CN103959152B - The manufacture method of liquid crystal orientation film, liquid crystal orientation film and liquid crystal display cells - Google Patents
The manufacture method of liquid crystal orientation film, liquid crystal orientation film and liquid crystal display cells Download PDFInfo
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- CN103959152B CN103959152B CN201280058353.6A CN201280058353A CN103959152B CN 103959152 B CN103959152 B CN 103959152B CN 201280058353 A CN201280058353 A CN 201280058353A CN 103959152 B CN103959152 B CN 103959152B
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Abstract
The present invention provides a kind of manufacture method that just can not introduced anisotropic liquid crystal orientation film by friction efficiently in film, it is provided that a kind of liquid crystal orientation film and liquid crystal display cells.The manufacture method of liquid crystal orientation film includes: [I] embodies the operation of the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate；Described side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And the operation of the side chain type polymeric membrane heating that [III] is to irradiating through described ultraviolet；It is characterized in that, the ultraviolet irradiation amount of [II] operation reaches in the range of the 1%～70% of maximum ultraviolet irradiation amount at Δ A, and Δ A is the difference of the ultraviolet absorbance in the ultraviolet absorbance in the described side chain type polymeric membrane direction parallel with the polarization direction of described polarized UV rays and the direction vertical with the polarization direction of described polarized UV rays.
Description
Technical field
The present invention relates to the manufacture method of liquid crystal orientation film, liquid crystal orientation film and liquid crystal display cells, particularly relate to liquid
The manufacture method of the liquid crystal orientation film used in crystal display element, by liquid crystal orientation film obtained by this manufacture method and make
With the liquid crystal display cells of this liquid crystal orientation film.
Background technology
Liquid crystal display cells as light weight, slim and low power consumption display device it is known that be applied to big in recent years
The television set purposes etc. of type, achieved with alarming development.Liquid crystal display cells is such as with a pair transparent base with electrode
Liquid crystal layer is clamped and is constituted by plate.Then, in liquid crystal display cells, for making liquid crystal in required state of orientation between substrate,
Use the organic membrane being made up of organic material as liquid crystal orientation film.
That is, liquid crystal orientation film is the member of formation of liquid crystal display cells, be formed at the substrate clamped by liquid crystal and liquid crystal
On the face of contact, play the effect being orientated at this substrate chien shih liquid crystal towards certain orientation.Then, for liquid crystal orientation film, except
Make liquid crystal towards such as with the effect of the certain orientation orientation such as the direction of substrate-parallel beyond, the most also require to control the pre-dumping of liquid crystal
The effect at angle.The ability (calling tropism control ability in the following text) controlling liquid crystal aligning of such liquid crystal orientation film is by constituting liquid
The organic membrane of brilliant alignment films carries out what orientation process gave.
As the method for orientation treatment of the liquid crystal orientation film for giving tropism control ability, the most known friction
Method.Friction refers to following method: for organic membrane such as the polyvinyl alcohol on substrate, polyamide, polyimides, used on its surface
The cloth of cotton, nylon, polyester etc., towards certain orientation wiping (friction), makes liquid crystal be orientated towards the direction (frictional direction) of wiping.This rubs
Rubbing method can realize the state of orientation of relatively stable liquid crystal easily, therefore in the manufacturing process of existing liquid crystal display cells
There is use always.Then, as the organic membrane used in liquid crystal orientation film, reliability and the electricity such as thermostability are mainly selected
The organic membrane of the polyimide of excellent.
But, in the friction that the liquid crystal orientation film surface being made up of polyimides etc. is rubbed, airborne dust and electrostatic
Generation sometimes become problem.Additionally, due to the high-precision refinement of liquid crystal display cells in recent years, by the electricity on corresponding substrate
It is concavo-convex that the switch active element of pole or liquid crystal drive is caused, and sometimes cannot carry out liquid crystal orientation film surface uniformly with cloth
Ground friction, it is impossible to realize uniform liquid crystal aligning.
Then, as not carrying out other method for orientation treatment of the liquid crystal orientation film rubbed, optical alignment method has been carried out greatly
Quantity research.
Optical alignment method has various method, but is all that the light utilizing rectilinearly polarized light or collimation is constituting liquid crystal aligning
Form anisotropy in the organic membrane of film, make liquid crystal aligning along this anisotropy.
As main optical alignment method, it is known that the optical alignment method of breakdown type.Such as polyimide film is irradiated polarized UV
Line, utilizes the polarization direction dependency of the ultra-violet absorption of molecular structure to bring it about anisotropic decomposition.Then, utilize not
The polyimides decomposed and remain makes liquid crystal aligning (with reference to patent documentation 1).
In addition, it is also known that photo-crosslinking type or the optical alignment method of photoisomerization type.Such as use poly-vinyl cinnamate, irradiate
Polarized UV rays, in double bond part generation dimerization (cross-linking reaction) of 2 side chains parallel with polarized light.Then, make
Liquid crystal is towards the direction orientation (with reference to non-patent literature 1) orthogonal with polarization direction.Additionally, use side chain to have the side chain of diphenyl diimide
In the case of type is high molecular, irradiate polarized UV rays, anti-at the diphenyl diimide part generation isomerization of the side chain parallel with polarized light
Should, make liquid crystal towards the direction orientation (with reference to non-patent literature 2) orthogonal with polarization direction.
As described in the above example, use in the method for orientation treatment of liquid crystal orientation film of optical alignment method, it is not necessary to friction, no
With worrying airborne dust and the generation of electrostatic.Then, the substrate even for the irregular liquid crystal display cells in surface also can be implemented to take
To process, it is suitable for the method for orientation treatment of the liquid crystal orientation film of the production technology of industrial circle.
