CN104937480B - Manufacture method, liquid crystal orientation film, liquid crystal display cells, polymer and the aligning agent for liquid crystal of liquid crystal orientation film - Google Patents

Manufacture method, liquid crystal orientation film, liquid crystal display cells, polymer and the aligning agent for liquid crystal of liquid crystal orientation film Download PDF

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CN104937480B
CN104937480B CN201380049349.8A CN201380049349A CN104937480B CN 104937480 B CN104937480 B CN 104937480B CN 201380049349 A CN201380049349 A CN 201380049349A CN 104937480 B CN104937480 B CN 104937480B
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liquid crystal
side chain
temperature
orientation film
polymeric membrane
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CN104937480A (en
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后藤耕平
根木隆之
川月喜弘
近藤瑞穗
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Nissan Chemical Corp
University of Hyogo
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Nissan Chemical Corp
University of Hyogo
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133726—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films made of a mesogenic material

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  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
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  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention provides autofrettage, liquid crystal orientation film and the liquid crystal display cells of a kind of efficient liquid crystal orientation film using light.Make polysiloxanes in the present invention and polymerize with liquid crystal liquid crystal property and the monomer of photosensitive group and free-radical polymerised group and obtain polymer, aligning agent for liquid crystal is prepared with this.After obtaining side chain type polymeric membrane (1) by the aligning agent for liquid crystal, irradiation polarized UV rays carry out orientation process, are then heated, re-align the side chain (2) of side chain type polymeric membrane (1).Then, further heated under high-temperature, state immobilization will be re-aligned, make liquid crystal orientation film.Heating-up temperature for reorientation is set to the temperature range of temperature of the temperature of 10 DEG C of the lower limit for height of such as 200 DEG C temperature ranges such as the following, that liquid crystal liquid crystal property is presented than side chain type polymeric membrane 1 to 10 DEG C lower than its upper limit.Liquid crystal display cells are manufactured using obtained liquid crystal orientation film.

Description

The manufacture method of liquid crystal orientation film, liquid crystal orientation film, liquid crystal display cells, polymer And aligning agent for liquid crystal
Technical field
The present invention relates to the polymer and liquid crystal aligning of the manufacture method of the suitable efficient liquid crystal orientation film using light Agent, and liquid crystal orientation film and liquid crystal display cells.
Background technology
Liquid crystal display cells are as light weight, slim and low power consumption display device it is well known that being applied in recent years big Television set purposes of type etc., has achieved alarming development.
Liquid crystal layer is for example clamped and formed by liquid crystal display cells with a pair of transparent substrates with electrode.Such In liquid crystal display cells, to make liquid crystal be in required state of orientation between substrate, made using the organic film being made up of organic material For liquid crystal orientation film.
That is, liquid crystal orientation film is the member of formation of liquid crystal display cells, is formed in the substrate and liquid crystal for clamping liquid crystal On the face of contact, play a part of making liquid crystal be orientated towards certain orientation between the substrate.
In addition, for liquid crystal orientation film, it is orientated except the certain orientation such as making liquid crystal court with the direction of substrate-parallel Beyond effect, the effect of the pre-tilt angle of control liquid crystal is also required sometimes.The energy of the control liquid crystal aligning of such liquid crystal orientation film Power (calls tropism control ability in the following text.) it is by carrying out orientation process to the organic film for forming liquid crystal orientation film to assign.
As the method for orientation treatment of the liquid crystal orientation film for assigning tropism control ability, all the time known friction Method.Rubbing manipulation refers to following method：For organic films such as the polyvinyl alcohol on substrate, polyamide, polyimides, its surface is used The cloth of cotton, nylon, polyester etc. wipes (friction) towards certain orientation, liquid crystal is orientated towards the direction (frictional direction) of wiping.This rubs Embrocation can easily realize the state of orientation of relatively stable liquid crystal, therefore in the manufacturing process of existing liquid crystal display cells There is use always.Then, it is in the past main to select reliability and the electricity such as heat resistance as the organic film used in liquid crystal orientation film The organic film of the polyimide of excellent.
However, in the rubbing manipulation to be rubbed to the liquid crystal orientation film surface being made up of polyimides etc., airborne dust and electrostatic Generation turn into problem sometimes.Further, since the electricity on the High precision of liquid crystal display cells in recent years or corresponding substrate Bumps caused by the switch active element of pole or liquid crystal drive, liquid crystal orientation film surface can not be carried out uniformly with cloth sometimes Ground friction, uniform liquid crystal aligning can not be realized.
Then, other method for orientation treatment as the liquid crystal orientation film without friction, optical alignment method has been carried out greatly Quantity research.
Optical alignment method has various methods, but is all to form liquid crystal aligning using the light of rectilinearly polarized light or collimation Anisotropy is formed in the organic film of film, makes liquid crystal aligning along the anisotropy.
As main optical alignment method, it is known that the optical alignment method of breakdown type.Such as polarized UV is irradiated to polyimide film Line, anisotropic decomposition is brought it about using the polarization direction dependence of the ultraviolet radiation absorption of molecular structure.Then, using not The polyimides for decomposing and remaining makes liquid crystal aligning (for example, referring to patent document 1).
In addition, it is also known that the optical alignment method of photo-crosslinking type or photoisomerization type.Such as use poly- vinyl cinnamate, irradiation Polarized UV rays, dimerization (cross-linking reaction) occurs in the double bond part of 2 side chains with polarizing parallel light.Then, make Liquid crystal is orientated (for example, referring to non-patent literature 1) towards the direction orthogonal with polarization direction.In addition, there is azobenzene using side chain Side chain type it is high molecular in the case of, irradiate polarized UV rays, with polarize parallel light side chain azobenzene part occur it is different Structureization is reacted, and liquid crystal is orientated towards the direction orthogonal with polarization direction (for example, referring to non-patent literature 2).
In addition, in recent years in optical alignment method, combined heated process while photo-irradiation treatment is investigated, improves liquid crystal The technology of the tropism control ability of alignment films (for example, referring to patent document 2~4).
Example as more than, the method for orientation treatment using the liquid crystal orientation film of optical alignment method be using photo-crosslinking or The reaction of the light such as photoisomerization reaction.Therefore, to the material of the formation for liquid crystal orientation film, it is desirable to the purpose can be realized Photoreactivity.For example, in above-mentioned non-patent literature 1, poly- vinyl cinnamate is used in the material of liquid crystal orientation film.
On the other hand, superior in reliability as described above etc. is required to liquid crystal orientation film.Therefore, utilize friction conventional In the liquid crystal orientation film of processing, it can be used the polyimide of the reliabilities such as heat resistance as described above and good electric performance organic Film.Therefore, in the liquid crystal orientation film using optical alignment method, also require to take into account photoreactivity and reliability.
Recently, in the field of high polymer material, it is known that for example gather acrylate copolymer and siloxane polymer respectively Compound and carrying out be obtained by mixing the high polymer materials of high reliability such as acrylic acid-siloxanes mixing material technology (for example, With reference to patent document 5~9).
However, in the field using the liquid crystal orientation film for the optical alignment method that must be adapted for light reaction, do not import also Cross mixing material of such high reliability etc..
Prior art literature
Patent document
Patent document 1：No. 3893659 specifications of Japanese Patent No.
Patent document 2：Japanese Patent Laid-Open 2007-304215 publications
Patent document 3：Japanese Patent Laid-Open 2007-232934 publications
Patent document 4：Japanese Patent Laid-Open 2008-276149 publications
Patent document 5：Japanese Patent Laid-Open 7-243173 publications
Patent document 6：Japanese Patent Laid-Open 9-208642 publications
Patent document 7：Japanese Patent Laid-Open 4-261454 publications
Patent document 8：Japanese Patent Laid-Open 2003-313233 publications
Patent document 9：Japanese Patent Laid-Open 1-168971 publications
Non-patent literature
Non-patent literature 1：M.Shadt etc., Jpn.J.Appl.Phys.31,2155 (1992)
Non-patent literature 2：K.Ichimura etc., Chem.Rev.100,1847 (2000)
The content of the invention
The technical problems to be solved by the invention
As described above, the method for orientation treatment as liquid crystal display cells, optical alignment method with it is in the past industrial applied Rubbing manipulation, which is compared, need not carry out friction process, therefore possess very big advantage.For example, can be to irregular liquid crystal display on surface The substrate of element implements orientation process, applies to the method for orientation treatment of the liquid crystal orientation film of industrial manufacture process.In addition, with By rubbing, the rubbing manipulation for making tropism control ability nearly constant is compared, can be by making the exposure of polarised light in optical alignment method Change to control tropism control ability.
However, in optical alignment method, in the case where to realize with the tropism control ability of same degree when using rubbing manipulation, Cause liquid crystal aligning that is poorly efficient, or can not realizing stable sometimes for the exposure of substantial amounts of polarised light.
Such as, it is necessary to irradiate source to polyimide film in the optical alignment method of the breakdown type described in above-mentioned patent document 1 Waited within 60 minutes, it is necessary to long-time and substantial amounts of ultraviolet irradiation in the ultraviolet light of power output 500W high-pressure sodium lamp.In addition, two In the case of the optical alignment method of dimerization type or photoisomerization type, several J (joule)~tens of J or so substantial amounts of purple is also required to sometimes Outside line is irradiated.Further, in the case of the optical alignment method of photo-crosslinking type or photoisomerization type, the heat endurance and light of the orientation of liquid crystal Stability is poor, therefore the problem of bad orientation or display burn-in occurs be present when being made liquid crystal display cells.
Although have studied combined heated process while photo-irradiation treatment as described above, the orientation of liquid crystal orientation film is improved The technology of control ability, but problem in the heat resistance of material be present, and it is molten in the case where heat resistance is enough solvent to be present The problems such as solution property extreme difference.
In addition, the material for optical alignment method for fully taking into account photoreactivity and reliability is not developed also.
Therefore, in optical alignment method, it is desirable to realize the high efficiency of orientation process and stable liquid crystal aligning, it is desirable to develop Liquid crystal orientation film can efficiently be assigned with the manufacture method of the liquid crystal orientation film of excellent tropism control ability.Moreover, the liquid crystal Preferably the manufacture method of alignment films is realized using the polymer of high reliability.
It is an object of the invention to provide the manufacture method and liquid crystal aligning of the efficient liquid crystal orientation film using light Film, and the liquid crystal display cells with gained liquid crystal orientation film are provided.
It is further an object that provide the poly- of the manufacture method for the efficient liquid crystal orientation film for being suitable for use with light Compound and the aligning agent for liquid crystal containing the polymer.
Technical scheme used by solution technical problem
That is, the present invention has following main points.
(1) a kind of manufacture method of liquid crystal orientation film, it is characterised in that have：
Formation embodies the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property within the temperature range of regulation on substrate Process [I]；
The process [II] of polarized UV rays is irradiated to above-mentioned side chain type polymeric membrane,
Above-mentioned side chain type polymeric membrane after ultraviolet irradiation is presented to the model of liquid crystal liquid crystal property in the side chain type polymeric membrane The process [III] heated at interior temperature is enclosed, and
By the above-mentioned side chain polymeric membrane after heating more than process [III] heating-up temperature at a temperature of further carry out The process [IV] of heating.
