < synthesizes > > magazine), the method proposing in 530 (1990), is used SnCl 2make 2-(bromomethyl) acrylic acid (2-(bromomethyl) propenoic acid) react to synthesize with aldehydes or ketones.In addition, Amberlyst15 is the strong-acid ion exchange resin of Rhom and Hass (ロ ー system ア Application De ハー ス society) system, and THF is tetrahydrofuran.
[changing 9]
(in formula, R ' represents any monovalent organic radical group.)
In addition, 2-(bromomethyl) acrylic acid can be by the K.Ramarajan such as La Malaen (Ramarajan) that represent with following reaction equation, K.Kamalingam, D.J.O'Donnell and K.D.Berlin are at OrganicSynthesis (< < organic synthesis > > magazine), vol.61, the method proposing in 56-59 (1983) is synthesized.
[changing 10]
As concrete synthesis example, at synthetic V, be-R 1o-, W is-OR 2-, R 1and R 2in the situation of the polymerizable compound that identical above formula (I-1) is represented, can exemplify 2 represented methods of following reaction equation.
[changing 11]
[changing 12]
In addition, at synthetic R 1and R 2in the situation of the polymerizable compound that different above formula (1) is represented, can exemplify the represented method of following reaction equation.
[changing 13]
In addition, in the situation that the represented polymerizable compound of above formula (I-1) that synthetic V and W are singly-bound can exemplify the represented method of following reaction equation.
[changing 14]
In the situation that lead-in light polymerizable group on the side chain of the contained polymkeric substance of aligning agent for liquid crystal, even polymerizable compound is few or do not have in the situation that in liquid crystal or in aligning agent for liquid crystal, also can access effect of the present invention.Certainly, in liquid crystal or in aligning agent for liquid crystal, also polymerizable compound can be there is, in this case, effect can be further expected.The side chain side chain of optical polymerism (below also referred to as) that has imported optical polymerism group refers to, contains at least one the side chain that is selected from methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base.Like this; the polyimide precursor that aligning agent for liquid crystal is contained and by this polyimide precursor imidizate and polyimide at least one etc. polymkeric substance become to have and contain at least one the polymkeric substance of side chain of optical polymerism that is selected from methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base; by with above-mentioned polymerizable compound simultaneously for aligning agent for liquid crystal; shown in embodiment, can significantly improve the ghost characteristic that AC stress wait as described later.
The side chain of optical polymerism can directly be combined on the main chain of the polymkeric substance such as polyimide precursor or polyimide, or also can be situated between and carry out combination by suitable conjugated group.As the side chain of optical polymerism, for example, can exemplify with the represented side chain of following formula (b).
[changing 15]
-R 8-R 9-R 10(b)
(in formula (b), R 8represent singly-bound or-CH 2-,-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-,-CH 2o-,-N (CH 3)-,-CON (CH 3)-,-N (CH 3) any in CO-; R 9the alkylidene that represents singly-bound or non-substituted or the carbon number 1～20 that replaced by fluorine atom, alkylidene-CH 2-can be by-CF 2-or-CH=CH-replaces arbitrarily, in the mutual non-conterminous situation of any group of below enumerating, also can be replaced by these groups :-O-,-COO-,-OCO-,-NHCO-,-CONH-,-NH-, the carbocyclic ring of divalence, the heterocycle of divalence.R 10represent methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base.)
In addition, although can form by conventional organic synthesis technology, from the viewpoint of synthetic easiness, consider the R in above formula (b) 8preferably-CH 2-,-O-,-COO-,-NHCO-,-NH-,-CH 2o-.
In addition, as replacing R 9arbitrarily-CH 2-the carbocyclic ring of divalence or carbocyclic ring or the heterocycle of the heterocycle of divalence, specifically can exemplify following structure, but be not limited to this.
[changing 16]
R 10from the viewpoint of optical polymerism, consider preferable methyl acryloyl group, acryloyl group, vinyl or alpha-methylene-gamma-butyrolactone base.
The amount of the side chain of optical polymerism, preferably can be by being reacted by the irradiation of ultraviolet to form in will the orientation curing scope of covalent bond, in order further to improve AC ghost characteristic, other characteristics are not had in influential scope preferably many as far as possible.
Like this, to manufacturing to be selected to have to contain, be selected from methacryl, acryloyl group, vinyl, allyl, the polyimide precursor of the side chain of the optical polymerism of at least one of styryl and alpha-methylene-gamma-butyrolactone base, and by this polyimide precursor imidizate and polyimide in the method for at least one polymkeric substance there is no particular limitation, for example, in the reaction by diamines and tetracarboxylic dianhydride, obtain in the method for polyamic acid, diamines or tetracarboxylic dianhydride can be carried out to copolymerization, described diamines or tetracarboxylic dianhydride have to contain and are selected from methacryl, acryloyl group, vinyl, allyl, the side chain of the optical polymerism of at least one of styryl and alpha-methylene-gamma-butyrolactone base.
< polymkeric substance >
The polymkeric substance that aligning agent for liquid crystal used in the present invention contains, polyimide precursor, by its imidizate and polyimide outside, preferably use polysiloxane or poly-(methyl) acrylate.Herein, polyimide precursor refers to polyamic acid (Ployamic acid also claims Polyamide acid) or poly amic acid ester.In addition, in aligning agent for liquid crystal, can contain these different polymkeric substance simultaneously, they can carry out various selections according to the characteristic of liquid crystal display cells containing proportional.The total amount of the polymkeric substance that aligning agent for liquid crystal contains is 0.1～20 (quality) % preferably.In addition, the polymkeric substance such as the polyimide precursor that aligning agent for liquid crystal of the present invention contains, polyimide, polysiloxane or poly-(methyl) acrylate, need can be dissolved in the contained solvent of aligning agent for liquid crystal.
< photoreactive group >
In the operation of the orientation process in manufacture method of the present invention, in the situation that using polarized UV rays, in the polymkeric substance containing at aligning agent for liquid crystal, need to import the photoreactive group that presents liquid crystal aligning ability by the utilization of polarized UV rays.Such photoreactive group can import on the main chain of polymkeric substance, also can import on side chain.
The liquid crystal orientation film obtaining by the aligning agent for liquid crystal to by containing the polymkeric substance that has imported photoreactive group irradiates polarized UV rays and carries out light reaction, give the anisotropy in the vertical direction with the same direction in polarization direction or polarization direction, liquid crystal is orientated.Light reaction has light decomposition, photodimerization, photoisomerization.If lift its concrete example, as the structure of carrying out photodimerization reaction, can exemplify following formula (A-3), (A-4), (A-5) represented structure.As the structure of carrying out photoisomerization reaction, can exemplify following formula (A-6), (A-7) represented structure.As the structure of carrying out photolysis reactions, can exemplify following formula (A-1), (A-2) represented structure.In addition, the photoreactive group with the structure that is selected from following formula (A-1)～(A-7) refers to, gets the group of group that in group that in group after the H of Arbitrary Digit, formula (A-1)～(A-2), N is key, formula (A-3), O is key or these structures and other structures (such as alkylidene etc.) combination in the structure of these formulas (A-1)～(A-7).
[changing 17]
< polyimide precursor and by its imidizate and polyimide >
The polyimide precursor that aligning agent for liquid crystal used in the present invention is contained, for example, have the represented repetitive (structural unit) of following formula (1).
[changing 18]
In formula (1), R 1alkyl for hydrogen atom or carbon number 1～4.From carry out the viewpoint of the complexity of imidizate, particularly preferably hydrogen atom or methyl by heating.X 2be 4 valency organic groups, its structure is not particularly limited.If enumerate concrete example, can exemplify following formula (X-1)～(X-43).From the viewpoint of liquid crystal aligning, X 2preferably (X-1)～(X-10), (X-26)～(X-28), (X-31)～(X-37).In addition, the viewpoint of the liquid crystal orientation film that the mitigation of the residual charge of accumulating under the effect of DC voltage from acquisition is fast is considered, preferably using the tetracarboxylic dianhydride with aromatic ring structure as raw material, as the X of formula (1) 2structure, more preferably (X-26), (X-27), (X-28), (X-32), (X-35) or (X-37).