Prior art literature
Patent documentation
Patent documentation 1: No. 3893659 publications of Japanese Patent No.
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)
Summary of the invention
Invent technical problem to be solved
As it has been described above, optical alignment method with all the time as liquid crystal display cells method for orientation treatment industrial circle should
Friction compare, it is not necessary to friction process itself, therefore there is the biggest advantage.And, with the tropism control by friction
The friction of ability constant is compared, and optical alignment method can change the irradiation dose of polarized light to control tropism control ability.But,
In optical alignment method, when being intended to realize and use friction in the case of the tropism control ability of same degree, it is sometimes desirable to substantial amounts of
The irradiation dose of polarized light, or stable liquid crystal aligning cannot be realized.
In the optical alignment method of the breakdown type described in the most above-mentioned patent documentation 1, need polyimide film is irradiated source
Ultraviolet light 60 minutes of high voltage mercury lamp in output 500W etc., needs long-time and substantial amounts of ultraviolet to irradiate.Additionally, two
In the case of the optical alignment method of dimerization type or photoisomerization type, sometimes it is also required to the substantial amounts of purple of several J (joule)～tens of about J
Outside line is irradiated.Further, in the case of the optical alignment method of photo-crosslinking type or photoisomerization type, the heat stability of the orientation of liquid crystal and light
Poor stability, exists when therefore making liquid crystal display cells and occurs orientation bad or the problem of display burn-in.
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
The liquid crystal orientation film manufacture method with the liquid crystal orientation film of highly oriented control ability can be given efficiently.
Then, it is an object of the invention to provide a kind of can using up to carry out the liquid crystal that good liquid crystal aligning controls efficiently and take
To the manufacture method of film.
Moreover, it is an object that a kind of manufacture method using this liquid crystal orientation film realizes the height making to use up
The orientation process of efficiency and the liquid crystal orientation film made.
The purpose of the present invention also provides for a kind of to be had the liquid crystal realizing making the high efficiency orientation process used up and make and takes
To the liquid crystal display cells of film.
Solve the technical scheme that technical problem is used
Present inventor has performed and conscientiously study, result obtains following discovery, thus completes the present invention.
The manufacture method of the liquid crystal orientation film of the present invention uses and uses the photosensitive side chain that can embody liquid crystal liquid crystal property
Type polymeric membrane, do not carry out friction treatment but the method that carries out orientation process by polarizing light irradiation.Then, at polarized light
After irradiation, the operation to the heating of this side chain type polymeric membrane is set, manufactures liquid crystal orientation film.Now, by optimizing polarized light
The heating-up temperature in heating process after irradiation dose and polarizing light irradiation, can realize high efficiency orientation position by liquid crystal orientation film
Reason, can give good tropism control ability with high efficiency.
The present invention has techniques below content.
(1) manufacture method of a kind of liquid crystal orientation film, comprising:
[I] embodies the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate
Operation；
Described side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And
The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；
It is characterized in that, the ultraviolet irradiation amount of [II] operation Δ A reach maximum ultraviolet irradiation amount 1%～
In the range of 70%, Δ A is the direction that described side chain type polymeric membrane is parallel with the polarization direction of described polarized UV rays
The difference of the ultraviolet absorbance in ultraviolet absorbance and the direction vertical with the polarization direction of described polarized UV rays.
(2) manufacture method of the liquid crystal orientation film described in above-mentioned (1), wherein, the ultraviolet irradiation amount of [II] operation is in institute
State Δ A to reach in the range of the 1%～50% of maximum ultraviolet irradiation amount.
(3) above-mentioned (1) or (2) described in the manufacture method of liquid crystal orientation film, wherein, the heating-up temperature of [III] operation is
Than the temperature range that described side chain type polymeric membrane embodies liquid crystal liquid crystal property lower limit for height 10 DEG C temperature～than this temperature range
The temperature in the range of temperature that the upper limit is low 10 DEG C.
(4) above-mentioned (1)～(3) according to any one of the manufacture method of liquid crystal orientation film, wherein, described in embody liquid crystal
Property photosensitive side chain type macromolecule in contained photonasty group be diphenyl diimide, cinnamic acid, cinnamate, look into ear
Ketone, coumarin, tolan, phenol benzoate or derivatives thereof.
(5) manufacture method of a kind of liquid crystal orientation film, comprising:
[I] embodies the side chain type macromolecule of the photocrosslinking reaction of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate
The operation of film；
Described photocrosslinking reaction side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And
The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；
Illuminated described ultraviolet, the side chain type polymeric membrane that is then passed through heating are irradiated unpolarized ultraviolet by [IV]
Operation；
It is characterized in that, the ultraviolet irradiation amount of [II] operation Δ A reach maximum ultraviolet irradiation amount 1%～
In the range of 70%, Δ A is the direction that described side chain type polymeric membrane is parallel with the polarization direction of described polarized UV rays
The difference of the ultraviolet absorbance in ultraviolet absorbance and the direction vertical with the polarization direction of described polarized UV rays.
(6) manufacture method of the liquid crystal orientation film described in above-mentioned (5), wherein, the ultraviolet irradiation amount of [II] operation is in institute
State Δ A to reach in the range of the 1%～50% of maximum ultraviolet irradiation amount.
(7) above-mentioned (5) or (6) described in the manufacture method of liquid crystal orientation film, wherein, the heating-up temperature of [III] operation is
Than the temperature range that described side chain type polymeric membrane embodies liquid crystal liquid crystal property lower limit for height 10 DEG C temperature～than this temperature range
The temperature in the range of temperature that the upper limit is low 10 DEG C.