(2) manufacture method of the liquid crystal orientation film described in above-mentioned (1), wherein, the heating-up temperature of process [III] is than above-mentioned The temperature of 10 DEG C of the lower limit for height of the temperature range of liquid crystal liquid crystal property is presented to the upper limit than the liquid crystal temperature range in side chain type polymeric membrane Temperature in the range of low 10 DEG C of temperature.
(3) manufacture method of the liquid crystal orientation film described in above-mentioned (1) or (2), wherein, the heating-up temperature of process [III] is Less than 200 DEG C of temperature.
(4) manufacture method of the liquid crystal orientation film any one of above-mentioned (1)~(3), wherein, process [III] adds The temperature that hot temperature is re-aligned for the side chain of above-mentioned side chain type polymeric membrane.
(5) manufacture method of the liquid crystal orientation film any one of above-mentioned (1)~(4), wherein, process [III] adds The temperature that hot temperature is re-aligned for the side chain of above-mentioned side chain type polymeric membrane, the heating-up temperature of process [IV] are to make process The temperature of the reorientation immobilization of [III].
(6) manufacture method of the liquid crystal orientation film any one of above-mentioned (1)~(5), wherein, above-mentioned presentation liquid crystal liquid crystal property Photosensitive side chain type polymeric membrane in contained photonasty group be selected from azobenzene, Stilbene, cinnamic acid, cinnamate, Chalcone, cumarin, tolans, at least one kind of derivative group of phenol benzoate.
(7) manufacture method of the liquid crystal orientation film any one of above-mentioned (1)~(6), wherein, above-mentioned side chain type high score Sub- film contains following structure：The structure possesses selected from polyamic acid, polyimides, poly amic acid ester, acrylate, methyl-prop Olefin(e) acid ester, maleimide, alpha-methylene-gamma-butyrolactone and siloxanes at least one kind of composition main chain, and selected from following formula (1) at least one kind of side chain of~formula (5), formula (7) and formula (8).
[changing 1]
(in formula (1), A1And B1Separately represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or- NH-CO-。Y1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or the base of these combinations , the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Group, alkyl or alkoxy substitution.X1Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。l1 1~12 integer is represented, m1 represents 1~3 integer, and n1 represents 1~12 integer.
In formula (2), A2、B2And D1Separately represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、 Or-NH-CO-.Y2Be selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon or these combine Group, the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Plain group, alkyl or alkoxy substitution.X2Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。 R1Represent the alkyl of hydrogen atom or carbon number 1~6.L2 represents 1~12 integer, and m2 represents 1~3 integer, and n2 represents 1~12 Integer.
In formula (3), A3Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.X3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。R2Represent the alkyl of hydrogen atom or carbon number 1~6.L3 is represented 1~12 integer, m3 represent 1~3 integer.
In formula (4), l4 represents 1~12 integer.
In formula (5), A4Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.X4Expression-COO-. Y3It is that the hydrogen atom being bonded on phenyl ring, naphthalene nucleus, cyclohexyl biphenyl or the group of these combinations, these groups can be independently Ground is by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.L5 represent 1~12 it is whole Number, m4 represent 1~3 integer.
In formula (7), A5Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.R3Represent that hydrogen is former Son ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~6, carbon number 1~6 alkoxy or Its group combined.L6 represents 1~12 integer.The hydrogen atom being bonded on phenyl ring in formula (7) can be separately By-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.
In formula (8), A6Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.B3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。W1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrroles Groups of ring, the cyclic hydrocarbon of carbon number 5~8 or these combinations, the hydrogen atom being bonded on these groups can separately by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.
L7 represents 1~12 integer, m5And m6Separately represent 1~3 integer.)
(8) manufacture method of the liquid crystal orientation film any one of above-mentioned (1)~(7), wherein, above-mentioned side chain type high score Sub- film contains polymer, and the polymer is the polysiloxanes (a) for making to have free-radical polymerised group, and with liquid crystal liquid crystal property and The monomer (b) of photosensitive group and free-radical polymerised group carries out polymer obtained by radical polymerization.
(9) manufacture method of the liquid crystal orientation film described in above-mentioned (8), wherein, the liquid crystal liquid crystal property and photonasty of above-mentioned monomer (b) Group be selected from azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolans, phenol benzoate at least Group derived from a kind.
(10) a kind of liquid crystal orientation film, it passes through the manufacturer of the liquid crystal orientation film any one of above-mentioned (1)~(9) Method and be made.
(11) a kind of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned (10).
(12) a kind of polymer, makes the polysiloxanes (a) with free-radical polymerised group, and with liquid crystal liquid crystal property and photosensitive Property group and free-radical polymerised group monomer (b) carry out radical polymerization and obtain.
(13) polymer described in above-mentioned (12), wherein, above-mentioned polysiloxanes (a) is the alkoxy that will contain following formula (10) The alkoxy silane of silane carries out polysiloxanes obtained by polycondensation.
R13 S1Si(OR14)S2 (10)
(in formula (10), R13For the alkyl substituted by acryloyl group, methylacryloyl, styryl or aryl.R14Table Show the alkyl of hydrogen or carbon number 1~5.S1 is 1 or 2, S2 are 2 or 3.)
(14) polymer described in above-mentioned (12) or (13), wherein, the liquid crystal liquid crystal property of above-mentioned monomer (b) and photosensitive group For selected from azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolans, phenol benzoate at least one kind of institute Derivative group.
(15) polymer any one of above-mentioned (12)~(14), wherein, above-mentioned monomer (b) be with by selected from Hydrocarbon, acrylate, methacrylate, maleimide and alpha-methylene-gamma-butyrolactone at least one kind of composition polymerization Property group, and the monomer of at least one kind of side chain selected from following formula (1)~formula (5), formula (7) and formula (8).
[changing 2]
(in formula (1), A1And B1Separately represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or- NH-CO-。Y1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or the base of these combinations , the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Group, alkyl or alkoxy substitution.X1Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。l1 1~12 integer is represented, m1 represents 1~3 integer, and n1 represents 1~12 integer.
In formula (2), A2、B2And D1Separately represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、 Or-NH-CO-.Y2Be selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon or these combine Group, the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Plain group, alkyl or alkoxy substitution.X2Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。 R1Represent the alkyl of hydrogen atom or carbon number 1~6.L2 represents 1~12 integer, and m2 represents 1~3 integer, and n2 represents 1~12 Integer.
In formula (3), A3Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.X3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。R2Represent the alkyl of hydrogen atom or carbon number 1~6.L3 is represented 1~12 integer, m3 represent 1~3 integer.
In formula (4), l4 represents 1~12 integer.
In formula (5), A4Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.X4Expression-COO-. Y3It is that the hydrogen atom being bonded on phenyl ring, naphthalene nucleus, cyclohexyl biphenyl or the group of these combinations, these groups can be independently Ground is by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.L5 represent 1~12 it is whole Number, m4 represent 1~3 integer.
In formula (7), A5Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.R3Represent that hydrogen is former Son ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~6, carbon number 1~6 alkoxy or Its group combined.L6 represents 1~12 integer.The hydrogen atom being bonded on phenyl ring in formula (7) can be separately By-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.
In formula (8), A6Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.B3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。W1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrroles Groups of ring, the cyclic hydrocarbon of carbon number 5~8 or these combinations, the hydrogen atom being bonded on these groups can separately by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.L7 represents 1~12 integer, m5、 And m6Separately represent 1~3 integer.)
(16) polymer any one of above-mentioned (12)~(15), wherein, obtain polysiloxanes relative to 1 mole (a) alkoxy silane when, the usage amount of above-mentioned monomer (b) is 0.5~50 mole.
(17) a kind of aligning agent for liquid crystal, it contains the polymer any one of above-mentioned (12)~(16).
In addition, the side chain type polymeric membrane in the present invention can be used in combination in the range of liquid crystal liquid crystal property and photoreactivity is not lost Side-chain structure without photoreactivity is as the structure included.
If enumerating the example of the side-chain structure without photoreactivity, can enumerate such as the structure of following formula (6).
[changing 3]
In above formula (6), E1Represent singly-bound ,-O- ,-CH2- ,-COO ,-OCO- ,-CONH- or-NH-CO-.
Z represents singly-bound ,-COO ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。
K1 represents 1~12 integer, and p1 and q1 separately represent 0~3 integer.
R4Represent hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alcoxyl of carbon number 1~6 Base, carboxyl or its group combined.
The effect of invention
If using the present invention, can be realized by the manufacture method for the liquid crystal orientation film that can carry out efficient orientation process Using the efficient orientation process of light, liquid crystal orientation film is obtained, the liquid crystal display cells for possessing the liquid crystal orientation film can be obtained.
If moreover, using the present invention, the polymer suitable for liquid crystal orientation film as described above can be obtained, and contain The aligning agent for liquid crystal of the polymer.
Brief description of the drawings
Fig. 1 be schematically to the present invention the first form liquid crystal orientation film manufacture method in anisotropic introducing Handle the figure illustrated；
(a) it is the figure that represents the side chain type polymeric membrane state before polarizing light irradiation,
(b) it is the figure that represents the side chain type polymeric membrane state after polarizing light irradiation,
(c) be represent heating after side chain type polymeric membrane state figure,
(d) it is to carry out the 2nd heating by the figure of the side chain type polymeric membrane state after being orientated immobilization after representing heating.
Fig. 2 be schematically to the present invention the first form liquid crystal orientation film manufacture method in anisotropic introducing Handle the figure illustrated；
(a) it is the figure that represents the side chain type polymeric membrane state before polarizing light irradiation,
(b) it is the figure that represents the side chain type polymeric membrane state after polarizing light irradiation,
(c) be represent heating after side chain type polymeric membrane state figure,
(d) it is to carry out the 2nd heating by the figure of the side chain type polymeric membrane state after being orientated immobilization after representing heating.
Fig. 3 be schematically to the present invention the second form liquid crystal orientation film manufacture method in anisotropic introducing Handle the figure illustrated；
(a) it is the figure that represents the side chain type polymeric membrane state before polarizing light irradiation,
(b) it is the figure that represents the side chain type polymeric membrane state after polarizing light irradiation,
(c) be represent heating after side chain type polymeric membrane state figure.
Fig. 4 be schematically to the present invention the second form liquid crystal orientation film manufacture method in anisotropic introducing Handle the figure illustrated；
(a) it is the figure that represents the side chain type polymeric membrane state before polarizing light irradiation,
(b) it is the figure that represents the side chain type polymeric membrane state after polarizing light irradiation,
(c) be represent heating after side chain type polymeric membrane state figure.
Fig. 5 be the liquid crystal orientation film of the gained of embodiment 4 with the ultraviolet linearly polarized light electric field vector parallel through irradiation and Vertical ultraviolet absorption spectrum.