[changing 19]
(in formula (X-1), R 2, R 3, R 4and R 5be the alkyl of hydrogen atom, halogen atom, carbon number 1～6, alkenyl, alkenyl or the phenyl of carbon number 2～6 independently respectively.From the viewpoint of liquid crystal aligning, R 2, R 3, R 4and R 5preferably hydrogen atom, halogen atom, methyl or ethyl, more preferably hydrogen atom or methyl, be further preferably selected from least a kind of the represented structure of following formula (X1-1)～(X1-2).)
[changing 20]
[changing 22]
[changing 23]
In the operation of the orientation process in manufacture method of the present invention, in the situation that using polarized UV rays, as X 2preferred structure, can exemplify (X1-1), (X1-2), (X-2), (X-3), (X-5), (X-7), (X-8), (X-9), (X-10), particularly preferably (X1-1), (X1-2) and (X-6).
In above-mentioned formula (1), Y 2for divalent organic group, its structure is not particularly limited.If enumerate Y 2concrete example, can exemplify following formula (Y-1)～(Y-73).
[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 polyimide, preferably contain to there is (Y-8), the structural unit of (Y-20), (Y-21), (Y-22), (Y-28), (Y-29) or structure (Y-30).
The contained polyimide precursor of aligning agent for liquid crystal used in the present invention obtains by two amine components (such as the diamines of the side chain with optical polymerism described later or have the diamines such as diamines of photoreactive group) and the reaction of tetracarboxylic dianhydride's composition (such as tetracarboxylic dianhydride described later, tetrabasic carboxylic acid diester diacid chloride or tetrabasic carboxylic acid diester etc.).Particularly, polyamic acid is to obtain with reacting of tetracarboxylic dianhydride by two amine components.Poly amic acid ester is to obtain by being reacted or reacted under the existence of suitable condensation agent, alkali with two amine components by tetrabasic carboxylic acid diester under alkali exists with tetrabasic carboxylic acid diester diacid chloride by two amine components.In addition, polyimide can be by making this polyamic acid carry out dehydration closed-loop or poly amic acid ester being heated so that its closed loop obtains.As for obtaining the polymkeric substance of liquid crystal orientation film, any in described polyamic acid, poly amic acid ester and polyimide is all useful.
< has the diamines > of the side chain of optical polymerism
As having, contain at least one the diamines of side chain of optical polymerism that is selected from methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base; for example, can exemplify the diamines with the represented side chain of above formula (b).More specifically, for example can exemplify the diamines representing with following general formula (2), but be not limited to this.
[changing 32]
(the R in formula (2) 8, R 9and R 10definition identical with above formula (b).)
To two amino (NH in formula (2) 2) binding site do not limit.Particularly, can exemplify with respect to 2,3,2,4,2,5,2,6,3,4,3,5 on the phenyl ring of the conjugated group of side chain.Wherein, the reactive viewpoint consideration during from synthesizing polyamides acid, preferably 2,4,2,5 or 3,5.If the easiness while also considering synthetic diamines, more preferably 2,4 or 3,5.
As having, contain at least one the diamines of side chain of optical polymerism that is selected from methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base; particularly can exemplify following compound, but be not limited to this.
[changing 33]
(in formula, X represents singly-bound, or the conjugated group of be selected from-O-,-COO-,-NHCO-,-NH-, and Y represents singly-bound, or the alkylidene of non-substituted or the carbon number 1～20 that replaced by fluorine atom.)
Above-mentioned have comprise be selected from least one the diamines of photoreactive side chain of methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base can be according to making liquid crystal aligning, tilt angle, voltage retention performance when liquid crystal orientation film, accumulate the characteristics such as electric charge, the liquid crystal response speed while making liquid crystal display cells etc., be used alone, or mixing two or more.
In addition; having like this contained at least one the diamines of side chain of optical polymerism that is selected from methacryl, acryloyl group, vinyl, allyl, styryl and alpha-methylene-gamma-butyrolactone base; preferably use the amount of 10～70 % by mole of the total amount that reaches two amine components that use when polyamic acid synthetic; more preferably 20～60 % by mole, particularly preferably 30～50 % by mole.
< has the diamines > of photoreactive group
In the operation of the orientation process in manufacture method of the present invention, in the situation that using polarized UV rays, in the polymkeric substance containing at aligning agent for liquid crystal, need lead-in light reactive group.
In the situation that use by the irradiation of polarized UV rays, carry out the method for orientation treatment that photolysis reactions produces anisotropy, the structure of above formula (A-1), (A-2) can be imported to the main chain of polyimide precursor and polyimide.
In the situation that use carries out photodimerization by the irradiation of polarized UV rays or photoisomerization reacts the method for orientation treatment that anisotropy is produced, the structure of above formula (A-3), (A-7) can be imported to main chain or the side chain of polymkeric substance.
As polymkeric substance contained in aligning agent for liquid crystal, in the situation that use polyimide precursor and by its imidizate and polyimide, have to use and in main chain or side chain, containing the tetracarboxylic dianhydride of structure or the method for diamines of above formula (A-3)～(A-7), but from the viewpoint of synthetic easiness, preferably use the diamines of the structure that contains above formula (A-3)～(A-7) in side chain.In addition, the side chain of diamines refers to branch's structure out from 2 amino structures of connection diamines.As the concrete example of such diamines, can exemplify the represented compound of following formula, but not be subject to these limitation.
[changing 34]
(in formula, X represents singly-bound, or the conjugated group of be selected from-O-,-COO-,-NHCO-,-NH-, and Y represents singly-bound, or the alkylidene of non-substituted or the carbon number 1～20 that replaced by fluorine atom.R represents hydrogen atom, or alkyl or the alkylether radicals of non-substituted or the carbon number 1～5 that replaced by fluorine atom.)
< tetracarboxylic dianhydride composition >
In order to obtain polyamic acid contained in aligning agent for liquid crystal used in the present invention, for the tetracarboxylic dianhydride who reacts with two amine components, be not particularly limited.Exemplify its concrete example below.
As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, can exemplify 1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic dianhydride, 2, 3, 4, 5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, 3, 4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1, 2, 3, 4-butane tetracarboxylic acid dianhydride, two rings [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base 2-Cyclopentylacetic acid dianhydride, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride, 4-(2,5-dioxo tetrahydrofuran-3-yl)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic anhydride etc.
Also have, if also use aromatic tetracarboxylic acid's dianhydride outward the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure, liquid crystal aligning improves, and can reduce the electric charge of accumulating of liquid crystal structure cell, thereby preferably.As aromatic tetracarboxylic acid's dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
Tetracarboxylic dianhydride can be when forming liquid crystal orientation film liquid crystal aligning, voltage retentivity, accumulate the characteristics such as electric charge, use a kind or two or more are used.
In order to obtain poly amic acid ester contained in aligning agent for liquid crystal used in the present invention, for the tetrabasic carboxylic acid dialkyl reacting with two amine components, be not particularly limited.Exemplify its concrete example below.
Object lesson as aliphatics tetrabasic carboxylic acid diester, can exemplify 1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl-1, 2, 3, 4-cyclo-butane tetrabasic carboxylic acid dialkyl, 1, 2, 3, 4-cyclopentane tetrabasic carboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran tetrabasic carboxylic acid dialkyl, 1, 2, 4, 5-cyclohexane tetrabasic carboxylic acid dialkyl, 3, 4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1, 2, 3, 4-butane tetracarboxylic acid dialkyl ester, two rings [3, 3, 0] octane-2, 4, 6, 8-tetrabasic carboxylic acid dialkyl, 3, 3 ', 4, 4 ' dicyclohexyl tetrabasic carboxylic acid dialkyl, 2, 3, 5-tricarboxylic base 2-Cyclopentylacetic acid dialkyl, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetrabasic carboxylic acid dialkyl, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxo tetrahydrofuran-3-yl)-1,2,3,4-tetrahydro-naphthalene-1,2-dicarboxylic acid dialkyl esters etc.
As aromatic tetracarboxylic acid's dialkyl, can exemplify Pyromellitic Acid dialkyl, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dialkyl, 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, two (3,4-dicarboxyl phenyl) ether dialkyl, two (3,4-dicarboxyl phenyl) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl etc.
The manufacture method > of < polyamic acid
Poly amic acid ester as polyimide precursor can synthesize by method shown below.