(8) above-mentioned (5)～(7) according to any one of the manufacture method of liquid crystal orientation film, wherein, by [IV] operation
Ultraviolet irradiates, and 20 moles of more than % of the photocrosslinking reaction group that described side chain type polymeric membrane is had react.
(9) above-mentioned (5)～(8) according to any one of the manufacture method of liquid crystal orientation film, wherein, described in embody liquid crystal
Property photocrosslinking reaction side chain type macromolecule in contained photonasty group be cinnamic acid, cinnamate, chalcone derivative, tonkabean
Element, tolan or derivatives thereof.
(10) above-mentioned (1)～(9) according to any one of the manufacture method of liquid crystal orientation film, wherein, described side chain type is high
Molecular film is the structure including main chain and side chain, and described main chain is by selected from hydrocarbon, acrylate and at least the one of methacrylate
Planting and constitute, described side chain represents with at least one in following formula (1)～(7)；
[changing 1]
In formula (1), A1、B1Separately represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-,
Y1It is at least one group of cyclic hydrocarbon selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, these bases
In group, the hydrogen atom of bonding can be separately by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or
Alkoxyl replaces；X1Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-, l1 (also referred to as l1) represent 1
～the integer of 12, m1 represents the integer of 1～3, and n1 represents the integer of 1～12；In formula (2), A2、B2、D1Separately represent single
Key ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-, Y2It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring
With at least one group of the cyclic hydrocarbon of carbon number 5～8, on these groups, the hydrogen atom of bonding can be separately by-NO2、-
CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl replace；X2Represent singly-bound ,-COO-,-OCO-,-N=
N-,-C=C-,-C ≡ C-or C6H4-, R1Represent hydrogen atom or the alkyl of carbon number 1～6；L2 (also referred to as l2) represent 1～12 whole
Number, m2 represents the integer of 1～3, and n2 represents the integer of 1～12；In formula (3), A3Represent singly-bound ,-O-,-CH2-、-COO-、-
OCO-,-CONH-or NH-CO-, X3Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-, R2Represent
Hydrogen atom or the alkyl of carbon number 1～6；L3 (also referred to as l3) represent 1～12 integer, m3 represents the integer of 1～3；In formula (4), l4
(also referred to as l4) represent 1～12 integer；In formula (5), A4Represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-
CO-, X4Expression-COO-, Y3It is at least one group selected from phenyl ring, naphthalene nucleus and cyclohexyl biphenyl, the hydrogen atom of bonding on these groups
Can be separately by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl replace；L5 is (also
Claim l5) represent 1～12 integer, m4 represents the integer of 1～3；In formula (6), A5Represent singly-bound ,-O-,-CH2-、-COO-、-
OCO-,-CONH-or NH-CO-, R3Represent selected from hydrogen atom ,-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, carbon
The alkyl of several 1～6 and at least one group of the alkoxyl of carbon number 1～6；L6 (also referred to as l6) represent 1～12 integer；Formula (6)
In phenyl ring on bonding hydrogen atom can be separately by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group,
Alkyl or alkoxyl replace；In formula (7), A6Represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-, B3Table
Show singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-；W1It is selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan
At least one group of the cyclic hydrocarbon of ring, pyrrole ring and carbon number 5～8, on these groups, the hydrogen atom of bonding can be independently
Ground is by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl replace；L7 represents the integer of 1～12,
M5, m6 represent the integer of 1～3 respectively.
(11) a kind of liquid crystal orientation film, it is by the manufacture of the liquid crystal orientation film according to any one of above-mentioned (1)～(10)
Method and make.
(12) a kind of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned (11).
The effect of invention
Pass through the present invention, it is possible to provide the manufacture method of a kind of liquid crystal orientation film that can realize high efficiency orientation process.
Additionally, use the manufacture method of this liquid crystal orientation film, it is possible to provide a kind of liquid that can realize high efficiency orientation process
Brilliant alignment films.Use this liquid crystal orientation film, may also provide and a kind of there is the liquid crystal realizing high efficiency orientation process and make take
To the liquid crystal display cells of film.
Accompanying drawing explanation
Fig. 1 be pattern to the anisotropic introducing in the manufacture method of the liquid crystal orientation film of first form of the present invention
Process the figure of the example illustrated.(a) be pattern represent the figure of state of the side chain type polymeric membrane before polarizing light irradiation,
The system of situation that the anisotropy that particularly introduces is little, the i.e. liquid crystal orientation film including above-mentioned [I]～[IV] operation of the present invention
Make the ultraviolet irradiation amount of [II] operation in method Δ A reach maximum ultraviolet irradiation amount 1%～15% scope
The ideograph of interior situation.(b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, (c) is
Pattern ground represents the figure of state of the side chain type polymeric membrane after heating, figure (d) be pattern represent after heating through non-polarized light
The figure of the state of the side chain type polymeric membrane irradiated.To above-mentioned first form as described later.
Fig. 2 be pattern to the anisotropic introducing in the manufacture method of the liquid crystal orientation film of first form of the present invention
Process the figure of an example illustrated, the including of situation that the anisotropy that particularly introduces is big, the i.e. present invention above-mentioned [I]～
The ultraviolet irradiation amount of [II] operation in the manufacture method of the liquid crystal orientation film of [IV] operation reaches the ultraviolet of maximum at Δ A
The ideograph of the situation in the range of the 15%～70% of irradiation dose.(a) be pattern represent the side chain type before polarizing light irradiation
The figure of the state of polymeric membrane, (b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, (c)
Be pattern represent the figure of state of the side chain type polymeric membrane after heating, figure (d) be pattern represent after heating through unpolarized
The figure of the state of the side chain type polymeric membrane that light irradiates.