Fig. 6 be the liquid crystal orientation film of the gained of embodiment 6 with the ultraviolet linearly polarized light electric field vector parallel through irradiation and Vertical ultraviolet absorption spectrum.
Embodiment
Present inventor has performed conscientiously studying, following discovery is as a result obtained, so as to complete the present invention.
The manufacture method of the liquid crystal orientation film of the present invention is using using the photosensitive side chain that can embody liquid crystal liquid crystal property Type polymeric membrane, without friction treatment but pass through polarizing light irradiation carry out orientation process method.
The photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property can be presented contains polymer and formed, and the polymer is to make tool There is the polysiloxanes (a) of free-radical polymerised group, and there is liquid crystal liquid crystal property and photosensitive group and free-radical polymerised group Monomer (b) carry out the polymer that forms of radical polymerization.
After polarizing light irradiation, the process heated to above-mentioned side chain type polymeric membrane is set, manufactures liquid crystal orientation film. Now, first heating process and second heating process 2 stages different from heating process temperature are arranged to.Further, pass through The heating-up temperature of the first heating process after polarizing light irradiation amount and polarizing light irradiation is optimized, it is real in liquid crystal orientation film Now efficient orientation process.Afterwards, in the second heating process, the state of orientation formed in liquid crystal orientation film is fixed Change.As a result, in the present invention, it be can be achieved in liquid crystal orientation film efficiently to assign good tropism control ability.
The present invention is described in detail below.
＜ side chain types macromolecule (polymer) and side chain type polymeric membrane ＞
Photosensitive side chain type being used in the manufacture method of the liquid crystal orientation film of the present invention, can embodying liquid crystal liquid crystal property is high Molecular film is photosensitive side chain type polymeric membrane, the i.e. film of polymer that liquid crystal liquid crystal property is embodied within the temperature range of regulation. Moreover, the side chain being bonded on the main chain of polymer has photonasty, light can be sensed and crosslink reaction, isomerization reaction or Light fries' rearrangement.
What is be bonded on main chain there is photosensitive group to be not particularly limited, and preferably senses light and crosslinks reaction or light The structure of fries' rearrangement.Now, if exposed to external pressures such as heat, realized orientation control can be also kept steadily in the long term Ability processed.
The present invention liquid crystal orientation film manufacture method in use, liquid crystal liquid crystal property can be presented under defined temperature range As long as the structure of photosensitive side chain type polymeric membrane can meet that its characteristic is then not particularly limited, it is preferably high in the side chain type There is rigid primitive (mesogen) composition in the side-chain structure of molecule.Now, the side chain type macromolecule is used for liquid crystal aligning During film, stable liquid crystal aligning can be obtained.
As the high molecular structure of such side chain type, such as can include main chain and side chain bonded thereto, the side Before chain has the primitive compositions such as xenyl, terphenyl base, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and is bonded in End, the structure for sensing light and carrying out the photonasty group of cross-linking reaction or isomerization reaction, or can include main chain It is also primitive composition with side chain bonded thereto, the side chain and there is the phenylamino benzoic acid ester group for carrying out light Fries rearrangement Structure.
In addition, below to photonasty used in the manufacture method of the liquid crystal orientation film of the present invention, that liquid crystal liquid crystal property can be presented Side chain type polymeric membrane be properly termed as presenting the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property, or referred to as this hair Bright side chain type polymeric membrane.
As the concrete example of the photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property is presented of the present invention, it is preferably provided with as follows Construction；The construction possesses by selected from acrylate, methacrylate, maleimide, alpha-methylene-gamma-butyrolactone, silicon It is oxygen alkane, itaconate, fumarate, maleate, styrene, vinyl, maleimide, ENB, polyamic acid, poly- Acid imide, polyureas, polyamide, polyethers and poly amic acid ester at least one kind of composition main chain, and selected from following formulas (1)~ At least one kind of side chain of formula (5), formula (7) and formula (8).
[changing 4]
In above formula (1), A1And B1Separately represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or- NH-CO-。
Y1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or the base of these combinations , the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Group, alkyl or alkoxy substitution.
X1Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。
L1 represents 1~12 integer, and m1 represents 1~3 integer, and n1 represents 1~12 integer.
In above formula (2), A2、B2And D1Separately represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、 Or-NH-CO-.
Y2It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or the base of these combinations , the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Group, alkyl or alkoxy substitution.
X2Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。
R1Represent the alkyl of hydrogen atom or carbon number 1~6.
L2 represents 1~12 integer, and m2 represents 1~3 integer, and n2 represents 1~12 integer.
In above formula (3), A3Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.
X3Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-, R2Represent hydrogen atom or carbon The alkyl of number 1~6.
L3 represents 1~12 integer, and m3 represents 1~3 integer.
In above formula (4), l4 represents 1~12 integer.
In above formula (5), A4Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.
X4Expression-COO-.
Y3It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl or groups of these combinations, the hydrogen atom being bonded on these groups can be with Separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution.
L5 represents 1~12 integer, and m4 represents 1~3 integer.
In above formula (7), A5Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.
R3Represent hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~6 alkyl, The alkoxy of carbon number 1~6 or its group combined.
L6 represents 1~12 integer.
The hydrogen atom being bonded on phenyl ring in formula (7) can be separately by-NO2,-CN ,-CH=C (CN)2,-CH= CH-CN, halogen group, alkyl or alkoxy substitution.
In above formula (8), A6Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-.
B3Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。
W1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or the base of these combinations , the hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen Group, alkyl or alkoxy substitution.
L7 represents 1~12 integer, m5And m6Separately represent 1~3 integer.
Side chain represented by above formula (1)~formula (5), formula (7) and formula (8) is included with biphenyl, terphenyl, benzyl ring Structure of the group of hexyl, phenol benzoate, azobenzene etc. as primitive composition.Moreover, its leading section has and following at least appointed One side's group, i.e. have and sense light and dimerization occurs, carries out the photonasty group of cross-linking reaction, or including master Chain and side chain bonded thereto, the side chain are also primitive composition and have the phenol benzoate for carrying out light Fries rearrangement Base.
The photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property is presented of the present invention can be following structure, and the structure is removed Outside at least one kind of side chain containing above-mentioned main chain and selected from above-mentioned formula (1)~formula (5), formula (7) and formula (8), not Lose in the range of liquid crystal liquid crystal property and photoreactivity and with the side-chain structure without photoreactivity.
If enumerating the example of the side-chain structure without photoreactivity, can enumerate such as the structure of following formula (6).
[changing 5]
In above formula (6), E1Represent singly-bound ,-O- ,-CH2- ,-COO ,-OCO- ,-CONH- or-NH-CO-.
Z represents singly-bound ,-COO ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-。
K1 represents 1~12 integer, and p1 and q1 separately represent 0~3 integer.
R4Represent hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alcoxyl of carbon number 1~6 Base, carboxyl or its group combined.
<Polysiloxanes (a)>
To the photosensitive side chain type that liquid crystal liquid crystal property the is presented height used in the manufacture method of the liquid crystal orientation film of the present invention The polysiloxanes (a) with free-radical polymerised group used in the formation of molecular film illustrates.
The polysiloxanes (a) of material as side chain type polymeric membrane is by the alkoxyl silicone represented by containing following formula (10) Polysiloxanes obtained by the alkoxy silane polycondensation of alkane.
R13 S1Si(OR14)S2 (10)
In above formula (10), R13For the alkyl substituted by acryloyl group, methylacryloyl, styryl or aryl.
R14Represent the alkyl of hydrogen or carbon number 1~5.
S1 is 1 or 2, S2 are 2 or 3.
The R of alkoxy silane represented by above formula (10)13(hereinafter also referred to as the second specific organic group) is by selected from third Enoyl-, methylacryloyl, at least one substituted alkyl of styryl and aryl.Substituted hydrogen atom is 1 More than, preferably 1.
The carbon number of alkyl preferably 1~30, more preferably 1~20.Further preferred 1~10.Alkyl can be that straight-chain also may be used To be branched, more preferably straight-chain.
The R of alkoxy silane represented by above formula (10)14For the alkyl of carbon number 1~5, preferably carbon number 1~3, particularly preferably Carbon number 1~2.
The concrete example of the alkoxy silane represented by above formula (10) is enumerated, but is not limited to this.
As the alkoxy silane represented by above formula (10), for example, 3- methacryloxypropyls trimethoxy silicon Alkane, 3- methacryloxypropyls, methacryloxymethyl trimethoxy silane, methacryl Epoxide MTES, 3- acryloxypropyls trimethoxy silane, 3- acryloxypropyl triethoxysilicanes Alkane, acryloyl-oxyethyl trimethoxy silane, acryloyl-oxyethyl triethoxysilane, styryl ethyl trimethoxy Silane, styryl ethyl triethoxysilane, 3- (N- styrylmethyl -2- aminoethylaminos) propyl trimethoxy silicon Alkane.
In the manufacture of polysiloxanes (a), beyond the alkoxy silane represented by above formula (10), to improve and substrate For the purpose of adaptation and the compatibility of liquid crystal molecule etc., in the range of the effect of the present invention is not damaged, it is possible to use Yi Zhonghuo Alkoxy silane represented by a variety of following formulas (11).It is various that alkoxy silane represented by following formula (11) can assign polysiloxanes Characteristic, therefore can be selected according to characteristic one or more.
(R18)nSi(OR19)4-n (11)
In above formula (11), R18For hydrogen atom or can be by hetero atom, halogen atom, amino, glycidoxy, sulfydryl, isocyanide The alkyl of the carbon number 1~10 of perester radical or Carbamido substituted.
In above formula (11), R19For carbon number 1~5, the alkyl of preferred carbon number 1~3.
In above formula (11), n is 0~3, preferably 0~2 integer.
The R of alkoxy silane represented by above formula (11)18For the alkyl of hydrogen atom or carbon number 1~10 (hereinafter also referred to as 3rd specific organic group).
As the example of the 3rd specific organic group, there is aliphatic alkyl；As aliphatic ring, aromatic ring and heterocycle The alkyl of ring structure；Alkyl with unsaturated bond；And can contain hetero atom such as oxygen atom, nitrogen-atoms, sulphur atom etc., The alkyl of carbon number 1~6 with branched structure.Moreover, the 3rd specific organic group can be by halogen atom, amino, epoxy third Epoxide, sulfydryl, NCO, urea groups etc. substitute.
The concrete example of alkoxy silane represented by above formula (11) exemplified below, but not limited to this.3- (2- amino can be enumerated Diethylaminobutyyl) trimethoxy silane, 3- (2- aminoethylaminopropyls) triethoxysilane, 2- aminoethylamino first Base trimethoxy silane, 2- (2- aminoethylthios ethyl) triethoxysilane, 3- Mercaptopropyltriethoxysilanes, sulfydryl MTMS, VTES, 3- NCOs propyl-triethoxysilicane, trifluoro propyl front three TMOS, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, dimethyl Diethoxy silane, dimethyldimethoxysil,ne, diethyldiethoxysilane, diethyldimethoxysilane, diphenyl Dimethoxysilane, diphenyl diethoxy silane, 3-amino propyl methyl diethoxy silane, 3-dimethyl Ethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-urea groups Propyl trimethoxy silicane and γ-ureido-propyl tripropoxy silane etc..