Particularly, can be by making tetracarboxylic dianhydride and diamines under the existence of organic solvent, in-20 ℃～150 ℃, preferably 0 ℃～50 ℃ reactions 30 minutes～24 hours, preferably within 1～12 hour, synthesize.
The organic solvent using in above-mentioned reaction, considers from the dissolubility of monomer and polymkeric substance, preferred DMF, METHYLPYRROLIDONE, gamma-butyrolacton, and these can use one kind or two or more mixing to use.The concentration of polymkeric substance, from being difficult for occurring the viewpoint of separating out and easily obtain high molecular body of polymkeric substance, preferably 1～30 quality %, more preferably 5～20 quality %.
The polyamic acid making as mentioned above can be according to the abundant stirring reaction solution in one side, Yi Bian the mode being injected in poor solvent makes polymkeric substance separate out and reclaim.In addition,, after carrying out that several is separated out and cleaning with poor solvent, by normal temperature or heat drying, can obtain the powder of sublimed polyamic acid.Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
The manufacture method > of < poly amic acid ester
As the poly amic acid ester of polyimide precursor, can synthesize by the method for (1)～(3) that illustrate below.
(1) by polyamic acid, carry out synthetic situation
Poly amic acid ester can synthesize by the polyamic acid being obtained by tetracarboxylic dianhydride and diamines is carried out to esterification.
Particularly, can be by making polyamic acid and esterifying agent under the existence of organic solvent, in-20 ℃～150 ℃, preferably 0 ℃～50 ℃ reactions 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
As esterifying agent, the esterifying agent that preferably can easily remove by purifying, can exemplify N, dinethylformamide dimethylacetal, N, dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, chlorination 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methyl morpholine salt etc.The addition of esterifying agent, with respect to the repetitive of 1 mole of polyamic acid, preferred 2～6 molar equivalents.
The solvent using in above-mentioned reaction, from the dissolubility of polymkeric substance, preferably DMF, METHYLPYRROLIDONE or gamma-butyrolacton, these solvents can be used a kind or two or more is mixed and is used.From being difficult for occurring the viewpoint consideration of separating out and easily obtain high molecular body of polymkeric substance, concentration when synthetic is 1～30 quality %, more preferably 5～20 quality % preferably.
(2) by the reaction of tetrabasic carboxylic acid diester diacid chloride and diamines, carry out synthetic situation
Poly amic acid ester can be synthetic by tetrabasic carboxylic acid diester diacid chloride and diamines.
Particularly, can be by making tetrabasic carboxylic acid diester diacid chloride and diamines under the existence of alkali and organic solvent, in-20～150 ℃, preferably 0～50 ℃ of reaction 30 minutes～24 hours, preferably within 1～4 hour, synthesize.
Above-mentioned alkali can be used pyridine, triethylamine, 4-dimethylaminopyridine etc., for reaction is leniently carried out, and preferred pyridine.The addition of alkali considers from the amount of easily removing and the viewpoint that easily obtains high molecular body, with respect to tetrabasic carboxylic acid diester diacid chloride, and preferably 2～4 times moles.
The solvent using in above-mentioned reaction, considers from the dissolubility of monomer and polymkeric substance, preferred METHYLPYRROLIDONE, gamma-butyrolacton, and these can use in one kind or two or more mixing.From be difficult for there is the viewpoint of separating out and easily obtain high molecular body of polymkeric substance, consider polymer concentration preferably 1～30 quality %, more preferably 5～20 quality % when synthetic.In addition,, in order to prevent the hydrolysis of tetrabasic carboxylic acid diester diacid chloride, the solvent using in poly amic acid ester synthetic is the state of dehydration as far as possible preferably, preferably in nitrogen atmosphere, carries out, to prevent sneaking into of extraneous gas body.
(3) by tetrabasic carboxylic acid diester and diamines, carried out the situation of synthesizing polyamides acid
Poly amic acid ester can be by synthesizing tetrabasic carboxylic acid diester and diamines polycondensation.
Particularly, can be by making tetrabasic carboxylic acid diester and diamines under the existence of condensation agent, alkali, organic solvent, in 0 ℃～150 ℃, preferably 0 ℃～100 ℃ reactions 30 minutes～24 hours, preferably within 3～15 hours, synthesize.
As above-mentioned condensation agent, can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-sulfo--3-benzo azoles base) phosphonic acid diphenyl ester etc.The addition of condensation agent is with respect to tetrabasic carboxylic acid diester, preferably 2～3 times moles.
Above-mentioned alkali can be used the tertiary amines such as pyridine, triethylamine.From the amount of easily removing and the viewpoint that easily obtains high molecular body, the addition of alkali is with respect to two amine components, preferably 2～4 times moles.
In addition,, in above-mentioned reaction, add lewis acid can make reaction carry out efficiently as adjuvant.As lewis acid, the lithium halides such as preferred lithium chloride, lithium bromide.Lewis acidic addition is preferably 0～1.0 times mole with respect to two amine components.
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, the synthetic method of above-mentioned (1) or above-mentioned (2) particularly preferably.
The solution of the poly amic acid ester making as mentioned above can be according to the abundant stirring reaction solution in one side, Yi Bian the mode being injected in poor solvent is separated out polymkeric substance.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of sublimed poly amic acid ester.Poor solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
The manufacture method > of < soluble polyimide
Above-mentioned polyimide can be by manufacturing above-mentioned polyamic acid or poly amic acid ester imidizate.In the situation that manufacturing polyimide by poly amic acid ester, easy is chemical imidization, this chemical imidization is to make above-mentioned polyamic acid ester solution or poly amic acid ester powder dissolution in organic solvent, in the polyamic acid solution of gained, adds base catalyst.Chemical imidization carries out imidization reaction at lower temperature, and in the process of imidizate, is difficult for occurring the reduction of polymer molecular weight, thereby preferably.
Chemical imidization can be by stirring the poly amic acid ester of wanting imidizate to carry out in organic solvent, under the existence of base catalyst.As organic solvent, solvent used in the time of can using above-mentioned polyreaction.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein triethylamine makes the reaction enough alkalescence of carrying out and preferably owing to having.
Temperature while carrying out imidization reaction can be-20 ℃～140 ℃, and preferably 0 ℃～100 ℃, the reaction time can be 1～100 hour.The amount of base catalyst is 0.5～30 mole times of amic acid ester group, is preferably 2～20 moles doubly.The acid imide rate of the polymkeric substance obtaining can be by regulating catalytic amount, temperature, reaction time to control.Therefore preferably in solution after imidization reaction, remain the catalyzer of interpolation etc., after reclaiming by following method the imide amination polymer making and dissolving again with organic solvent, be used as aligning agent for liquid crystal.
By polyamic acid, manufactured in the situation of polyimide, easy is chemical imidization, and this chemical imidization is to add catalyzer in the solution of the above-mentioned polyamic acid that makes in the reaction by two amine components and tetracarboxylic dianhydride.Chemical imidization is at lower temperature, to carry out imidization reaction, and in the process of imidizate, is difficult for occurring the reduction of polymer molecular weight, thereby preferably.
The polymkeric substance that chemical imidization can be wanted by stirring in organic solvent, under the existence of base catalyst and acid anhydrides imidizate carries out.As organic solvent, solvent used in the time of can using above-mentioned polyreaction.As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein pyridine because have makes suitable alkalescence that reaction carries out and preferably.In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc., wherein, while using acetic anhydride, be easy to react the purifying after finishing, thereby preferably.
Temperature while carrying out imidization reaction can be-20 ℃～140 ℃, and preferably 0 ℃～100 ℃, the reaction time can be 1～100 hour.The amount of base catalyst is 0.5～30 mole times of acid amides acidic group, and preferably 2～20 moles times, the amount of acid anhydrides is 1～50 mole times of acid amides acidic group, preferably 3～30 moles times.The acid imide rate of the polymkeric substance obtaining can be by regulating catalytic amount, temperature, reaction time to control.
In solution after the imidization reaction of poly amic acid ester or polyamic acid, remain the catalyzer of interpolation etc., therefore preferably by following method, the imide amination polymer that recovery makes and with organic solvent, dissolve again after, be used as aligning agent for liquid crystal of the present invention.
The solution of the polyimide making as mentioned above can be by separate out polymkeric substance well-beaten in being injected into poor solvent simultaneously.After carrying out that several is separated out and cleaning with poor solvent, at normal temperatures or heat drying, can obtain the powder of sublimed poly amic acid ester.