Fig. 3 be pattern to the anisotropic introducing in the manufacture method of the liquid crystal orientation film of second form of the present invention
Process the figure of an example illustrated, particularly side chain type macromolecule be above formula (6) represent the situation of structure, i.e. the present invention
In manufacture method including above-mentioned [I]～[III] operation, when using the side chain type polymeric membrane of formula (6) structure that represents, [II]
The ultraviolet irradiation amount of operation reaches the pattern of the situation in the range of the 1%～70% of the ultraviolet irradiation amount of maximum at Δ A
Figure.(a) be pattern represent the figure of state of the side chain type polymeric membrane before polarizing light irradiation, (b) be pattern represent polarization
Light irradiate after the figure of state of side chain type polymeric membrane, (c) be pattern represent the shape of the side chain type polymeric membrane after heating
The figure of state.To above-mentioned second form as described later.
Fig. 4 be pattern to the anisotropic introducing in the manufacture method of the liquid crystal orientation film of second form of the present invention
Process the figure of an example illustrated, particularly side chain type macromolecule be above formula (7) represent the situation of structure, i.e. the present invention
In manufacture method including above-mentioned [I]～[III] operation, when using the side chain type macromolecule of formula (7) structure that represents, [II] work
The ultraviolet irradiation amount of sequence reaches the ideograph of the situation in the range of the 1%～70% of the ultraviolet irradiation amount of maximum at Δ A.
(a) be pattern represent the figure of state of the side chain type polymeric membrane before polarizing light irradiation, (b) be pattern represent that polarized light shines
The figure of the state of the side chain type polymeric membrane after penetrating, (c) be pattern represent the state of the side chain type polymeric membrane after heating
Figure.
Detailed description of the invention
Photosensitive side chain type that use in the manufacture method of the liquid crystal orientation film of the present invention, that can embody liquid crystal liquid crystal property is high
Molecular film is the photosensitive side chain type polymeric membrane embodying liquid crystal liquid crystal property within the temperature range of regulation.And, key on main chain
The side chain closed has photonasty, can sense that light crosslinks reaction, isomerization reaction or light fries' rearrangement.Key on main chain
The photosensitive group that has closed is not particularly limited, and preferably senses that light crosslinks reaction or the knot of light fries' rearrangement
Structure.Now, if exposed to external pressures such as heat, realized tropism control ability can also be kept steadily in the long term.Can embody
As long as the structure going out the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property meets this characteristic and is just not particularly limited, preferential side chains
Structure has the primitive composition (Japanese: メ ソ ゲ Application composition) of rigidity.
Now, when this side chain type macromolecule is made liquid crystal orientation film, stable liquid crystal aligning can be obtained.This is high molecular
Structure can be such as include main chain and side chain bonded thereto, this side chain have xenyl, terphenylyl, phenylcyclohexyl,
Primitive compositions such as phenylamino benzoic acid ester group, azobenzene and be bonded in leading section, sense that light carries out cross-linking reaction or isomery
Change the structure of the photonasty group of reaction, or can be to include that main chain and side chain bonded thereto, this side chain are also that primitive becomes
Divide and have the structure of the phenylamino benzoic acid ester group carrying out light Fries rearrangement.
As the more specifically example of the structure of the photosensitive side chain type polymeric membrane that can embody liquid crystal liquid crystal property, preferably wrap
Include by selected from hydrocarbon, acrylate, methacrylate, maleimide and hexamethylene at least one main chain constituted and by
The structure of the side chain that at least one in following formula (1)～(7) is constituted.
[changing 2]
(the A in formula (1)1、B1、X1、Y1, l1, m1, n1 the most as defined above, A in formula (2)2、B2、D1、X2、Y2、R1、
L2, m2, n2 are the most as defined above, the A in formula (3)3、X3、R2, l3, m3 the most as defined above, l4 in formula (4) is as the most fixed
Justice, the A in formula (5)4、X4、Y3, l5, m4 the most as defined above, A in formula (6)5、R3, l6 the most as defined above.In formula (7)
A6、B3、W1, l7, m5, m6 the most as defined above.)
The side chain that above formula (1)～(7) represent includes having biphenyl, terphenyl, phenylcyclohexyl, phenol benzoate, azo
The groups such as benzene are as the structure of primitive composition.And, its leading section have in following structure at least any one, i.e. there is sense
Light should be arrived and dimerization occur, carries out the photonasty group of cross-linking reaction, or include main chain and side chain bonded thereto,
This side chain is also primitive composition and has the phenylamino benzoic acid ester group carrying out light Fries rearrangement.
In the present invention, side chain type polymeric membrane not losing in the range of liquid crystal liquid crystal property and photoreactivity and can not have light
Reactive side-chain structure is also used.If illustrated, then can enumerate the structure of following formula (8).
[changing 3]
In above formula (8), E1Represent singly-bound ,-O-,-CH2-,-COO ,-OCO-,-CONH-,-NH-CO-, Z represent singly-bound ,-
COO ,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-, k1 represents the integer of 1～12, p1, q1 separately represent 0～
The integer of 3, R4Represent hydrogen atom ,-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, the alkoxyl of carbon number 1～6,
Carboxyl or by the group of a combination thereof.
Hereinafter, for the photonasty that use in the manufacture method of the liquid crystal orientation film of the present invention, liquid crystal liquid crystal property can be embodied
Side chain type polymeric membrane, be referred to as the side chain type polymeric membrane of the present invention.