In the alkoxy silane represented by above formula (11), the alkoxy silane that n is 0 is tetraalkoxysilane.Due to four Alkoxy silane is easily condensed to yield polysiloxanes (a) used in the present invention with the alkoxy silane represented by formula (10), because And it is preferred that.
As the alkoxy silane that n in formula (11) is 0, more preferably tetramethoxy-silicane, tetraethoxysilane, four propoxyl group Silane or four butoxy silanes, particularly preferred tetramethoxy-silicane or tetraethoxysilane.
In the present invention, 1~30 mole of % formula is contained in the whole alkoxy silanes used in the manufacture of polysiloxanes (a) (10) alkoxy silane represented by, particularly preferably containing 5~20 moles of %.
<Monomer (b)>
The photosensitive side chain type high score that liquid crystal liquid crystal property is presented used in the manufacture method of the liquid crystal orientation film of the present invention Monomer (b) used in the formation of sub- film has liquid crystal liquid crystal property and photosensitive group and free-radical polymerised group.
The liquid crystal liquid crystal property of monomer (b) and photosensitive group be selected from azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, Cumarin, tolans, at least one kind of derivative group of phenol benzoate.
For example, monomer (b) is with by selected from hydrocarbon, acrylate, methacrylate, maleimide and α-methylene The polymerizable group of at least one kind of composition of base-gamma-butyrolacton, and selected from above formula (1)~formula (5), formula (7) and formula (8) The monomer of at least one kind of side chain.
Monomer (b) can be used together with above-mentioned polysiloxanes (a), form polymer, available for the side for forming the present invention Chain polymeric membrane.
<The high molecular manufacture of side chain type>
Side chain type macromolecule in the side chain type polymeric membrane of the present invention contains by making above-mentioned polysiloxanes (a) and tool There is liquid crystal liquid crystal property and the monomer (b) of photosensitive group and free-radical polymerised group carries out polymer obtained by radical polymerization.
Polymer can for example be obtained by following polymerisation：Make polysiloxanes (a) and with liquid crystal liquid crystal property and photosensitive The monomer (b) of group and free-radical polymerised group is in the solvent coexisted with polymerization initiator etc., in 50~110 DEG C of temperature The polymerisation of lower progress.
The alkoxy silane when usage amount of monomer (b) obtains polysiloxanes (a) relative to 1 mole, preferably 0.5~50 rubs You, further preferred 1~10 mole.
As long as used solvent can dissolve polysiloxanes (a) and with liquid crystal liquid crystal property and photosensitive when obtaining polymer The monomer (b) of group and free-radical polymerised group, the polymerization initiator being added as needed on etc., are not particularly limited.
As the concrete example of solvent, such as ethylene glycol single methyl ether, ethylene glycol monomethyl ether, methyl cellosolve second can be enumerated Acid esters, ethyl cellosolve acetate, diethylene glycol monomethyl ether, TC, propane diols, propylene glycol monomethyl Ether, propylene glycol methyl ether acetate, propylene glycol monopropyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, hexamethylene Ketone, 2- butanone, 3- methyl -2 pentanone, 2 pentanone, 2-HEPTANONE, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyls Ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyls methyl butyrate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxyl ethyl propionates, 3- ethoxypropanoates, methyl pyruvate, ethyl pyruvate, acetic acid Ethyl ester, butyl acetate, ethyl lactate, butyl lactate, DMF, DMA, N- methylpyrroles Alkanone, N- ethyl pyrrolidones etc..
As above-mentioned polymerization initiator, such as 2 can be enumerated, 2 '-azodiisobutyronitrile (AIBN), 2,2 '-azo two- The azo-compound such as (2,4- methyl pentane nitrile), 2,2 '-azo two-(4- methoxyl groups -2,4- methyl pentane nitrile), benzoyl peroxide first The organic peroxide such as acyl, lauroyl peroxide, tert-Butyl peroxypivalate, 1,1 '-bis--(t-butylperoxy) hexamethylene And hydrogen peroxide.Wherein, such as preferred azodiisobutyronitrile (AIBN).
The content of polymerization initiator is relative to 1 mole of above-mentioned monomer (b) preferably 3~50 moles of %, and further preferred 5~30 Mole %.
<The manufacture method of liquid crystal orientation film>
Then, the manufacture method of the liquid crystal orientation film of the present invention is illustrated.
In the manufacture method of the liquid crystal orientation film of the present invention, after forming film on substrate with above-mentioned side chain type macromolecule, Irradiate polarized UV rays.Then, efficiently realized to side chain type polymeric membrane introducing anisotropy by carrying out the 1st heating, Possesses the liquid crystal orientation film of excellent liquid crystal aligning control ability by the 2nd being fixed of heating, manufacture again.
In more detail, using the light reaction in the side chain type macromolecule of above-mentioned side chain type polymeric membrane and by based on liquid crystal Property self assembly and the principle of molecular reorientation that induces, efficiently introduce anisotropy to side chain type polymeric membrane.
Moreover, in the manufacture method of the liquid crystal orientation film of the present invention, as the high molecular photoreactivity base of side chain type In the case of structure of the group with photocrosslinking reaction group, after forming film on substrate using the side chain type macromolecule, irradiation is inclined The ultraviolet that shakes carries out first orientation processing, then, is carried out at a temperature of side chain type polymeric membrane is presented in the range of liquid crystal liquid crystal property 1st heating (claims first to heat), implements the reorientation process as second orientation processing.
Then, after carrying out above-mentioned reorientation process, more than above-mentioned 1st heating-up temperature at a temperature of, then carry out the 2nd time Heating (claim second heat), make containing polysiloxane structure partial condensates.Then, carried out in heating by second The anisotropic immobilization introduced in side chain type polymeric membrane is heated with light irradiation and first, high efficiency can be completed Liquid crystal orientation film manufacture.Simultaneously, it is possible to provide the high liquid crystal orientation film of the reliability based on polysiloxane structure.
More specifically, the manufacture method of liquid crystal orientation film of the invention includes：
[I] forms the photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property is embodied within the temperature range of regulation on substrate Process,
The process that [II] irradiates polarized UV rays to the side chain type polymeric membrane obtained in process [I],
The process that [III] heats to the side chain type polymeric membrane through polarized UV rays irradiation in process [II], and
[IV] to the side chain type polymeric membrane of heating in process [III] at the temperature different from process [III] further The process heated.
Hereinafter, high molecular hair of side chain type of the structure as photoreactive group with photocrosslinking reaction group will be used It is bright to be referred to as the first form, the side chain type macromolecule of the structure as photoreactive group with light fries' rearrangement group will be used The present invention be referred to as the second form, reference picture 1 (a)~(d), Fig. 2 (a)~(d), Fig. 3 (a)~(c) and Fig. 4 (a)~(c) It is further illustrated.
Pass through the side chain type in the manufacture method of the liquid crystal orientation film of the first form of the invention shown in Fig. 1 (a)~(d) Anisotropic introducing processing in polymeric membrane, the ultraviolet irradiation amount of process [II] reach maximum ultraviolet in Δ A and shone In the case of in the range of the 1%~15% of the amount of penetrating, the side chain type polymeric membrane 1 of the present invention is formed on substrate first.Such as Fig. 1 (a) shown in, forming side chain 2 in the side chain type polymeric membrane 1 on substrate has the structure of random alignment.Along side chain type high score The random alignment of the side chain 2 of sub- film 1, the primitive composition and photonasty group of side chain 2 also random orientation, the side chain type polymeric membrane 1 is in isotropism.
In addition, Δ A refers in the side chain type polymeric membrane of the present invention, parallel with the polarization direction of polarized UV rays side To ultraviolet absorbance and and polarized UV rays the vertical direction in polarization direction ultraviolet absorbance difference.
Pass through the side chain type in the manufacture method of the liquid crystal orientation film of the first form of the invention shown in Fig. 2 (a)~(d) Anisotropic introducing processing in polymeric membrane, the ultraviolet irradiation amount of process [II] reach maximum ultraviolet in Δ A and shone In the case of in the range of the 15%~70% of the amount of penetrating, the side chain type polymeric membrane 3 of the present invention is formed on substrate first.Such as figure Shown in 2 (a), forming side chain 4 in the side chain type polymeric membrane 3 on substrate has the structure of random alignment.Along side chain type height The random alignment of the side chain 4 of molecular film 3, the primitive composition and photonasty group of side chain 4 also random orientation, the side chain type macromolecule Film 3 is in isotropism.
Pass through the side chain type in the manufacture method of the liquid crystal orientation film of the second form of the invention shown in Fig. 3 (a)~(c) Anisotropic introducing processing in polymeric membrane, is using the knot with light fries' rearrangement group represented by above formula (7) In the case of the high molecular liquid crystal orientation film of side chain type of structure, the ultraviolet irradiation amount of process [II] reaches maximum purple in Δ A In the case of in the range of the 1%~70% of outside line exposure, side chain type polymeric membrane 5 is formed first on substrate.Such as Fig. 3 (a) shown in, forming side chain 6 in the side chain type polymeric membrane 5 on substrate has the structure of random alignment.Along side chain type high score The random alignment of the side chain 6 of sub- film 5, the primitive composition and photonasty group of side chain 6 also random orientation, the side chain type polymeric membrane 5 be in isotropism.
Pass through the side chain type in the manufacture method of the liquid crystal orientation film of the second form of the invention shown in Fig. 4 (a)~(c) Anisotropic introducing processing in polymeric membrane, is using the knot with light fries' rearrangement group represented by above formula (8) In the case of the high molecular liquid crystal orientation film of side chain type of structure, the ultraviolet irradiation amount of process [II] reaches maximum purple in Δ A In the case of in the range of the 1%~70% of outside line exposure, side chain type polymeric membrane 7 is formed first on substrate.Such as Fig. 4 (a) shown in, forming side chain 8 in the side chain type polymeric membrane 7 of the present embodiment on substrate has the structure of random alignment.It is suitable The random alignment of the side chain 8 of side chain type polymeric membrane 7, the primitive composition and photonasty group of side chain 8 also random orientation, the side Chain polymeric membrane 7 is in isotropism.
In the first form of the invention shown in Fig. 1 (a)~(d), the ultraviolet irradiation amount of process [II] reaches most in Δ A In the case of in the range of the 1%~15% of big ultraviolet irradiation amount, isotropic side chain type polymeric membrane 1 is irradiated Polarized UV rays.Then, as shown in Fig. 1 (b), in the side chain 2 arranged on the direction parallel with the polarization direction of ultraviolet The light reactions such as dimerization occur for the photonasty group priorities of the side chain 2a with photonasty group.As a result, light reaction The density of side chain 2a afterwards is slightly elevated on the polarization direction of irradiation ultraviolet, as a result assigns side chain type polymeric membrane 1 with non- Often small anisotropy.