Aforementioned poor solvent is not particularly limited, can exemplifies methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.
The manufacture method > of < polysiloxane
The method of the polysiloxane that obtains using in the present invention is not particularly limited, for example, alkoxy silane carried out to condensation in organic solvent and obtain.Conventionally, polysiloxane can be used as and obtains being dissolved in equably the solution forming in organic solvent after above-mentioned alkoxy silane polycondensation.
As by the method for alkoxy silane polycondensation, for example can exemplify by alkoxy silane in alcohol or solvents such as glycols, be hydrolyzed, the method for condensation.
Now, hydrolysis-condensation reaction can be any in partial hydrolysis and complete hydrolysis.During complete hydrolysis, add in theory the water of 0.5 times mole of the whole alkoxys in alkoxy silane, but conventionally preferably add the water of the amount that surpasses 0.5 times mole.
In the present invention, the amount of the water that above-mentioned reaction is used can suitably be selected as required, but 0.5～2.5 times mole of the whole alkoxys in alkoxy silane conventionally preferably.
In addition, conventionally under the object of facilitation of hydrolysis, condensation reaction, use the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid, the alkali such as ammonia, methylamine, ethamine, monoethanolamine, triethylamine, the catalyzer such as slaine of hydrochloric acid, sulfuric acid, nitric acid etc.In addition, general also by the solution that has dissolved alkoxy silane is heated, further facilitation of hydrolysis, condensation reaction.Now, heating-up temperature and heat time can suitably be selected as required.For example can exemplify heating at 50 ℃, stir the method for 24 hours, heating under refluxing, the stirring method of 1 hour etc.
In addition, as other method, for example, can exemplify the potpourri method of carrying out polycondensation of heating alkoxy silane, solvent and oxalic acid.Particularly, for add in advance oxalic acid in alcohol, form after the alcoholic solution of oxalic acid, will under the state of this solution heating, sneak into the method for alkoxy silane.Now, the consumption of oxalic acid is with respect to 1 mole of the contained whole alkoxy of alkoxy silane, preferably 0.2～2 mole.Heating in the method can be carried out at 50～180 ℃ of liquid temperatures.For fear of occur liquid evaporation, wave loosely etc., preferably under refluxing, heat dozens of minutes～tenss' hour method.
The in the situation that of using multiple alkoxy silane when manufacturing polysiloxane, the form of the potpourri that alkoxy silane can be obtained to be pre-mixed is mixed, and also can mix successively multiple alkoxy silane.
As the alkoxy silane using in order to obtain polysiloxane, the compound that illustration is following.
As the alkoxysilane compound containing trialkylsilyl group in molecular structure on side chain with optical polymerism group, can exemplify 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, methacryloxy methyltrimethoxy silane, methacryloxy methyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, acryloxy ethyl trimethoxy silane, acryloxy ethyl triethoxysilane, styrene ethyl trimethoxy silane, styrene ethyl triethoxysilane, 3-(N-styrene methyl-2-amino ethylamino) propyl trimethoxy silicane, ethenylphenyl ethyl trimethoxy silane, ethenylphenyl ethyl triethoxysilane, vinyltrimethoxy silane etc.
As other alkoxysilane compound containing trialkylsilyl group in molecular structure, can exemplified by methyl trimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, ethyl triethoxysilane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy silane, 3-TSL 8330, APTES, N-2 (amino-ethyl) APTES, N-2 (amino-ethyl) 3-TSL 8330, 3-(2-aminoethylamino propyl group) trimethoxy silane, 3-(2-aminoethylamino propyl group) triethoxysilane, 2-aminoethylamino methyltrimethoxy silane, 2-(2-amino-ethyl thio-ethyl) triethoxysilane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl trimethoxy silane, vinyltriethoxysilane, 3-isocyanate group propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, diethyl diethoxy silane, diethyl dimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl dimethylethoxysilane, trimethylethoxysilane, trimethyl methoxy silane, γ-urea groups propyl-triethoxysilicane, γ-urea groups propyl trimethoxy silicane and γ-urea groups propyl group tripropoxy silane etc.
Solvent (below also referred to as polymer solvent) used during alkoxy silane polycondensation is so long as the solvent of dissolvane TMOS, and there is no particular limitation.In addition, even in the undissolved situation of alkoxy silane, so long as the solvent dissolving when the polycondensation reaction of alkoxy silane is carried out.Generally speaking, because the polycondensation reaction by alkoxy silane generates alcohol, therefore use alcohols, di-alcohols, dibasic alcohol ethers or the organic solvent good with alcohols intermiscibility.
As the concrete example of above-mentioned polymer solvent, can exemplify the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol, ethylene glycol, diglycol, propylene glycol, dipropylene glycol, hexanediol, 1,3-PD, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-PD, 2,4-pentanediol, 2,3-pentanediol, 1, the glycolss such as 6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol one propyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate propyl ether, ethylene glycol bisthioglycolate butyl ether, diglycol monomethyl ether, diglycol monoethyl ether, diglycol one propyl ether, diethylene glycol-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol dipropyl ether, diglycol dibutyl ethers, Glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol one propyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol Anaesthetie Ether, propylene glycol dipropyl ether, the glycol ethers such as propylene glycol dibutyl ethers, METHYLPYRROLIDONE, DMF, DMA, gamma-butyrolacton, dimethyl sulfoxide, tetramethylurea, HMPA, metacresol etc.
In the present invention, above-mentioned polymer solvent can will be used after multiple mixing.
The manufacture method > of poly-(methyl) acrylate of <
To obtaining the method for poly-(methyl) acrylate used in the present invention, there is no particular limitation.Can be by making the monomer of acrylate compounds or methacrylate compound etc., the monomer with optical polymerism group or photoreactive group of use, and the polymerization initiator using as required as required etc. carries out polyreaction and obtains with the temperature of 50 ℃～110 ℃ in solvent.At this moment the solvent that used so long as the solvent of dissolved monomer and the polymkeric substance that obtains be not particularly limited.
As acrylate compounds, for example can exemplified by acrylic methyl esters, ethyl acrylate, isopropyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthryl methyl esters, phenyl acrylate, acrylic acid 2, 2, 2-trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, acrylic acid Isobornyl, acrylic acid 2-methoxyl ethyl ester, acrylic acid methoxyl triglycol ester, acrylic acid 2-ethoxy ethyl ester, acrylic acid tetrahydro furfuryl ester, acrylic acid 3-methoxyl butyl ester, acrylic acid 2-methyl-2-adamantane esters, acrylic acid 2-propyl group-2-adamantane esters, acrylic acid 8-methyl-8-tri-ring esters in the last of the ten Heavenly stems and acrylic acid 8-ethyl-8-tri-ring esters in the last of the ten Heavenly stems etc.
As methacrylate compound, for example can exemplified by methyl methyl acrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthryl methyl esters, phenyl methacrylate, methacrylic acid 2, 2, 2-trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, methacrylic acid Isobornyl, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid methoxy base triglycol ester, methacrylic acid 2-ethoxy ethyl ester, methacrylic acid tetrahydro furfuryl ester, methacrylic acid 3-methoxyl butyl ester, methacrylic acid 2-methyl-2-adamantane esters, methacrylic acid 2-propyl group-2-adamantane esters, methacrylic acid 8-methyl-8-tri-ring esters in the last of the ten Heavenly stems and methacrylic acid 8-ethyl-8-tri-ring esters in the last of the ten Heavenly stems etc.
Concrete example as solvent, can exemplify ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, TC, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2 pentanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, dinethylformamide, N, N-dimethyl acetamide and 1-METHYLPYRROLIDONE etc.
By as above and the solution of polymkeric substance drop into stir in lower methyl alcohol, ethanol, water etc. and precipitate again, after the sediment generating is filtered and cleaned, at normal pressure or under reducing pressure, by normal temperature or heat drying, can be made into the powder of desired polymkeric substance.By such operation, can remove the polymerization initiator or the unreacted monomer that coexist with polymkeric substance, consequently can obtain the powder of sublimed polymkeric substance.In single job, fully purifying in the situation that, the powder obtaining can be dissolved in solvent again, repeat aforesaid operations.