In the manufacture method of the liquid crystal orientation film of the present invention, on substrate, form film with the side chain type macromolecule of the present invention
After, irradiate polarized UV rays.Then, to introduce in side chain type polymeric membrane efficiently anisotropy by carrying out heating, make
Become to have the liquid crystal orientation film of the tropism control ability of liquid crystal.In the manufacture method of the liquid crystal orientation film of the present invention, utilize this
The photoreaction of bright side chain type polymeric membrane and the principle of molecular reorientation induced by self assembly based on liquid crystal liquid crystal property are high
Effect ground introduces anisotropy in side chain type polymeric membrane.Further, in the manufacture method of the liquid crystal orientation film of the present invention, it is to have
In the case of photocrosslinking reaction group is as the structure of photoreactive group, formed on substrate with the side chain type macromolecule of the present invention
After film, irradiate polarized UV rays, after then heating, irradiate unpolarized ultraviolet, thereby can be introduced in polymeric membrane
Anisotropy immobilization.
Fig. 1 be pattern in the manufacture method of the liquid crystal orientation film of the present invention, use there is photocrosslinking reaction group conduct
Anisotropic introducing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group processes
The figure of the example illustrated.Fig. 1 (a) be pattern represent the figure of state of the side chain type polymeric membrane before polarizing light irradiation,
Fig. 1 (b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 1 (c) be pattern represent and add
The figure of the state of the side chain type polymeric membrane after heat, Fig. 1 (d) be pattern represent the side chain type macromolecule after illumination
The figure of the state of film, situation that the anisotropy that particularly introduces is little, the i.e. present invention include above-mentioned [I]～the liquid of [IV] operation
The ultraviolet irradiation amount of [II] operation in the manufacture method of brilliant alignment films reaches the 1% of the ultraviolet irradiation amount of maximum at Δ A
～the ideograph of the situation in the range of 15%.
Fig. 2 be pattern in the manufacture method of the liquid crystal orientation film of the present invention, use there is photocrosslinking reaction group conduct
Anisotropic introducing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group processes
The figure of the example illustrated.Fig. 2 (a) be pattern represent the figure of state of the side chain type polymeric membrane before polarizing light irradiation,
Fig. 2 (b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 2 (c) be pattern represent and add
The figure of the state of the side chain type polymeric membrane after heat, Fig. 2 (d) be pattern represent the side chain type macromolecule after illumination
The figure of the state of film, situation that the anisotropy that particularly introduces is big, the i.e. present invention include above-mentioned [I]～the liquid of [IV] operation
The ultraviolet irradiation amount of [II] operation in the manufacture method of brilliant alignment films reaches the 15% of the ultraviolet irradiation amount of maximum at Δ A
～the ideograph of the situation in the range of 70%.
Fig. 3 be pattern in the manufacture method of the liquid crystal orientation film of the present invention, use and there is light that above formula (6) represents not
Li Si resets each as in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group of group
Heterotropic introducing processes the figure of the example illustrated.Fig. 3 (a) be pattern represent the side chain type high score before polarizing light irradiation
The figure of the state of sub-film, Fig. 3 (b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 3
(c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, situation that the anisotropy that particularly introduces is little,
The i.e. ultraviolet irradiation amount of [II] operation in the manufacture method including above-mentioned [I]～[III] operation of the present invention reaches at Δ A
The ideograph of the situation in the range of the 1%～70% of maximum ultraviolet irradiation amount.
Fig. 4 be pattern in the manufacture method of the liquid crystal orientation film of the present invention, use and there is light that above formula (7) represents not
Li Si resets each as in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photoreactive group of group
Heterotropic introducing processes the figure of the example illustrated.Fig. 4 (a) be pattern represent the side chain type high score before polarizing light irradiation
The figure of the state of sub-film, Fig. 4 (b) be pattern represent the figure of state of the side chain type polymeric membrane after polarizing light irradiation, Fig. 4
(c) be pattern represent the figure of state of the side chain type polymeric membrane after heating, situation that the anisotropy that particularly introduces is big,
The i.e. ultraviolet irradiation amount of [II] operation in the manufacture method including above-mentioned [I]～[III] operation of the present invention reaches at Δ A
The ideograph of the situation in the range of the 1%～70% of maximum ultraviolet irradiation amount.
Hereinafter, use is had the high molecular enforcement of side chain type as the structure of photoreactive group of the photocrosslinking reaction group
Mode is referred to as the first form, and use has the light fries' rearrangement group side chain type high score as the structure of photoreactive group
The embodiment of son is referred to as the second form, illustrates.
By in the side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film of first form of the present invention each to
The introducing of the opposite sex processes, and the ultraviolet irradiation amount of [II] operation reaches 1%～the 15% of the ultraviolet irradiation amount of maximum at Δ A
In the case of in the range of, on substrate, first form the side chain type polymeric membrane 1 of the present invention.As shown in Fig. 1 (a), it is formed at base
The side chain type polymeric membrane 1 of the present invention on plate has the structure of side chain 2 random alignment.Side along side chain type polymeric membrane 1
The random alignment of chain 2, the primitive composition of side chain 2 and photonasty group also random orientation, this side chain type polymeric membrane 1 in each to
Property.
By in the side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film of first form of the present invention each to
The introducing of the opposite sex processes, and the ultraviolet irradiation amount of [II] operation reaches the 15%～70% of the ultraviolet irradiation amount of maximum at Δ A
In the case of in the range of, on substrate, first form the side chain type polymeric membrane 3 of present embodiment.As shown in Fig. 2 (a), shape
The side chain type polymeric membrane 3 becoming the present invention on substrate has the structure of side chain 4 random alignment.Along side chain type polymeric membrane
The random alignment of the side chain 4 of 3, the primitive composition of side chain 4 and photonasty group also random orientation, this side chain type polymeric membrane 2 in
Isotropism.