In the first form of the invention shown in Fig. 2 (a)~(d), the ultraviolet irradiation amount of process [II] reaches most in Δ A In the case of in the range of the 15%~70% of big ultraviolet irradiation amount, isotropic side chain type polymeric membrane 3 is shone Penetrate polarized UV rays.Then, as shown in Fig. 2 (b), in the side chain 4 arranged on the direction parallel with the polarization direction of ultraviolet The photonasty group priorities of the side chain 4a with photonasty group the light reaction such as dimerization occurs.As a result, light is anti- The density of side chain 4a after answering raises on the polarization direction of irradiation ultraviolet, as a result assigns side chain type polymeric membrane 3 with smaller Anisotropy.
In the second form of the invention shown in Fig. 3 (a)~(c), using light fries of the use with above formula (7) expression The high molecular liquid crystal orientation film of side chain type of the structure of group is reset, the ultraviolet irradiation amount of process [II] reaches maximum in Δ A Ultraviolet irradiation amount 1%~70% in the range of in the case of, isotropic side chain type polymeric membrane 5 is irradiated partially Shake ultraviolet.Then, as shown in Fig. 3 (b), the tool in the side chain 6 arranged on the direction parallel with the polarization direction of ultraviolet The light reactions such as light fries' rearrangement occur for the photonasty group priorities for having the side chain 6a of photonasty group.As a result, light reaction The density of side chain 6a afterwards is slightly elevated on the polarization direction of irradiation ultraviolet, as a result assigns the side chain type macromolecule of the present invention Film 5 is with very small anisotropy.
In the second form of the invention shown in Fig. 4 (a)~(c), using light fries of the use with above formula (8) expression The high molecular liquid crystal orientation film of side chain type of the structure of group is reset, the ultraviolet irradiation amount of process [II] reaches maximum in Δ A Ultraviolet irradiation amount 1%~70% in the range of in the case of, isotropic side chain type polymeric membrane 7 is irradiated partially Shake ultraviolet.Then, as shown in Fig. 4 (b), the tool in the side chain 8 arranged on the direction parallel with the polarization direction of ultraviolet The light reactions such as light fries' rearrangement occur for the photonasty group priorities for having the side chain 8a of photonasty group.As a result, light reaction The density of side chain 8a afterwards raises on the polarization direction of irradiation ultraviolet, as a result assigns side chain type polymeric membrane 7 with less Anisotropy.
Then, in the first form of the invention shown in Fig. 1 (a)~(d), the ultraviolet irradiation amount of process [II] is in Δ A reach maximum ultraviolet irradiation amount 1%~15% in the range of in the case of, to the side of the invention after polarizing light irradiation Chain polymeric membrane 1 heats, and it is in mesomorphic state to make it.Then, as shown in Fig. 1 (c), in side chain type polymeric membrane 1, with irradiation The amount of the cross-linking reaction occurred between the parallel direction in polarization direction of ultraviolet and vertical direction is different.Now, with It is very small that the amount of the cross-linking reaction occurred is irradiated on the parallel direction in polarization direction of ultraviolet, therefore the cross-linking reaction position is risen To the effect of plasticizer.Therefore, liquid crystal of the liquid crystal liquid crystal property in the direction vertical with irradiating the polarization direction of ultraviolet than parallel direction Property high, the self assembly on the parallel direction in the polarization direction with irradiating ultraviolet, the side chain 2 comprising primitive composition refetches To.As a result, the very small anisotropy of the side chain type polymeric membrane 1 induced by photo-crosslinking is in the presence of heat It is exaggerated, so as to assign side chain type polymeric membrane 1 with bigger anisotropy.
Similarly, in the first form of the invention shown in Fig. 2 (a)~(d), the ultraviolet irradiation amount of process [II] exists Δ A reach maximum ultraviolet irradiation amount 15%~70% in the range of in the case of, to the side chain type after polarizing light irradiation Polymeric membrane 3 heats, and it is in mesomorphic state to make it.Then, as shown in Fig. 2 (c), in side chain type polymeric membrane 3, ultraviolet with irradiation The amount of the cross-linking reaction occurred between the parallel direction in polarization direction of line and vertical direction is different.Therefore, with photograph Self assembly on the parallel direction in polarization direction of ultraviolet is penetrated, the side chain 4 comprising primitive composition re-aligns.As a result, The less anisotropy of the side chain type polymeric membrane 3 induced by photo-crosslinking is exaggerated in the presence of heat, so as to assign Side chain type polymeric membrane 3 is given with bigger anisotropy.
Similarly, in the second form of the invention shown in Fig. 3 (a)~(c), represented using using with above formula (7) Light fries' rearrangement group structure the high molecular liquid crystal orientation film of side chain type, the ultraviolet irradiation amount of process [II] is in Δ A reach maximum ultraviolet irradiation amount 1%~70% in the range of in the case of, to the side chain type high score after polarizing light irradiation Sub- film 5 heats, and it is in mesomorphic state to make it.Then, as shown in Fig. 3 (c), in side chain type polymeric membrane 5, with irradiating ultraviolet The amount of the light Fries rearrangement occurred between the parallel direction in polarization direction and vertical direction is different.Now, with The liquid crystal aligning power of the light fries' rearrangement body generated is irradiated on the vertical direction in polarization direction of ultraviolet than the side before reaction The liquid crystal aligning power of chain is strong, therefore the self assembly on the vertical direction in the polarization direction with irradiating ultraviolet, includes primitive composition Side chain 6 re-align.As a result, the side chain type polymeric membrane 5 induced by light Fries rearrangement is very small Anisotropy is exaggerated in the presence of heat, so as to assign side chain type polymeric membrane 5 with bigger anisotropy.
Similarly, in the second form of the invention shown in Fig. 4 (a)~(c), represented using using with above formula (8) Light fries' rearrangement group structure the high molecular liquid crystal orientation film of side chain type, the ultraviolet irradiation amount of process [II] is in Δ A reach maximum ultraviolet irradiation amount 1%~70% in the range of in the case of, to the side chain type high score after polarizing light irradiation Sub- film 7 heats, and it is in mesomorphic state to make it.Then, as shown in Fig. 4 (c), in side chain type polymeric membrane 7, with irradiating ultraviolet The amount of the light Fries rearrangement occurred between the parallel direction in polarization direction and vertical direction is different.Light fries The anchor force of body 8 (a) is reset than the side chain Final 8 before rearrangement, so if generating light fries' rearrangement more than some ormal weight Body, then the self assembly on the parallel direction in the polarization direction with irradiating ultraviolet, the side chain 8 comprising primitive composition refetch To.As a result, work of the less anisotropy of the side chain type polymeric membrane 7 induced by light Fries rearrangement in heat It is exaggerated with lower, so as to assign side chain type polymeric membrane 7 with bigger anisotropy.
Further, in the first form of the present invention, the side chain type macromolecule has from above-mentioned polysiloxanes (a) Polysiloxane structure.Therefore, shown in side chain type polymeric membrane such as Fig. 1 (c) or Fig. 2 (c) of the present invention, by primitive from group After filling Induced Anisotropy, by entering at temperature caused by the thermal response (cross-linking reaction) as caused by the polysiloxane structure Row second heats, can be by the anisotropy immobilization.That is, side chain type polymeric membrane such as Fig. 1 (d) or Fig. 2 (d) of the invention It is shown, it can heat by second and fix the larger anisotropy for inducing the differently- oriented directivity for being side chain 2B or side chain 4B Change.Second temperature heated is preferably set to temperature caused by the thermal response of siloxanes, such as can be set to more than 200 DEG C Temperature.
Further, in the second form of the present invention, the side chain type macromolecule, which also has, derives from above-mentioned polysiloxanes (a) Polysiloxane structure.Therefore, shown in side chain type polymeric membrane such as Fig. 3 (c) or Fig. 4 (c) of the present invention, by primitive from After assembling Induced Anisotropy, by temperature caused by the thermal response (cross-linking reaction) as caused by the polysiloxane structure Second is carried out to heat, can be by the anisotropy immobilization.I.e., although not shown, but the present invention side chain type polymeric membrane with Above-mentioned first homomorphosis, it can heat by second by the larger anisotropy immobilization of induction.Second heats Temperature and above-mentioned first homomorphosis, be preferably set to temperature caused by the thermal response of siloxanes, for example, can be set to 200 DEG C with On temperature.
Therefore, in the manufacture method of liquid crystal orientation film of the invention, by carrying out successively to the inclined of side chain type polymeric membrane The ultraviolet that shakes, which irradiates and heats and be further used for the second of immobilization for the first of reorientation, to be heated, can Efficiently obtain and introduce anisotropic liquid crystal orientation film.
In addition, in the manufacture method of the liquid crystal orientation film of the present invention, to the polarized UV rays of side chain type polymeric membrane Heating-up temperature in exposure and the first heating and the second heating optimizes according to respective purpose.Thereby, energy Efficiently anisotropy is introduced into side chain type polymeric membrane.
Efficiently to the side chain type polymeric membrane of the present invention introduce anisotropic optimal polarization ultraviolet irradiation amount with The photonasty group in the side chain type polymeric membrane is set to carry out photo-crosslinking, photoisomerization reaction or light Fries rearrangement Amount reach optimal polarized UV rays exposure it is corresponding.
If to the side chain type polymeric membrane irradiation polarized UV rays as a result, progress photo-crosslinking, light of the present invention The photonasty group of the side chain of isomerization reaction or light Fries rearrangement is few, then can not reach enough light reaction amounts.This When, it can not also carry out sufficient self assembly even if then being heated.
On the other hand, in side chain type polymeric membrane of the invention, the structured illumination with photocrosslinking reaction group is polarized purple If outside line as a result, carrying out the photonasty group excess of the side chain of cross-linking reaction, the cross-linking reaction on side chain is excessively entered OK.Now, the film of gained sometimes interferes with the progress then by heating the self assembly implemented in rigidity.
In addition, in the side chain type polymeric membrane of the present invention, the structured illumination with light fries' rearrangement group is polarized purple If outside line as a result, carry out light Fries rearrangement side chain photonasty group excess, side chain type polymeric membrane Liquid crystal liquid crystal property excessively reduce.Now, the liquid crystal liquid crystal property of the film of gained also reduces, sometimes interfere with then implemented by heating from group The progress of dress.
Moreover, in the case of to the structured illumination polarized UV rays with light fries' rearrangement group, ultraviolet irradiation If amount is excessive, photodissociation occurs for the side chain type macromolecule of the present invention, sometimes interferes with then by heating the self assembly implemented Progress.
Therefore, in side chain type polymeric membrane of the invention, by the irradiation of polarized UV rays, the photonasty group of side chain enters The optimal amount of row photo-crosslinking, photoisomerization reaction or light Fries rearrangement is preferably the side chain type polymeric membrane institute 0.1~40 mole of % of the photonasty group having, more preferably 0.1~20 mole of %.By the way that the side chain of light reaction will be carried out The amount of photonasty group is arranged in such scope, self assembly can be made efficiently to carry out in heating afterwards, in film In efficiently formed anisotropy.