< aligning agent for liquid crystal >
In the situation that use polyimide precursor or polyimide as the contained polymkeric substance of aligning agent for liquid crystal, the molecular weight of polyimide precursor or polyimide, in weight-average molecular weight preferably 2000～500000, more preferably 5000～300000, further preferably 10000～100000.In addition, number-average molecular weight preferably 1000～250000, more preferably 2500～150000, further preferably 5000～50000.
In the situation that use polysiloxane as the contained polymkeric substance of aligning agent for liquid crystal, the molecular weight of polysiloxane, in weight-average molecular weight preferably 2000～500000, more preferably 5000～300000, further preferably 10000～100000.In addition number-average molecular weight preferably 1000～250000, more preferably 2500～150000, further preferably 5000～50000.
In the situation that use poly-(methyl) acrylate as the contained polymkeric substance of aligning agent for liquid crystal, the molecular weight of poly-(methyl) acrylate, in weight-average molecular weight preferably 2000～500000, more preferably 5000～300000, further preferably 10000～100000.In addition number-average molecular weight preferably 1000～250000, more preferably 2500～150000, further preferably 5000～50000.
The organic solvent containing in aligning agent for liquid crystal used in the present invention, so long as can uniform dissolution the contained above-mentioned polymkeric substance of aligning agent for liquid crystal or the solvent of polymerizable compound, there is no particular limitation.If enumerate its concrete example, in the situation that using polyimide precursor or polyimide as polymkeric substance, can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.In addition, in the situation that using polysiloxane as polymkeric substance, such as exemplifying the polyol compounds such as ethylene glycol, 1,2-PD, the amide compounds such as N-METHYLFORMAMIDE, DMF etc.In addition, in the situation that using poly-(methyl) acrylate as polymkeric substance, such as exemplifying alcoholic compound, ketonic compound, amide compound or ester compounds or other non-proton property compound etc.These solvents can be used a kind or two or more mix is used.In addition, even can not be individually the solvent of dissolve polymer or polymerizable compound equably, as long as in the scope that polymkeric substance or polymerizable compound are not separated out, also can mix with above-mentioned organic solvent.
Aligning agent for liquid crystal of the present invention be take the organic solvent that dissolve polymer or polymerizable compound be object except comprising, and can also comprise to improve the solvent that painting film uniformity when aligning agent for liquid crystal is coated to substrate is object.This solvent is conventionally used and compares the solvent of low surface tension with above-mentioned organic solvent.If exemplify its concrete example, can enumerate ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, mono-ether-the 2-of propylene glycol-1-acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can and be used two or more.
In aligning agent for liquid crystal used in the present invention, except mentioned component, as long as in not damaging the scope of effect of the present invention, also can add above-mentioned polymkeric substance polymkeric substance in addition, dielectric or conductive materials that the electrical characteristics such as changing the specific inductive capacity of liquid crystal orientation film or electric conductivity of take are object, take and improve the silane coupling agent that the adaptation of liquid crystal orientation film and substrate is object, take and improve the hardness of the film while making liquid crystal orientation film or the cross-linked compound that density is object, and to take burning till the imidizate that makes polyimide precursor while filming be imidizate promoter of object etc. efficiently.
The manufacture > of < liquid crystal orientation film
The liquid crystal orientation film that manufacture method of the present invention is used is that above-mentioned aligning agent for liquid crystal is coated on substrate, after being dried as required, burn till, to the coated surface of gained carry out orientation process and.
Substrate as coating of liquid crystalline alignment agent, so long as the high substrate of the transparency is not particularly limited, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate or polycarbonate substrate etc., from the viewpoint that production technology is simplified, preferably use the substrate of ITO (Indium TinOxide) electrode that is formed with for liquid crystal drive etc.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but only limit to the substrate of a side, electrode now also can be used the reflectorized materials such as aluminium.The coating process of the aligning agent for liquid crystal of recording as the present invention, can exemplify spin-coating method, print process, ink-jet method etc.
Dry, firing process after coating of liquid crystalline alignment agent can be selected arbitrary temp and time.Conventionally, in order fully to remove the organic solvent containing, preferably at 50 ℃～120 ℃, preferably make its dry 1 minute～10 minutes, then preferably at 150 ℃～300 ℃, preferably burn till 5 minutes～120 minutes.Therefore the thickness of filming after burning till is not particularly limited, if but excessively thin, the reliability of liquid crystal display cells can reduce sometimes, preferably 5～300nm, more preferably 10～200nm.
< orientation process >
The orientation process of using in manufacture method of the present invention, is by the orientation process of friction, and by irradiating the what is called of polarized UV rays, utilizes the orientation process of optical alignment method.
As the preferred concrete example that utilizes the orientation process of optical alignment method, can exemplify in above-mentioned film coated surface irradiate contain below the above 400nm of wavelength 200nm, preferably below the above 380nm of 210nm, the ultraviolet ultraviolet ray to certain orientation polarization below the above 350nm of for example 300nm, according to circumstances, further with the temperature of 150～250 ℃, carry out heat treated, give the method for liquid crystal aligning ability.In addition,, in order to improve liquid crystal aligning, can at 50～250 ℃, heat irradiation ultraviolet radiation when filming substrate.Aforementioned ultraviolet irradiation amount is 1～10000mJ/cm preferably 2scope, 1～2000mJ/cm particularly preferably 2scope.
Further, also water or contact processing containing the solution of specific organic solvent subsequently of the above-mentioned film that irradiated polarized UV rays.To above-mentioned organic solvent, there is no particular limitation, can exemplify water, methyl alcohol, ethanol, 2-propyl alcohol, acetone, methyl ethyl ketone, 1-methoxyl-2-acetone, 1-methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-methoxy methyl propionate, 3-ethoxyl ethyl propionate, propyl acetate, butyl acetate, and cyclohexyl acetate etc.In above-mentioned solvent, high from easy acquisition anisotropy, without the aspect of uneven liquid crystal orientation film, be preferably selected from 1-methoxy-2-propanol, 1-methoxy-2-propanol acetic acid esters, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3-methoxy methyl propionate, 3-ethoxyl ethyl propionate, propyl acetate, butyl acetate and cyclohexyl acetate at least a kind.Particularly preferably be selected from 1-methoxy-2-propanol and ethyl lactate at least a kind.
The film that irradiated polarized UV rays is processed preferably and by dip treating, spraying processing etc., the processing that film fully contacts with liquid is carried out with contacting of the solution that comprises organic solvent.Wherein, preferably by film containing dip treating 10 seconds～1 hour in the solution of organic solvent, the more preferably method of 1～30 minute.Contact is processed and can be carried out at normal temperatures also can under heating, carrying out, preferably 10～80 ℃, more preferably implement at 20～50 ℃.In addition, can implement as required the method for the contact-enhancings such as ultrasound wave.
After above-mentioned contact is processed, in order to remove the organic solvent in used solution, can water, the low boiling point solvent such as methyl alcohol, ethanol, 2-propyl alcohol, acetone, methyl ethyl ketone wash (flushings) and be dried in either one or both.Temperature when dry, preferably 80～250 ℃, more preferably 80～150 ℃.
The liquid crystal orientation film obtaining as mentioned above can make liquid crystal molecule stably be orientated towards certain orientation.
< transverse electric field drives the manufacture method > with liquid crystal display cells
It is after obtaining the above-mentioned substrate with liquid crystal orientation film with liquid crystal display cells that the transverse electric field of manufacture method manufacturing of the present invention drives, by known method, manufacture the liquid crystal structure cell that transverse electric field drives use, use this transverse electric field to drive the liquid crystal structure cell of use to make transverse electric field driving liquid crystal display cells.In addition, the liquid crystal display cells of transverse electric field type of drive (IPS:In-Plane Switching) refers to, for substrate, applies electric field on (transverse direction) in the horizontal direction and drives the liquid crystal display cells of the mode of liquid crystal molecule.
As transverse electric field, drive the example by the manufacture method of liquid crystal display cells, the liquid crystal display cells of passive-matrix structure of take describes as example.In addition, can be also in each pixel portion of composing images demonstration, to be provided with the transverse electric field driving liquid crystal display cells of the active matrix structure of the on-off elements such as TFT (thin film transistor (TFT) (Thin Film Transistor)).