By in the side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film of second form of the present invention each to
The introducing of the opposite sex processes, and employing use has the side chain type macromolecule of the structure of the light fries' rearrangement group that above formula (6) represents
Liquid crystal orientation film in the case of, the ultraviolet irradiation amount of [II] operation Δ A reach maximum ultraviolet irradiation amount 1%～
In the case of in the range of 70%, on substrate, first form the side chain type polymeric membrane 5 of the present invention.As shown in Fig. 3 (a), shape
The side chain type polymeric membrane 5 becoming the present invention on substrate has the structure of side chain 6 random alignment.Along side chain type polymeric membrane
The random alignment of the side chain 6 of 5, the primitive composition of side chain 6 and photonasty group also random orientation, this side chain type polymeric membrane 5 in
Isotropism.
By in the side chain type polymeric membrane in the manufacture method of the liquid crystal orientation film of second form of the present invention each to
The introducing of the opposite sex processes, use use to have light fries' rearrangement group that above formula (7) represents as the side chain type of structure high
In the case of the liquid crystal orientation film of molecule, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet irradiation amount of maximum at Δ A
In the case of in the range of 1%～70%, on substrate, first form the side chain type polymeric membrane 7 of the present invention.Such as Fig. 4 (a) institute
Showing, the side chain type polymeric membrane 7 of the present invention being formed on substrate has the structure of side chain 8 random alignment.High along side chain type
The random alignment of the side chain 8 of molecular film 7, the primitive composition of side chain 8 and photonasty group also random orientation, this side chain type macromolecule
Film 7 is in isotropism.
In first form of the present invention, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet irradiation amount of maximum at Δ A
1%～15% in the range of in the case of, the side chain type polymeric membrane 1 of this isotropic present invention is irradiated polarized UV
Line.Then, as shown in Fig. 1 (b), having in the side chain 2 arranged on the direction parallel with the polarization direction of ultraviolet is photosensitive
The photoreactions such as the photonasty group priorities generation dimerization of side chain 2a of property group.As a result of which it is, the side chain after photoreaction
The density of 2a is slightly elevated on the polarization direction of irradiation ultraviolet radiation, and result gives the side chain type polymeric membrane 1 of the present invention with non-
The least anisotropy.
In first form of the present invention, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet irradiation amount of maximum at Δ A
15%～70% in the range of in the case of, the side chain type polymeric membrane 3 of this isotropic present invention is irradiated polarization purple
Outside line.Then, as shown in Fig. 2 (b), on the direction parallel with the polarization direction of ultraviolet arrangement side chain 4 in there is sense
The photoreactions such as the photonasty group priorities generation dimerization of the side chain 4a of photosensitiveness group.As a result of which it is, the side after photoreaction
The density of chain 4a raises on the polarization direction of irradiation ultraviolet radiation, and result gives the side chain type polymeric membrane 3 of the present invention with less
Anisotropy.
In second form of the present invention, employing use has the structure of the light fries' rearrangement group that above formula (6) represents
In the case of the high molecular liquid crystal orientation film of side chain type, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet of maximum at Δ A
In the case of in the range of the 1%～70% of irradiation dose, the side chain type polymeric membrane 5 of this isotropic present invention is irradiated partially
Shake ultraviolet.Then, as shown in Fig. 3 (b), the tool in the side chain 6 of arrangement on the direction parallel with the polarization direction of ultraviolet
The photoreactions such as the photonasty group priorities generation light fries' rearrangement having the side chain 6a of photonasty group.As a result of which it is, photoreaction
After the density of side chain 6a slightly elevated on the polarization direction of irradiation ultraviolet radiation, result gives the side chain type macromolecule of the present invention
Film 5 is with the least anisotropy.
In second form of the present invention, employing use has the structure of the light fries' rearrangement group that above formula (7) represents
In the case of the high molecular liquid crystal orientation film of side chain type, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet of maximum at Δ A
In the case of in the range of the 1%～70% of irradiation dose, the side chain type polymeric membrane 7 of this isotropic present invention is irradiated partially
Shake ultraviolet.Then, as shown in Fig. 4 (b), the tool in the side chain 8 of arrangement on the direction parallel with the polarization direction of ultraviolet
The photoreactions such as the photonasty group priorities generation light fries' rearrangement having the side chain 8a of photonasty group.As a result of which it is, photoreaction
After the density of side chain 8a raise on the polarization direction of irradiation ultraviolet radiation, result gives the side chain type polymeric membrane 7 of the present invention
With less anisotropy.
Then, in first form of the present invention, the ultraviolet irradiation amount of [II] operation reaches maximum ultraviolet at Δ A and shines
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 after polarizing light irradiation is heated,
Making it is mesomorphic state.Then, as shown in Fig. 1 (c), in side chain type polymeric membrane 1, put down in the polarization direction with irradiation ultraviolet radiation
Between direction and the vertical direction of row, the amount of the cross-linking reaction of generation is different.Now, with the polarization side of irradiation ultraviolet radiation
The amount of the cross-linking reaction occurred on parallel direction is the least, and therefore the effect of plasticizer is played at this cross-linking reaction position.Cause
This, the liquid crystal liquid crystal property in the direction vertical with the polarization direction of irradiation ultraviolet radiation is higher than the liquid crystal liquid crystal property of parallel direction, with irradiate ultraviolet
Self assembly on the direction that the polarization direction of line is parallel, the side chain 2 comprising primitive composition re-aligns.As a result of which it is, handed over by light
The least anisotropy of the side chain type polymeric membrane 1 of the present invention of connection reaction induction is exaggerated under the effect of heat, from
And give the side chain type polymeric membrane 1 of the present invention with bigger anisotropy.