In the manufacture method of the liquid crystal orientation film of the present invention, by the optimization of the exposure of polarized UV rays, to optimize side The photo-crosslinking of photonasty group on the side chain of chain polymeric membrane, photoisomerization reaction or light Fries rearrangement Amount.Then, along with subsequent heating, anisotropy efficiently can be introduced into side chain type polymeric membrane.In this case, On the amount of suitable polarized UV rays, can be determined based on the evaluation of the UV absorption of side chain type polymeric membrane.
That is, for the side chain type polymeric membrane of the present invention, after polarized UV rays irradiation and polarized UV rays are determined respectively The ultraviolet radiation absorption in the parallel direction in polarization direction and the ultraviolet in the direction vertical with the polarization direction of polarized UV rays inhale Receive.Δ A is evaluated according to the measurement result of ultraviolet radiation absorption, Δ A is in side chain type polymeric membrane and polarized UV rays The ultraviolet absorbance in the parallel direction in polarization direction and the ultraviolet in the direction vertical with the polarization direction of polarized UV rays are inhaled The difference of luminosity.Then, obtain the Δ A realized in the side chain type polymeric membrane of the present invention maximum (Δ Amax) and realize and be somebody's turn to do The exposure of the polarized UV rays of maximum.
In the manufacture method of the liquid crystal orientation film of the present invention, can using realize Δ Amax polarized UV rays exposure as Benchmark determines the preferable polarized UV rays amount irradiated in the manufacturing process of liquid crystal orientation film.
It is excellent to the exposure of the polarized UV rays of side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film of the present invention It is selected in the range of the 1~70% of the amount for the polarized UV rays for realizing Δ Amax, more preferably in the range of 1~50%.
The present invention side chain type polymeric membrane in, realize Δ Amax polarized UV rays amount 1~50% in the range of Polarized UV rays exposure equivalent to making 0.1~20 of all photonasty groups possessed by the side chain type polymeric membrane to rub Your % carries out the amount of the polarized UV rays of photo-crosslinking.
Then, in the manufacture method of liquid crystal orientation film of the invention, after irradiating polarized UV rays to side chain type polymeric membrane, Carry out the heating of the side chain type polymeric membrane (first heats).
The side chain type polymeric membrane of the present invention is the polymeric membrane that liquid crystal liquid crystal property can be embodied within the temperature range of regulation.
First after polarized UV rays irradiation heat can be to embody the liquid crystal liquid crystal property of the side chain type polymeric membrane Determined on the basis of temperature.That is, the first heating-up temperature heated after polarized UV rays irradiation is set to the side chain of the present invention The temperature in the range of liquid crystal liquid crystal property is presented in type polymeric membrane.Then, the heating-up temperature after polarized UV rays irradiation is preferably than this hair Bright side chain type polymeric membrane embodies 10 DEG C of the lower limit for height of the temperature range (hereinafter referred to as liquid crystal temperature range) of liquid crystal liquid crystal property Temperature in the range of temperature to 10 DEG C lower than the upper limit of the liquid crystal temperature range of temperature.
The present invention side chain type polymeric membrane after the irradiation of polarized UV rays be heated, turn into mesomorphic state, with it is inclined Shake self assembly on the parallel or vertical direction in direction, re-align.As a result, reacted by photo-crosslinking, photoisomerization Or the less anisotropy of the side chain type polymeric membrane of light Fries rearrangement induction is exaggerated in the presence of heat.But It is, even if in the case that side chain type polymeric membrane is in mesomorphic state by heating, if heating-up temperature is low, mesomorphic state The viscosity of side chain type polymeric membrane is high, it is difficult to is re-aligned by self assembly.For example, heating-up temperature is not more than than this hair In the case of in the range of the temperature of 10 DEG C of the lower limit for height of the liquid crystal temperature range of bright side chain type polymeric membrane, it is impossible to obtain side The anisotropic amplification effect as caused by heat in chain polymeric membrane, this is not sufficiently effective.
In addition, even if the side chain type polymeric membrane of the present invention is in mesomorphic state by heating, if heating-up temperature is high, The state of side chain type polymeric membrane is close to isotropic liquid condition, it is difficult to is refetched in one direction by self assembly To.For example, heating-up temperature is higher than the temperature of low 10 DEG C of the upper limit of the liquid crystal temperature range of the side chain type polymeric membrane of the present invention In the case of temperature, it is impossible to obtain the anisotropic amplification effect as caused by heat in side chain type polymeric membrane, the effect Deficiency.
Moreover, the first heating-up temperature heated is than the liquid crystal temperature range of the side chain type polymeric membrane of the present invention The high temperature of the temperature that low 10 DEG C of the upper limit, for example, 200 DEG C with more than the reaction temperature of first-class siloxanes in the case of, exist sometimes The thermal response of oxyalkylene segment can be carried out before reorientation.In this case, side chain type polymeric membrane becomes to be difficult to pass through self assembly Re-aligned to a direction.For example, in the case where heating-up temperature is the temperature more than 200 DEG C, can not produce enough The anisotropic amplification effect as caused by heat in side chain type polymeric membrane.
As described above, in the manufacture method of the liquid crystal orientation film of the present invention, in order to efficiently into side chain type polymeric membrane Anisotropy is introduced, is come on the basis of the liquid crystal temperature range of side chain type polymeric membrane and oxyalkylene segment range of reaction temperature It is determined that suitable heating-up temperature.As described above, the temperature of the heating after polarized UV rays are irradiated is set to higher than the side chain type The temperature of 10 DEG C of the lower limit for height of the liquid crystal temperature range of molecular film be lower limit, below 200 DEG C, with upper than liquid crystal temperature range The temperature for limiting low 10 DEG C is the temperature in the range of the upper limit.Thus, for example the liquid crystal temperature of the side chain type polymeric membrane of the present invention In the case that scope is 100 DEG C~200 DEG C, oxyalkylene segment is reacted at a high temperature of higher than 200 DEG C, polarized UV rays are shone The temperature of heating after penetrating is preferably 110 DEG C~190 DEG C.Thereby, side chain type polymeric membrane can be assigned with bigger anisotropy.
Then, each operation of the manufacture method of the liquid crystal orientation film of the present invention is further specifically described.
As described above, the manufacture method of liquid crystal orientation film of the invention has following [I]~[IV's] in the following order Process.Thereby, it can manufacture and anisotropic liquid crystal orientation film is introduced with high efficiency.
[I] forms the photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property is embodied within the temperature range of regulation on substrate Process,
The process that [II] irradiates polarized UV rays to the side chain type polymeric membrane obtained in process [I],
The process that [III] heats to the side chain type polymeric membrane through polarized UV rays irradiation in process [II], and
The temperature of [IV] to the side chain type polymeric membrane of heating in process [III] more than process [III] heating-up temperature Under the process that is further heated,
Hereinafter, manufacture method possessed [I]~[IV] each operation of the liquid crystal orientation film of the present invention is illustrated.
In process [I], the side chain type polymeric membrane of the present invention is formed on substrate.
Substrate is not particularly limited.For example, in addition to glass substrate, acrylic acid substrate and polycarbonate substrate etc. can be used The transparency carriers such as plastic base.In view of the application of gained liquid crystal orientation film, from the simplification of the manufacturing process of liquid crystal display cells From the viewpoint of, ITO (the Indium Tin Oxide formed with liquid crystal drive can also be used：Tin indium oxide) electrode etc. Substrate.Furthermore, it is contemplated that the application in reflection type liquid crystal display element, can also use the opaque substrates such as silicon wafer, this When electrode can also use the material of the reflected light such as aluminium.
In the case that the side chain type polymeric membrane of the present invention is in the solution shape for being dissolved in required solvent, the film on substrate is formed Carried out by being coated with the side chain type polymeric membrane of the solution shape.
Coating method is not particularly limited, industrial generally use by silk-screen printing, hectographic printing, flexographic printing, The method that ink-jet method etc. is coated.As other coating methods, there are dip coating, rolling method, slot coated method, spin-coating method (rotation Turn rubbing method), spraying process etc., these methods can be used according to purpose.
On substrate after the side chain type polymeric membrane of the invention of coating solution shape, heating plate, heat-circulation type can be passed through The heaters such as stove, IR (infrared ray) type stove evaporate solvent at 20~180 DEG C, preferably 40~150 DEG C, so as to obtain side chain Type polymeric membrane.
If the thickness of side chain type polymeric membrane is blocked up, in the power consumption side of the liquid crystal display cells using liquid crystal orientation film Face is unfavorable；If excessively thin, the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5~300nm, more preferably 10~ 100nm。
Alternatively, it is also possible to which setting will be formed with side chain type polymeric membrane after process [I], before follow-up process [II] The substrate process that is cooled to room temperature.
In process [II], first orientation is carried out to the side chain type polymeric membrane irradiation polarized UV rays obtained by process [I] Processing.In the case of to the film surface of side chain type polymeric membrane irradiation polarized UV rays, from certain orientation across polarizer to substrate Irradiate polarized UV rays.
As ultraviolet used, the ultraviolet in the range of 100~400nm of wavelength can be used.It is preferred that used in The species of side chain type polymeric membrane pass through the suitable wavelength of the selections such as wave filter.For example, handed in order to optionally induce light Connection reaction, it can select to use the ultraviolet in the range of 290~400nm of wavelength.As ultraviolet, such as can use by height The light that pressure mercury lamp is launched.
On the exposure of polarized UV rays, as described above, it is preferred in used side chain type polymeric membrane of the invention The polarized UV rays for realizing Δ Amax amount 1~70% in the range of, more preferably in the range of 1~50%.
In process [III], heat as first, to the side chain type high score irradiated in process [II] through polarized UV rays Sub- film is heated.Heat using mode of heatings such as heating plate, heat-circulation type stove, IR (infrared ray) type stoves.
On the temperature of heating, as set forth above, it is possible to which liquid crystal liquid crystal property is presented in view of the side chain type polymeric membrane of the present invention Temperature determines.That is, the heating-up temperature of this process is the temperature re-aligned in above-mentioned side chain type polymeric membrane.
The heating-up temperature of this process in process [II] after polarized UV rays irradiation is preferably with more of the invention than used Side chain type polymeric membrane embody the temperature of 10 DEG C of the lower limit for height of the liquid crystal temperature range of liquid crystal liquid crystal property for lower limit, below 200 DEG C, Using 10 DEG C lower than the upper limit of liquid crystal temperature range of temperature as the temperature in the range of the upper limit.The side chain type polymeric membrane of the present invention Liquid crystal liquid crystal property can be shown, moreover, as the temperature range for not producing thermal response, preferably less than more than 60 DEG C 180 DEG C.
In process [IV], heat as second, the side chain type polymeric membrane that will be heated through process [III] further exists Heated at the temperature different from the heating-up temperature of process [III].In process [III], selection makes the side chain type of the present invention high The temperature that molecular film is formed as the temperature of mesomorphic state and its oxyalkylene segment does not occur in the range of thermal response is carried out at heating Reason (first heats).Therefore, in this process, the heating-up temperature for being selected above the heating-up temperature of process [III] is heated Processing (second heats).The heating-up temperature of this process is to make the reorientation of the side chain type polymeric membrane using process [III] The temperature of immobilization.