As for manufacturing of the present invention transverse electric field drive the substrate with liquid crystal display cells, so long as the high substrate of the transparency is not particularly limited, normally on substrate, be formed with for driving the substrate of the transparency electrode of liquid crystal.As concrete example, can exemplify the same substrate of substrate of recording in the manufacture with above-mentioned liquid crystal orientation film.
In addition, liquid crystal orientation film is to burn till be coated with above-mentioned aligning agent for liquid crystal on this substrate after, forms as required by friction treatment or irradiation polarized UV rays isoradial.Then, on a side substrate, with liquid crystal aligning face each other overlapping the opposing party's of mode in opposite directions substrate, periphery is engaged with encapsulant.In order to control substrate gap, in encapsulant, conventionally sneak in advance sept.In addition, be better that part is not scattered in advance for controlling the sept of substrate gap yet in the face of encapsulant is set.In the part of encapsulant, setting in advance can be from the peristome of outside filling liquid crystal.
Then,, by being arranged at the peristome of encapsulant, in the space being surrounded by two substrates and encapsulant, inject liquid crystal material.As liquid crystal material, such as exemplifying liquid crystal MLC-2041 (Merck joint-stock company (メル Network Co., Ltd.) system) etc.Then, this peristome is sealed with cement.Injection can be used vacuum impregnation, also can use the method for utilizing capillarity in atmosphere.Make by this liquid crystal structure cell that transverse electric field drives use.
Then, to this transverse electric field, drive the light such as liquid crystal structure cell irradiation ultraviolet radiation of use.Here, ultraviolet irradiation amount is for example 1～60J, and preferably, below 40J, ultraviolet irradiation amount can suppress the reliability decrease producing because forming the destruction of the member of liquid crystal display cells less, and reduce ultraviolet irradiation time and can improve manufacture efficiency, thereby suitable.The ultraviolet wavelength irradiating is for example 200nm～400nm.
If to the light such as liquid crystal structure cell irradiation ultraviolet radiation that make above,, to light such as liquid crystal orientation film or liquid crystal irradiation ultraviolet radiations, the optical polymerism group being positioned on the face joining with liquid crystal orientation film and liquid crystal reacts, and the orientation that is positioned at the surperficial liquid crystal of liquid crystal orientation film is cured.Thus, shown in embodiment, the orientation limitations power of liquid crystal is reinforced as described later, consequently, has obtained the transverse electric field driving liquid crystal display cells that electrical characteristics chaotic by liquid crystal aligning and ghost phenomena that cause etc. are improved.
Then, carry out the setting of polaroid.Particularly, on the face of the side contrary with liquid crystal layer of 2 substrates, paste a pair of polaroid.Through above operation, can obtain transverse electric field driving liquid crystal display cells.
By transverse electric field of the present invention as above, drive the transverse electric field driving liquid crystal display cells of manufacturing by the manufacture method of liquid crystal display cells, due to be the orientation limitations power of liquid crystal strong, suppressed the element that ghost produces, therefore can perform well in the LCD TV of large picture and high-resolution etc.
Embodiment
Below, the present invention will be described in more detail to exemplify embodiment, but the present invention is not limited thereto.
The preparation > of < aligning agent for liquid crystal
The abbreviation of using 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-cyclo-butane tetracarboxylic dianhydride
(diamines)
P-PDA: p-phenylenediamine (PPD)
DA-1: (E)-2,4 diaminobenzene ethyl 3-(4-cyclohexyl phenyl) acrylate that following formula is represented
[changing 35]
DA-2: the diamine compound that following formula is represented
[changing 36]
DA-3: the diamine compound that following formula is represented
[changing 37]
BEM-S: 2-(methacryloxy) ethyl 3 that following formula is represented, 5-diaminobenzoic acid ester
[changing 38]
(methacrylic acid monomer)
MA1: the methacrylic acid monomer that following formula is represented
[changing 39]
The synthetic method that MA1 is recorded with Japanese Patent Laid-Open 2010-18807 communique is synthetic.
(radical polymerization initiator)
AIBN:2,2 '-azoisobutyronitrile
(organic solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: butyl cellosolve
(polymerizable compound)
RM1: 5,5 ' (4,4 '-(two phenyl-4,4 '-bis-bases two (oxygen base)) two (butane-4,1-bis-bases)) two (3-methylene dihydrofuran-2 (3H)-one) that following formula is represented
[changing 40]
RM2: the polymerizable compound that following formula is represented
[changing 41]
RM3: the polymerizable compound that following formula is represented
[changing 42]
In addition, the molecule measuring fixed condition of polymkeric substance (polyamic acid, polyimide) is as follows.
Device: normal temperature gel permeation chromatography (GPC) device (SSC-7200) of Sen Xiu science Co., Ltd. (セ Application シ ュー science society) system,
Post: the post (KD803, KD805) of Showa Denko K. K (Shodex society) system
Column temperature: 50 ℃
Eluent: N, and N'-dimethyl formamide (as adjuvant, lithium bromide hydrate (LiBrH 2o) be that 30 mM/ls, phosphoric anhydride crystallization (orthophosphoric acid) are that 30 mM/ls, tetrahydrofuran (THF) are 10 milliliters/liter)
Flow velocity: 1.0 ml/min
Calibration curve making standard sample: Dong Cao company (Eastソ ー society) TSK standard polyethylene oxide processed (molecular weight is about 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ トリ ー society) polyglycol processed (molecular weight is about 12000,4000,1000).
(synthesis example 1)
At DA-1 (5.10g, 14.0 mMs) in, add NMP (22.0g), after at room temperature stirring is dissolved it completely, add CBDA (2.66g, 13.6 mMs) and NMP (22.0g), at room temperature react and within 10 hours, obtain polyamic acid solution.In this polyamic acid solution (40g), add NMP (40.0g) and BCS (20.0g), by room temperature stirring, within 5 hours, obtain aligning agent for liquid crystal (A1).The number-average molecular weight of this polyamic acid is 6500, and weight-average molecular weight is 26000.
In addition, add the polymerizable compound RM1 of 60mg (being 10 quality % with respect to solid composition) with respect to the above-mentioned aligning agent for liquid crystal (A1) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (A2).
(synthesis example 2)
At DA-1 (3.57g, 9.8 mMs) and BEM-S (1.11g, 4.2 mMs) in, add NMP (20.8g), after at room temperature stirring is dissolved it completely, add CBDA (2.66g, 13.6 mMs) and NMP (20.8g), at room temperature react and within 10 hours, obtain polyamic acid solution.In this polyamic acid solution (40g), add NMP (40.0g) and BCS (20.0g), by room temperature stirring, within 5 hours, obtain aligning agent for liquid crystal (B1).The number-average molecular weight of this polyamic acid is 7500, and weight-average molecular weight is 25000.
In addition, add the polymerizable compound RM1 of 60mg (being 10 quality % with respect to solid composition) with respect to the above-mentioned aligning agent for liquid crystal (B1) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (B2).
The making 1> of < liquid crystal structure cell
(comparative example 1)
Use the aligning agent for liquid crystal (A2) obtaining in synthesis example 1, according to step as follows, carry out the manufacture of liquid crystal structure cell.Substrate is the glass substrate of 30mm * 40mm size, thickness 0.7mm, use configured by ITO film patterning form, the substrate of comb-shaped pixel electrode.Pixel electrode has the comb-shaped shape of arranging electrode members a plurality of middle body bendings, " く " word shape and forming.The short side direction width of each electrode member is 3 μ m, between electrode member, is spaced apart 6 μ m.The pixel electrode that forms each pixel forms by arranging electrode member a plurality of middle body bendings, " く " word shape, so the shape of each pixel is not oblong-shaped, but have with similarly middle body bending of electrode member, as the shape of thick " く " word.So each pixel be take its central sweep and is cut apart up and down as boundary, has the 1st region of upside and the 2nd region of downside of sweep.When the 1st region of each pixel and the 2nd region are compared, the formation direction of electrode member of finding to form their pixel electrode is different., using the orientation process direction of liquid crystal orientation film described later in the situation of benchmark, in the 1st region of pixel, the electrode member of pixel electrode being+mode of the angle (clockwise direction) of 10 ° forms, in the 2nd region of pixel, the electrode member of pixel electrode forms to be the mode of the angle (clockwise direction) of-10 °., in the 1st region and the 2nd region of each pixel, take and applied and mode that the direction of the liquid crystal that the evokes spinning movement (in-plane changes) in real estate is opposite directions forms by the voltage between pixel electrode and opposite electrode.The aligning agent for liquid crystal that synthesis example 1 is obtained (A2) is spun on ready above-mentioned electroded substrate.Then, on the hot plate of 90 ℃, be dried after 60 seconds, in the heated air circulation type stove of 200 ℃, burn till 30 minutes, form the liquid crystal orientation film of thickness 100nm.Then, across polarization plates, to coated surface, irradiate the ultraviolet 20mJ/cm of 313nm 2, obtain the substrate with liquid crystal orientation film.In addition, on the glass substrate with the column spacer that is highly 4 μ m that is not formed with electrode as substrate in opposite directions, also use same formation of aligning agent for liquid crystal (A2) to film, implementation orientation processing.Printing and sealing agent on the liquid crystal orientation film of a side group plate (XN-1500T processed of Xie Li KCC (the vertical chemistry of Association)).Then, by the substrate of opposite side so that after the condition that the relative orientation direction of liquid crystal orientation film is 0 ° fits, curing sealant, makes negative crystal born of the same parents.To this negative crystal born of the same parents, utilize decompression injection method to inject liquid crystal MLC-2041 (Merck joint-stock company), sealing inlet, the liquid crystal structure cell of (In-Plane Switching) mode liquid crystal display element (liquid crystal display cells of transverse electric field type of drive) structure that obtains possessing IPS.