Similarly, in first form of the present invention, the ultraviolet irradiation amount of [II] operation reaches the ultraviolet of maximum at Δ A
In the case of in the range of the 15%～70% of irradiation dose, the side chain type polymeric membrane 3 of the present invention after polarizing light irradiation is added
Heat so that it is in mesomorphic state.Then, as shown in Fig. 2 (c), in side chain type polymeric membrane 3, in the polarization side with irradiation ultraviolet radiation
To between parallel direction and vertical direction, the amount of the cross-linking reaction of generation is different.Therefore, with irradiation ultraviolet radiation
Self assembly on the direction that polarization direction is parallel, the side chain 4 comprising primitive composition re-aligns.As a result of which it is, it is anti-by photo-crosslinking
The less anisotropy of the side chain type polymeric membrane 3 of the present invention that should induce is exaggerated under the effect of heat, thus gives
The side chain type polymeric membrane 3 of the present invention is with bigger anisotropy.
Similarly, in second form of the present invention, use use to have light fries' rearrangement group that above formula (6) represents
In the case of the high molecular liquid crystal orientation film of side chain type of structure, the ultraviolet irradiation amount of [II] operation reaches maximum at Δ A
Side chain type macromolecule in the case of in the range of the 1%～70% of ultraviolet irradiation amount, to the present invention after polarizing light irradiation
Film 5 heats so that it is in mesomorphic state.Then, as shown in Fig. 3 (c), in side chain type polymeric membrane 5, inclined with irradiation ultraviolet radiation
Shaking between parallel direction and vertical direction, direction, the amount of the light Fries rearrangement of generation is different.Now, with photograph
Penetrate the side chain before the liquid crystal aligning force rate reaction of the light fries' rearrangement body generated on the direction that the polarization direction of ultraviolet is vertical
Liquid crystal aligning power strong, therefore self assembly on the direction vertical with the polarization direction of irradiation ultraviolet radiation, comprises primitive composition
Side chain 6 re-aligns.As a result of which it is, the side chain type polymeric membrane 5 of the present invention induced by light Fries rearrangement is non-
The least anisotropy is exaggerated under the effect of heat, thus gives the side chain type polymeric membrane 5 of the present invention with bigger each
Anisotropy.
Similarly, in second form of the present invention, use use to have light fries' rearrangement group that above formula (7) represents
In the case of the high molecular liquid crystal orientation film of side chain type of structure, the ultraviolet irradiation amount of [II] operation reaches maximum at Δ A
Side chain type macromolecule in the case of in the range of the 1%～70% of ultraviolet irradiation amount, to the present invention after polarizing light irradiation
Film 7 heats so that it is in mesomorphic state.Then, as shown in Fig. 4 (c), in side chain type polymeric membrane 7, inclined with irradiation ultraviolet radiation
Shaking between parallel direction and vertical direction, direction, the amount of the light Fries rearrangement of generation is different.Light fries
Reset the side chain Final 8 before the anchor force ratio rearrangement of body 8 (a), if therefore generating the light fries' rearrangement of more than certain ormal weight
Body, then self assembly on the direction parallel with the polarization direction of irradiation ultraviolet radiation, the side chain 8 comprising primitive composition refetches
To.As a result of which it is, the less anisotropy of the side chain type polymeric membrane 7 of the present invention induced by light Fries rearrangement exists
It is exaggerated under the effect of heat, thus gives the side chain type polymeric membrane 7 of the present invention with bigger anisotropy.
Further, in first form of the present invention, as shown in Fig. 1 (d) and Fig. 2 (d), the high molecular light of side chain type of the present invention
In the case of reactive group is photocrosslinking reaction group, by the self assembly of primitive at side chain as shown in Fig. 1 (c) and Fig. 2 (c)
In polymeric membrane after Induced Anisotropy, carry out illumination, thereby the anisotropy largely of induction is fixed
Change.
Therefore, in the manufacture method of the liquid crystal orientation film of the present invention, by carrying out the side chain type high score to the present invention successively
The polarized UV rays of sub-film irradiate and after heat treated in the case of first form of heat treated and the present invention non-partially
The light that shakes irradiates.Can obtain efficiently and introduce anisotropic liquid crystal orientation film.
And, in the manufacture method of the liquid crystal orientation film of the present invention, optimize the inclined of the side chain type polymeric membrane to the present invention
Shake the heating-up temperature in ultraviolet irradiation amount and heat treated.Thereby, can introduce respectively in side chain type polymeric membrane efficiently
Anisotropy.
The present inventor, after conscientiously research, has obtained following knowledge.I.e., efficiently to the side chain type polymeric membrane of the present invention
Introduce anisotropic optimal polarization ultraviolet irradiation amount and carry out light with making the photonasty group in this side chain type polymeric membrane
The irradiation dose that the amount of the reaction of cross-linking reaction, photoisomerization or light Fries rearrangement reaches optimal polarized UV rays is relative
Should.It is to carry out photo-crosslinking, photoisomerization reaction to the result of the side chain type polymeric membrane irradiation polarized UV rays of the present invention
If or the photonasty group of the side chain of light Fries rearrangement is few, then do not reach enough photoreaction amounts.Now, though with
After carry out heating and also cannot be carried out sufficient self assembly.