Heating is identical with process [III], can use the heating such as heating plate, heat-circulation type stove, IR (infrared ray) type stove Mode.
To heating-up temperature, as described above, it is contemplated that the reaction of the oxyalkylene segment in side chain type polymeric membrane of the invention Temperature determines.For example, the heating-up temperature of this process is preferably set to more than 200 DEG C.Furthermore it is preferred that it is set to side chain type polymeric membrane Low less than 300 DEG C of the temperature of heat deterioration possibility, particularly preferred less than 250 DEG C of temperature.
By including above process, by the manufacture method of the liquid crystal orientation film of the present invention, can efficiently realize to side chain Anisotropy is introduced in type polymeric membrane.
And the liquid crystal orientation film of the invention of high reliability can efficiently be made.
[embodiment]
Embodiment is enumerated below the present invention is further described in detail.In addition, the present invention is not necessarily to be construed as limiting to In this.
Following synthesis example, the abbreviation of embodiment and compound and organic solvent used in comparative example and structure As described below.
(silane monomer)
TEOS：Tetraethoxysilane
ACPS：3- acryloxypropyl trimethoxy silanes
(methacrylate monomers)
[changing 6]
[changing 7]
(organic solvent)
NMP：METHYLPYRROLIDONE
BCS：Butyl cellosolve
PGME：Propylene glycol monomethyl ether
(polymerization initiator)
AIBN：Azodiisobutyronitrile
[molecular weight determination]
The number-average molecular weight and weight average molecular weight of acrylic copolymer use Japan Spectroscopy Corporation's (Japan's light splitting Society) system GPC devices (SHODEX (registration mark) post KF803L and KF804L), be measured according to following condition：Make work For eluting solvent tetrahydrofuran with flow 1mL (milliliter)/minute in post (40 DEG C of column temperature) circulation make its elution.In addition, Following number-average molecular weights (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented with polystyrene scaled value.
<The synthesis of polysiloxanes>
<Synthesis example 1>
Polysiloxanes (A)：Be put into 4 mouthfuls of reaction flasks with return duct PGME (15.6g), TEOS (18.8g), with And ACPS (2.3g), it is stirred at room temperature 10 minutes.Then, dripped in the solution PGME (7.8g), oxalic acid (0.1g) and H2O (5.4g) mixture.After dripping, it is heated to reflux 3 hours, afterwards, lets cool to room temperature.After cooling, carried out with PGME (50g) Dilution, prepares polysiloxanes (A) solution.
[assay method of remaining alkoxy silane monomer]
With gas chromatography (hereinafter referred to as GC.) measure prepare polysiloxanes (A) solution in remaining alkoxyl silicone Alkane monomer.
The Shimadzu GC-14B that GC measure is made using Shimadzu Scisakusho Ltd (Island Tianjin System Zuo Suo societies) are following Under the conditions of carry out.
Post：Capillary column CBP1-W25-100 (long 25mm, diameter 0.53mm, 1 μm of wall thickness)
Column temperature：From start temperature, 50 DEG C are heated up with 15 DEG C/min, are reached temperature and are set to 290 DEG C (being kept for 3 minutes).
Sample injection rate：1 μ L, injector temperature：240 DEG C, detector temperature：290 DEG C, carrier gas：Nitrogen (30mL/ points of flow Clock), detection method：FID methods.
The result of measure is not detect alkoxy silane monomer in polysiloxanes (A) solution.
<Polysiloxanes-synthesis of polymethacrylates mixture and the preparation of aligning agent for liquid crystal>
<Synthesis example 2>
Polysiloxanes (A) 1.0g, M6CB2g (3.9mmol) that synthesis example 1 is obtained, as polymerization initiator AIBN0.08g (0.47mmol) is added in 20ml NMP, is stirred at room temperature untill solid all dissolving, in reaction system After interior progress nitrogen displacement, reaction temperature is slowly improved, makes its reaction by being stirred 15 hours at 50 DEG C., will after reaction terminates In reaction solution injection 500ml Anaesthetie Ether, isolating polymer, after removing AIBN, sediment is separated by filtration, obtains poly- silica Alkane-polymethacrylates mixing (P6CBS) powder (B).
The P6CBS powder (B) is heated up under petrographic microscope while observed, be more than 60~300 DEG C Liquid crystal liquid crystal property is presented within the temperature range of only.Afterwards, continue that continuous heating, the condensation for carrying out siloxanes are anti-at 300 DEG C by P6CBS Should, P6CBS is changed into thermosetting compound, slowly loses liquid crystal liquid crystal property.The polysiloxanes-polymethacrylates mixture (P6CBS) Phase transfer behavior, which collects, is shown in table 1.
<Synthesis example 3>
Polysiloxanes (A) 2.5g, M6CA2g (6.0mmol) that synthesis example 1 is obtained, as polymerization initiator AIBN0.13g (0.79mmol) is added in 22ml NMP, is stirred at room temperature untill solid all dissolving, in reaction system After interior progress nitrogen displacement, reaction temperature is slowly improved, makes its reaction by stirring 15h at 50 DEG C.After reaction terminates, it will react Solution injection 500ml Anaesthetie Ether in, isolating polymer, remove AIBN after, be separated by filtration sediment, obtain polysiloxanes- Polymethacrylates mixing (P6CAS) powder (C).
The P6CBS powder (C) is heated up under petrographic microscope while observed, presented at 80~190 DEG C Liquid crystal liquid crystal property.Afterwards, continue P6CAS being heated to more than 200 DEG C, carry out the condensation reaction of siloxanes, P6CAS is changed into heat cure Thing, lose liquid crystal liquid crystal property.The phase transfer behavior of the polysiloxanes-polymethacrylates mixture (P6CAS), which collects, is shown in table 1.
[table 1]
Liquid crystal temperature range (DEG C) Polymer curing temperatures
Synthesis example 2 (P6CBS) 60~300 DEG C More than 300 DEG C
Synthesis example 3 (P6CAS) 80~190 DEG C More than 190 DEG C
<Embodiment 1>
Added in synthesis example 2 obtains polysiloxanes-polymethacrylates mixing (P6CBS) (powder (B)) NMP and BCS, 4 mass % are diluted to, obtain aligning agent for liquid crystal (I).Confirm muddy without finding in the aligning agent for liquid crystal Or precipitation etc. is abnormal, resin component is dissolves uniformly in wherein.By determining the aligning agent for liquid crystal with GPC, P6CBS is determined Molecular weight, Mn 35000.
[assay method of the content of siloxane in mixed polymer]
Content of siloxane in polysiloxanes-polymethacrylates mixture (powder (B)) is calculated by GPC.Pass through ratio Compared with peak and polysiloxanes-polymethacrylates mixture of the methacrylate monomers of the GPC figures after radical polymerization The ratio at peak, calculates content of siloxane.
Siloxane-methyl acrylate ratio in the P6CBS calculated is using weight ratio meter as 1: 5.
<Embodiment 2>
Added in synthesis example 3 obtains polysiloxanes-polymethacrylates mixing (P6CAS) (powder (C)) NMP and BCS, 4 mass % are diluted to, obtain aligning agent for liquid crystal (II).Confirm muddy without finding in the aligning agent for liquid crystal Or precipitation etc. is abnormal, resin component is dissolves uniformly in wherein.By determining the aligning agent for liquid crystal with GPC, P6CAS is determined Molecular weight, Mn 48000.In addition the siloxane-methyl acrylate ratio in the P6CAS calculated by GPC is with weight ratio meter For 2: 3.5.
<The manufacture of liquid crystal orientation film>
<Embodiment 3>
At the liquid crystal aligning containing polysiloxane-polymethacrylates mixture (P6CBS) obtained using embodiment 1 Agent (I) is managed, spin coating is carried out on quartz base plate (vertical 10 × horizontal stroke, 10 × thickness 1 (mm)), is dried 5 minutes in 80 DEG C of heating plate Afterwards, thickness 50nm film, the substrate of the liquid crystal orientation film before obtaining with orientation process are formed.
<Embodiment 4>
The substrate with the liquid crystal orientation film before orientation process obtained using embodiment 3, from certain direction on substrate Liquid crystal aligning film surface across polarization plates irradiate polarized UV rays.The intensity of polarized UV rays is calculated as 14mW with wavelength 365nm, purple Outside line exposure is 600mJ.Afterwards, the substrate through ultraviolet irradiation is heated 5 minutes at 150 DEG C, in the P6CBS of film Reorientation process is implemented to film (polymeric membrane) in the case of for mesomorphic state, obtains liquid crystal orientation film of the band through orientation process Substrate.As described later, the obtained substrate with liquid crystal orientation film is used for the measure of ultraviolet absorption spectrum (Fig. 5).
<Embodiment 5>
The substrate with the liquid crystal orientation film before orientation process obtained using embodiment 3, from certain direction on substrate Liquid crystal aligning film surface across polarization plates irradiate polarized UV rays.The intensity of polarized UV rays is calculated as 14mW with wavelength 365nm, purple Outside line exposure is 600mJ.Afterwards, the substrate through ultraviolet irradiation is heated 5 minutes at 150 DEG C, in the P6CBS of film Reorientation process is implemented to film in the case of for mesomorphic state.Then, the substrate for implementing reorientation process is heated to 200 DEG C, siloxanes is carried out condensation reaction, fixed orientation by burning till at such a temperature.So, band is obtained through orientation position The substrate of the liquid crystal orientation film of reason.
<Embodiment 6>
The substrate with the liquid crystal orientation film before orientation process obtained using embodiment 3, from certain direction on substrate Liquid crystal aligning film surface across polarization plates irradiate polarized UV rays.The intensity of polarized UV rays is calculated as 14mW with wavelength 365nm, purple Outside line exposure is 800mJ.Afterwards, the substrate through ultraviolet irradiation is heated 5 minutes at 150 DEG C, in the P6CBS of film Reorientation process is implemented to film in the case of for mesomorphic state, obtains the substrate of liquid crystal orientation film of the band through orientation process.
As described later, the obtained substrate with liquid crystal orientation film is used for the measure of ultraviolet absorption spectrum (Fig. 6).
<Embodiment 7>
The substrate with the liquid crystal orientation film before orientation process obtained using embodiment 3, from certain direction on substrate Liquid crystal aligning film surface across polarization plates irradiate polarized UV rays.The intensity of polarized UV rays is calculated as 14mW with wavelength 365nm, purple Outside line exposure is 800mJ.Afterwards, the substrate through ultraviolet irradiation is heated 5 minutes at 150 DEG C, in the P6CBS of film Reorientation process is implemented to film in the case of for mesomorphic state.Then, the substrate for implementing reorientation process is heated to 200 DEG C, siloxanes is carried out condensation reaction, fixed orientation by burning till at such a temperature.So, band is obtained through orientation position The substrate of the liquid crystal orientation film of reason.