(embodiment 1)
For carrying out with comparative example 1 the liquid crystal structure cell that identical operation is manufactured, from the outside of liquid crystal structure cell, irradiate the ultraviolet 20J/cm of 365nm 2(2 times irradiate), obtain the liquid crystal structure cell of embodiment 1.
(comparative example 2)
Except using aligning agent for liquid crystal (B2) replacement aligning agent for liquid crystal (A2), carry out the operation identical with comparative example 1, obtain the liquid crystal structure cell of comparative example 2.
(embodiment 2)
For carrying out with comparative example 2 the liquid crystal structure cell that identical operation is manufactured, from the outside of liquid crystal structure cell, irradiate the ultraviolet 20J/cm of 365nm 2(2 times irradiate), obtain the liquid crystal structure cell of embodiment 2.
(comparative example 3)
Except using aligning agent for liquid crystal (A1) replacement aligning agent for liquid crystal (A2), carry out the operation identical with comparative example 1, obtain the liquid crystal structure cell of comparative example 3.
(ghost evaluates 1)
The IPS pattern that each embodiment 1～2 and comparative example 1～3 are prepared is arranged between two Polarizers that the mode with polarizing axis quadrature configures with liquid crystal structure cell, make backlight luminous not executing under alive state, so that the brightness of transmitted light reaches the arrangement angles that minimum condition has been adjusted liquid crystal structure cell.Then, the 2nd region from pixel being reached to the darkest angle plays the anglec of rotation that the 1st region reaches while making the rotation of liquid crystal structure cell till the darkest angle and calculates as initial stage orientation position angle.Then,, under room temperature environment, with frequency 30Hz, apply the 8V of 24 hours pPalternating voltage.Then, make between the pixel electrode of liquid crystal structure cell and opposite electrode, in short-circuit condition, under this state, in room temperature, to place 1 hour.After placement, measure in the same manner orientation position angle, the azimuthal difference of orientation exchanging before and after driving is calculated as angle delta (deg.).
[table 1]
This result is as shown in table 1, add polymerizable compound or the manufacture of liquid crystal structure cell and irradiated afterwards the embodiment 1 and 2 of UV, compare with 2 with the comparative example 1 that does not add polymerizable compound, do not have UV to irradiate the comparative example 3 of (irradiating for 2 times) after liquid crystal structure cell is made or do not have UV to irradiate after the making of liquid crystal structure cell, the azimuthal difference of orientation exchanging before and after driving is very little.But, can think that the orientation limitations power of embodiment 1 and 2 is strong, ghost characteristic is very good.This thinks after the manufacture of liquid crystal structure cell from outside UV, to irradiate by carrying out, and the optical polymerism compound having added forms polymer layer at alignment layer surface, makes to be by this orientated curing cause.In addition, because embodiment 1 is the zero comparison that is difficult to embodiment 2 the two azimuthal differences of orientation that exchange before and after driving, but from the azimuthal difference of orientation of using the comparative example 2 of the polymkeric substance that has imported the BEM-S with optical polymerism to exchange before and after driving, than comparative example 1 I, confirm, the polymkeric substance that has imported the BEM-S with optical polymerism by use can 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), at room temperature react and within 10 hours, obtain polyamic acid solution.In this polyamic acid solution (32.1g), add NMP (32.1g) and BCS (42.9g) and be diluted to after 6 % by weight, by room temperature stirring, within 10 hours, obtaining aligning agent for liquid crystal (C).The number-average molecular weight of this polyamic acid is 13000, and weight-average molecular weight is 19000.
In addition, add the polymerizable compound RM1 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (C) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (C1).
In addition, add the polymerizable compound RM2 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (C) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (C2).
In addition, add the polymerizable compound RM3 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (C) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (C3).
(synthesis example 4)
By BODA (2.50g, 10.0 mMs), DA-3 (9.65g, 20.0 mMs) in NMP (42.3g), mix, with 80 ℃, react after 5 hours, add CBDA (1.92g, 10.0 mMs) and NMP (14.1g), with 40 ℃ of reactions, within 10 hours, obtain polyamic acid solution.In this polyamic acid solution (70.4g), add NMP (70.4g) and BCS (93.8g) and be diluted to after 6 % by weight, by room temperature stirring, within 10 hours, obtaining aligning agent for liquid crystal (D).The number-average molecular weight of this polyamic acid is 12000, and weight-average molecular weight is 21000.
In addition, add the polymerizable compound RM1 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (D) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (D1).
(synthesis example 5)
CBDA (1.92g, 10.0 mMs), p-PDA (0.54g, 5.0 mMs), DA-2 (2.24g, 5.0 mMs) are mixed in NMP (18.9g), at room temperature react and within 10 hours, obtain polyamic acid solution.In this polyamic acid solution (23.6g), add NMP (23.6g) and BCS (31.5g) and be diluted to after 6 % by weight, by room temperature stirring, within 10 hours, obtaining aligning agent for liquid crystal (E).The number-average molecular weight of this polyamic acid is 19000, and weight-average molecular weight is 28000.
In addition, add the polymerizable compound RM1 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (E) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (E1).
(synthesis example 6)
MA1 (5.54g, 16.0 mMs) is dissolved in NMP (51.1g), with membrane pump carry out 6 minutes degassed after, add AIBN (0.131g, 0.8 mM) again carry out 6 minutes degassed.With 65 ℃ of reactions 20 hours, obtain methacrylate polymers solution afterwards.In this polymer solution, add BCS (37.8g) and be diluted to 6 quality %, by room temperature stirring, within 5 hours, obtain aligning agent for liquid crystal (F).The number-average molecular weight of this polymkeric substance is 16000, and weight-average molecular weight is 39000.
In addition, add the polymerizable compound RM1 of 30mg (being 5 quality % with respect to solid composition) in the aligning agent for liquid crystal (F) of 10.0g, at room temperature 3 times stirred it are dissolved, and prepared aligning agent for liquid crystal (F1).
The making 2> of < liquid crystal structure cell
(embodiment 3)
Use the aligning agent for liquid crystal (C1) obtaining in synthesis example 3, according to step as follows, carry out the manufacture of liquid crystal structure cell.Substrate is the glass substrate of 30mm * 40mm size, thickness 0.7mm, use configured by ITO film patterning form, the substrate of comb-shaped pixel electrode.Pixel electrode has the comb-shaped shape of arranging electrode members a plurality of middle body bendings, " く " word shape and forming.The short side direction width of each electrode member is 10 μ m, between electrode member, is spaced apart 20 μ m.The pixel electrode that forms each pixel forms by arranging electrode member a plurality of middle body bendings, " く " word shape, so the shape of each pixel is not oblong-shaped, but have with similarly middle body bending of electrode member, as the shape of thick " く " word.So each pixel be take its central sweep and is cut apart up and down as boundary, has the 1st region of upside and the 2nd region of downside of sweep.When the 1st region of each pixel and the 2nd region are compared, the formation direction of electrode member of finding to form their pixel electrode is different., using the orientation process direction of liquid crystal orientation film described later in the situation of benchmark, in the 1st region of pixel, the electrode member of pixel electrode being+mode of the angle (clockwise direction) of 15 ° forms, in the 2nd region of pixel, the electrode member of pixel electrode forms to be the mode of the angle (clockwise direction) of-15 °., in the 1st region and the 2nd region of each pixel, take and applied and mode that the direction of the liquid crystal that the evokes spinning movement (in-plane changes) in real estate is opposite directions forms by the voltage between pixel electrode and opposite electrode.The aligning agent for liquid crystal that synthesis example 3 is obtained (C1) is spun on ready above-mentioned electroded substrate.Then, on the hot plate of 80 ℃, be dried after 90 seconds, in the heated air circulation type stove of 160 ℃, burn till 30 minutes, form the liquid crystal orientation film of thickness 100nm.Then, across polarization plates, to coated surface, irradiate the polarized UV rays 50mJ/cm of 313nm 2(irradiating for 1 time), obtains the substrate with liquid crystal orientation film.In addition, on the glass substrate with the column spacer that is highly 4 μ m that is not formed with electrode as substrate in opposite directions, also use same formation of aligning agent for liquid crystal (C1) to film, implementation orientation processing.Printing and sealing agent on the liquid crystal orientation film of a side group plate (XN-1500T processed of Xie Li KCC).Then, by the substrate of opposite side so that after the condition that the relative orientation direction of liquid crystal orientation film is 0 ° fits, curing sealant, makes negative crystal born of the same parents.To this negative crystal born of the same parents, utilize decompression injection method to inject liquid crystal MLC-2041 (Merck joint-stock company), sealing inlet, the liquid crystal structure cell of (In-Plane Switching) mode liquid crystal display element (liquid crystal display cells of transverse electric field type of drive) structure that obtains possessing IPS.
Manufacture after liquid crystal structure cell, by the reorientation that the baking ovens of 120 ℃ carry out 60 minutes, process.Afterwards, make between the pixel electrode of liquid crystal structure cell and opposite electrode, in short-circuit condition, to liquid crystal structure cell, to irradiate by the ultraviolet 20J/cm of 365nm bandpass filter 2(irradiating for 2 times).
(ghost evaluates 2)
The IPS pattern that embodiment 3 is prepared is arranged between two Polarizers that the mode with polarizing axis quadrature configures with liquid crystal structure cell, make backlight luminous not executing under alive state, so that the brightness of transmitted light reaches the arrangement angles that minimum condition has been adjusted liquid crystal structure cell.Then, the 2nd region from pixel being reached to the darkest angle plays the anglec of rotation that the 1st region reaches while making the rotation of liquid crystal structure cell till the darkest angle and calculates as initial stage orientation position angle.Then,, in 60 ℃ of baking ovens, with frequency 30Hz, apply the 16V of 168 hours pPalternating voltage.Then, make between the pixel electrode of liquid crystal structure cell and opposite electrode, in short-circuit condition, under this state, in room temperature, to place 1 hour.After placement, measure in the same manner orientation position angle, the azimuthal difference of orientation exchanging before and after driving is calculated as angle delta (deg.).Ghost evaluation result is shown in table 2.
(embodiment 4)
Except using aligning agent for liquid crystal (C2) replacement aligning agent for liquid crystal (C1), with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(embodiment 5)
Except using aligning agent for liquid crystal (C3) replacement aligning agent for liquid crystal (C1), with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(embodiment 6)
Except using aligning agent for liquid crystal (D1) to replace aligning agent for liquid crystal (C1), the exposure of polarized UV rays is made as to 500mJ/cm 2in addition, with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(embodiment 7)
Except using aligning agent for liquid crystal (E1) replacement aligning agent for liquid crystal (C1), with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(embodiment 8)
Except using aligning agent for liquid crystal (F1) to replace aligning agent for liquid crystal (C1), the exposure of polarized UV rays is made as to 500mJ/cm 2in addition, with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(embodiment 9)
Except using aligning agent for liquid crystal (C) replacement aligning agent for liquid crystal (C1), with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(comparative example 4)
Except using aligning agent for liquid crystal (C) to replace aligning agent for liquid crystal (C1), beyond not carrying out irradiating for 2 times, with the step identical with embodiment 3, manufacture after liquid crystal structure 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 exposure of polarized UV rays is made as to 500mJ/cm 2, beyond not carrying out irradiating for 2 times, with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
(comparative example 6)
Except using aligning agent for liquid crystal (E) to replace aligning agent for liquid crystal (C1), beyond not carrying out irradiating for 2 times, with the step identical with embodiment 3, manufacture after liquid crystal structure 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 exposure of polarized UV rays is made as to 500mJ/cm 2, beyond not carrying out irradiating for 2 times, with the step identical with embodiment 3, manufacture after liquid crystal structure cell, carry out ghost evaluation.
[table 2]
Results verification by table 2, significantly depart from any orientation position angle after AC drives of not adding in the comparative example 4～7 of polymerizable compound, but added polymerizable compound and after the manufacture of liquid crystal structure cell, carry out UV irradiation (2 times irradiate) even embodiment 3～8 after AC drives, compare with comparative example 4～7, does not almost depart from its orientation position angle yet.In addition, the known embodiment 9 that has the polymkeric substance of optical polymerism group and carry out UV irradiation (2 times irradiate) on side chain after the manufacture of liquid crystal structure cell that contains compares with the comparative example 4 that does not carry out irradiating for 2 times, be orientated azimuthal depart from little.Its reason is presumed as follows: embodiment 3～9 is by being radiated at the optical polymerism group generation polymerization of polymerizable compound on alignment films interface or polymkeric substance for 2 times, by liquid crystal orientation film surface cure, be therefore orientated azimuthal depart from very little.

Claims (11)

1. a transverse electric field drives the manufacture method with liquid crystal display cells, it is characterized in that, being included in coating of liquid crystalline alignment agent on substrate forms after liquid crystal orientation film implementation orientation processing, Jie by liquid crystal by a pair of substrate that has formed this liquid crystal orientation film according to the condition subtend that described liquid crystal orientation film is relative is configured, make liquid crystal structure cell, then this liquid crystal structure cell is carried out to irradiation, the operation that the optical polymerism group in liquid crystal and/or in liquid crystal orientation film is reacted.
2. transverse electric field as claimed in claim 1 drives the manufacture method with liquid crystal display cells, it is characterized in that, described liquid crystal contains the polymerizable compound with described optical polymerism group.
3. transverse electric field as claimed in claim 1 or 2 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains described optical polymerism group.
4. the transverse electric field as described in any one in claim 1～3 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains the polymkeric substance on side chain with described optical polymerism group.
5. the transverse electric field as described in any one in claim 1～4 drives the manufacture method with liquid crystal display cells, it is characterized in that, described aligning agent for liquid crystal contains the polymerizable compound with described optical polymerism group.
6. the transverse electric field as described in any one in claim 3～5 drives the manufacture method with liquid crystal display cells, it is characterized in that, described optical polymerism group is the group being selected from optical polymerism group shown below;
[changing 1]
In formula, Me represents methyl.
7. the transverse electric field as described in any one in claim 1～6 drives the manufacture method with liquid crystal display cells, it is characterized in that, described orientation process is undertaken by the irradiation of polarized UV rays.
8. the transverse electric field as described in any one in claim 1～7 drives the manufacture method with liquid crystal display cells, it is characterized in that, in described orientation process, the photoreactive group with the structure that is selected from following formula (A-1)～(A-7) reacts,
[changing 2]
9. the transverse electric field as described in any one in claim 1～8 drives the manufacture method with liquid crystal display cells, it is characterized in that, the polymkeric substance that described aligning agent for liquid crystal comprises contain be selected from polyimide precursor and by its imidizate and at least a kind of polyimide.
10. the transverse electric field as described in any one in claim 1～9 drives the manufacture method with liquid crystal display cells, it is characterized in that, the contained polymkeric substance of described aligning agent for liquid crystal comprises polysiloxane.
11. transverse electric fields as described in any one in claim 1～10 drive the manufacture method with liquid crystal display cells, it is characterized in that, the contained polymkeric substance of described aligning agent for liquid crystal comprises poly-(methyl) acrylate.
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