<The evaluation of liquid crystal orientation film>
<Embodiment 8>
Using the substrate of liquid crystal orientation film of the band that embodiment 4 obtains through orientation process, the ultraviolet of liquid crystal orientation film is determined Line absorption spectrum.
Fig. 5 be the liquid crystal orientation film of the gained of embodiment 4 with the ultraviolet linearly polarized light electric field vector parallel through irradiation and Vertical ultraviolet absorption spectrum.
In Fig. 5, show that the ultraviolet absorption spectrum for the liquid crystal orientation film that embodiment 4 obtains (in figure, is shown as " putting down after heating OK " and " after heating vertically "), as comparison other, show only to carry out (at the heating of embodiment 4 of polarized UV rays irradiation Before reason) ultraviolet absorption spectrum of liquid crystal orientation film (in figure, is shown as " parallel after polarizing light irradiation " and " after polarizing light irradiation Vertically ").
If as shown in figure 5, ultraviolet absorption spectrum to the liquid crystal orientation film of embodiment 4 and only carry out polarized UV rays The ultra-violet absorption spectrum of substrate of the irradiation (before the heating of embodiment 4) is compared, then the ultraviolet radiation absorption light of embodiment 4 Difference in spectrum with the polarised light field parallel directions of the polarized UV rays of irradiation and the ultraviolet absorption spectrum of vertical direction is more than Only carry out the polarization optical electric field with irradiating polarized UV rays of the substrate of polarized UV rays irradiation (before the heating of embodiment 4) The difference of the ultraviolet absorption spectrum of parallel direction and vertical direction, it is known that the heating after being irradiated by polarized UV rays, embodiment 4 Obtained liquid crystal orientation film is re-aligned processing.
Fig. 6 be the liquid crystal orientation film of the gained of embodiment 6 with the ultraviolet linearly polarized light electric field vector parallel through irradiation and Vertical ultraviolet absorption spectrum.
In Fig. 6, show that the ultraviolet absorption spectrum for the liquid crystal orientation film that embodiment 6 obtains (in figure, is shown as " putting down after heating OK " and " after heating vertically "), as comparison other, show only to carry out (at the heating of embodiment 6 of polarized UV rays irradiation Before reason) ultraviolet absorption spectrum of liquid crystal orientation film (in figure, is shown as " parallel after polarizing light irradiation " and " after polarizing light irradiation Vertically ").
As shown in fig. 6, the liquid crystal orientation film that embodiment 6 obtains is also identical with the liquid crystal orientation film that embodiment 4 obtains, pass through Heating after polarized UV rays irradiation, ultraviolet radiation absorption and Vertical Square with the polarised light field parallel of the polarized UV rays of irradiation To ultraviolet radiation absorption difference be more than only carry out polarized UV rays irradiation (before the heating of embodiment 4) substrate and irradiation Polarized UV rays polarised light field parallel direction and vertical direction ultraviolet absorption spectrum difference, it is known that pass through polarize it is purple Heating after outside line irradiation, the liquid crystal orientation film that embodiment 6 obtains are re-aligned processing.
<The manufacture of liquid crystal cell>
<Embodiment 9>
Aligning agent for liquid crystal (I) the manufacture liquid crystal orientation film obtained using embodiment 1, and manufacture and used the liquid crystal to take To the liquid crystal cell of film.The characteristic of corresponding liquid crystal orientation film, parallel-oriented liquid crystal cell is set to by liquid crystal cell.Can be by using A pair of polarization plates seize obtained liquid crystal cell on both sides by the arms, form liquid crystal display cells.
As the manufacture method of liquid crystal cell, aligning agent for liquid crystal (I) is spun on the glass substrate with ITO electrode On, after being dried 5 minutes in 80 DEG C of heating plate, the film of the thickness 50nm as liquid crystal orientation film is formed, obtains band orientation The substrate of the liquid crystal orientation film of before processing.The uniformity of the thickness of the liquid crystal orientation film formed on substrate is all excellent, it is known that Aligning agent for liquid crystal (I) shows excellent coating.
Using the obtained substrate with the liquid crystal orientation film before orientation process, the liquid crystal on substrate is taken from certain direction To film surface polarized UV rays are irradiated across polarization plates.The intensity of polarized UV rays is calculated as 14mW, ultraviolet irradiation with wavelength 365nm Measure as 600mJ.Afterwards, the substrate through ultraviolet irradiation is heated 5 minutes at 150 DEG C, is liquid crystal shape in the P6CBS of film Reorientation process is implemented to film in the case of state.Then, the substrate for implementing reorientation process is heated at 250 DEG C, led to Crossing to burn till at such a temperature makes siloxanes carry out condensation reaction, fixed orientation for 15 minutes.So, liquid of the band through orientation process is obtained The substrate of brilliant alignment films.
The preparation two panels substrate with liquid crystal orientation film, 14 μm of sept is spread on a piece of liquid crystal aligning film surface Afterwards, sealant is coated with thereon.Then, will after being bonded in a manner of making liquid crystal orientation film relative with the substrate of the opposing party Sealant cures manufacture negative crystal born of the same parents.Capillarity is utilized to negative crystal born of the same parents, more than the isotropic phase temperature of liquid crystal At 105 DEG C, nematic crystal (Merck ＆ Co., Inc. (メ ルク societies) ZLI-4792 processed) is injected, obtains liquid crystal cell.
<Embodiment 10>
In addition to the ultraviolet irradiation amount of polarization is set into 800mJ, according to the identical method system of above-described embodiment 9 Make liquid crystal cell.
<The evaluation of liquid crystal display cells>
<Embodiment 11>
The liquid crystal cell obtained using embodiment 9 and embodiment 10, the orientation shape of liquid crystal is carried out using polarizing microscope The evaluation of state.That is, the liquid crystal display cells seized on both sides by the arms liquid crystal cell with a pair of polarization plates and formed are carried out using polarizing microscope Evaluation.It is it was observed that good without orientation defect, the state of orientation of liquid crystal in liquid crystal cell.Evaluation result, which collects, is shown in table 2.
[table 2]
The state of orientation of liquid crystal
Embodiment 9 Well
Embodiment 10 Well
Utilization possibility in industry
The present invention provides the polymer and aligning agent for liquid crystal for the manufacture for being adapted to the efficient liquid crystal orientation film using light, Liquid crystal orientation film and liquid crystal display cells can be as light weight, slim and low power consumption displays as obtained by the aligning agent for liquid crystal Device uses.
In addition, the explanation for the Japanese patent application 2012-163989 filed an application July 24 in 2012 is quoted herein The announcement of book, claims, all the elements of accompanying drawing and summary as description of the invention.
Symbol description
1,3,5,7 side chain type polymeric membrane
2,2a, 2b, 4,4a, 4b, 6,6a, 8,8a side chains

Claims (11)

1. a kind of manufacture method of liquid crystal orientation film, it is characterised in that have：
The process that the photosensitive side chain type polymeric membrane that liquid crystal liquid crystal property is embodied within the temperature range of regulation is formed on substrate [I],
The process [II] of polarized UV rays is irradiated to the side chain type polymeric membrane,
By the side chain type polymeric membrane after ultraviolet irradiation in the range of liquid crystal liquid crystal property is presented in the side chain type polymeric membrane At a temperature of the process [III] that is heated, and
By the side chain polymeric membrane after heating more than process [III] heating-up temperature at a temperature of further heated Process [IV].
2. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the heating-up temperature of process [III] is Than the side chain type polymeric membrane present liquid crystal liquid crystal property temperature range 10 DEG C of lower limit for height temperature to than the liquid crystal temperature range Low 10 DEG C of the upper limit temperature in the range of temperature.
3. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that the heating-up temperature of process [III] For the temperature below 200 DEG C.
4. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the heating-up temperature of process [III] is The temperature that the side chain of the side chain type polymeric membrane is re-aligned.
5. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the heating-up temperature of process [III] is The temperature that the side chain of the side chain type polymeric membrane is re-aligned, the heating-up temperature of process [IV] are to make process [III] weight It is orientated the temperature of immobilization.
6. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the photonasty that liquid crystal liquid crystal property is presented Side chain type polymeric membrane in contained photonasty group be selected from azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, perfume (or spice) Legumin, tolans, at least one kind of derivative group of phenol benzoate.
7. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the side chain type polymeric membrane contains Following structure：The structure possess selected from polyamic acid, polyimides, poly amic acid ester, acrylate, methacrylate, The main chain of at least one kind of composition of maleimide, alpha-methylene-gamma-butyrolactone and siloxanes, and selected from following formula (1)~formula (5), at least one kind of side chain of formula (7) and formula (8)；
[changing 1]
In formula (1), A1And B1Separately represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH- CO-, Y1It is to be selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or groups of these combinations, The hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen radical Group, alkyl or alkoxy substitution, X1Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-, l1 tables Show 1~12 integer, m1 represents 1~3 integer, and n1 represents 1~12 integer；
In formula (2), A2、B2And D1Separately represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH- CO-, Y2It is to be selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 or groups of these combinations, The hydrogen atom being bonded on these groups can be separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen radical Group, alkyl or alkoxy substitution, X2Represent singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-, R1Table Show the alkyl of hydrogen atom or carbon number 1~6, l2 represents 1~12 integer, and m2 represents 1~3 integer, n2 represent 1~12 it is whole Number；
In formula (3), A3Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-, X3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-, R2The alkyl of hydrogen atom or carbon number 1~6 is represented, l3 is represented 1~12 integer, m3 represent 1~3 integer；
In formula (4), l4 represents 1~12 integer；
In formula (5), A4Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-, X4Expression-COO-, Y3It is Selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl or groups of these combinations, the hydrogen atom being bonded on these groups can separately by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution, l5 represent 1~12 integer, m4 Represent 1~3 integer；
In formula (7), A5Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-, R3Expression hydrogen atom ,- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6 or its group Close the group that forms, l6 represents 1~12 integer, the hydrogen atom being bonded on the phenyl ring in formula (7) can separately by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution；
In formula (8), A6Represent singly-bound ,-O- ,-CH2- ,-COO- ,-OCO- ,-CONH- or-NH-CO-, B3Expression singly-bound ,- COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- or C6H4-, W1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrroles Groups of ring, the cyclic hydrocarbon of carbon number 5~8 or these combinations, the hydrogen atom being bonded on these groups can separately by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy substitution, l7 represent 1~12 integer, m5、 And m6Separately represent 1~3 integer.
8. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the side chain type polymeric membrane contains Polymer, the polymer are the polysiloxanes (a) for making to have free-radical polymerised group, and with liquid crystal liquid crystal property and photosensitive The monomer (b) of group and free-radical polymerised group carries out polymer obtained by radical polymerization.
9. the manufacture method of liquid crystal orientation film as claimed in claim 8, it is characterised in that the liquid crystal liquid crystal property of the monomer (b) and Photosensitive group is selected from azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolans, phenol benzoate At least one kind of derivative group.
10. a kind of liquid crystal orientation film, it is characterised in that pass through the system of liquid crystal orientation film according to any one of claims 1 to 9 Make method and be made.
11. a kind of liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 10.
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