On the other hand, in the side chain type polymeric membrane of the present invention, the structured illumination with photocrosslinking reaction group is polarized purple
The result of outside line is, if carrying out the photonasty group excess of the side chain of cross-linking reaction, then the cross-linking reaction on side chain is excessively entered
OK.Now, the film of gained is rigidity, sometimes interferes with the carrying out of the self assembly implemented subsequently by heating.Additionally, the present invention
In side chain type polymeric membrane, it is to carry out light not to the result of the structured illumination polarized UV rays with light fries' rearrangement group
If the photonasty group excess of the side chain of this rearrangement reaction of profit, then the liquid crystal liquid crystal property of side chain type polymeric membrane excessively reduces.Now,
The liquid crystal liquid crystal property of the film of gained also reduces, and sometimes interferes with the carrying out of the self assembly implemented subsequently by heating.And, to having light
In the case of the structured illumination polarized UV rays of fries' rearrangement group, if ultraviolet irradiation amount is too much, then the present invention
Side chain type macromolecule generation photodissociation, sometimes interferes with the carrying out of the self assembly implemented subsequently by heating.
Therefore, in the side chain type polymeric membrane of the present invention, by the irradiation of polarized UV rays, the photonasty group of side chain enters
The optimal amount of the reaction of row photo-crosslinking, photoisomerization or light Fries rearrangement is preferably this side chain type polymeric membrane institute
0.1 mole of %～40 moles of % of the photonasty group having, more preferably 0.1 mole %～20 moles of %.In the present invention, logical
Crossing the amount of the photonasty group making to carry out the side chain of photoreaction within the range, the self assembly by heat treated subsequently is efficient
Ground is carried out, and can form anisotropy efficiently in film.
In the manufacture method of the liquid crystal orientation film of the present invention, by the optimization of the irradiation dose of polarized UV rays, optimize side
The photo-crosslinking of photonasty group, photoisomerization reaction or light Fries rearrangement on the side chain of chain polymeric membrane
Amount.Then, add heat treated subsequently, anisotropy can be introduced efficiently in side chain type polymeric membrane.Now, about
The suitably amount of polarized UV rays, can be carried out in the evaluation of uv absorption of side chain type polymeric membrane based on the present invention.
That is, for the side chain type polymeric membrane of the present invention, after polarized UV rays is irradiated and polarized UV rays is measured respectively
The ultra-violet absorption in parallel direction, polarization direction and the ultraviolet in the direction vertical with the polarization direction of polarized UV rays inhale
Receive.Measurement result according to uv absorption evaluates Δ A, and what this Δ A was this side chain type polymeric membrane with polarized UV rays is inclined
Shake the ultraviolet absorbance in parallel direction, direction and the UV absorbance in the direction vertical with the polarization direction of polarized UV rays
The difference of degree.Then, obtain the maximum (Δ Amax) of the Δ A realized in the side chain type polymeric membrane of the present invention and realize this
The irradiation dose of the polarized UV rays of big value.In the manufacture method of the liquid crystal orientation film of the present invention, can be to realize this Δ Amax's
The preferred polarized UV rays amount irradiated in the manufacture process of liquid crystal orientation film is determined on the basis of polarized UV rays irradiation dose.
In the manufacture method of the liquid crystal orientation film of the present invention, to the polarized UV rays of the side chain type polymeric membrane of the present invention
Irradiation dose is preferably in the range of the 1%～70% of the amount of the polarized UV rays realizing Δ Amax, more preferably 1%～50%
In the range of.In the side chain type polymeric membrane of the present invention, it is achieved in the range of the 1%～50% of the amount of the polarized UV rays of Δ Amax
The irradiation dose of polarized UV rays be equivalent to 0.1 mole of % of all photonasty groups making this side chain type polymeric membrane be had
～20 moles of % carry out the amount of polarized UV rays of photo-crosslinking.
Then, in the manufacture method of the liquid crystal orientation film of the present invention, the side chain type polymeric membrane of the present invention is irradiated polarization
After ultraviolet, carry out the heating of this side chain type polymeric membrane.The side chain type polymeric membrane of the present invention is can be at the temperature model of regulation
The polymeric membrane of liquid crystal liquid crystal property is embodied in enclosing.Heat treated after polarized UV rays is irradiated can be to embody this side chain type high score
Determine on the basis of the temperature of the liquid crystal liquid crystal property of sub-film.That is, the heating-up temperature after polarized UV rays is irradiated is preferably than the side of the present invention
Chain polymeric membrane embodies the temperature of the lower limit for height 10 DEG C of the temperature range (calling liquid crystal temperature range in the following text) of liquid crystal liquid crystal property～than being somebody's turn to do
Temperature in the range of the temperature of low 10 DEG C of the upper limit of liquid crystal temperature range.
The side chain type polymeric membrane of the present invention is heated after the irradiation of polarized UV rays, becomes mesomorphic state, with partially
Shake self assembly on parallel direction, direction, re-align.As a result of which it is, by photo-crosslinking, photoisomerization reaction and light not
The less anisotropy of the side chain type polymeric membrane of the present invention of profit this rearrangement reaction induction is exaggerated under the effect of heat.
But, even if the side chain type polymeric membrane of the present invention by heating and in mesomorphic state in the case of, if heating-up temperature is low, then
The viscosity of the side chain type polymeric membrane of mesomorphic state is high, it is difficult to re-aligned by self assembly.Such as, heating-up temperature the highest not
In the case of in the range of the temperature of the lower limit for height 10 DEG C exceeding the liquid crystal temperature range of side chain type polymeric membrane than the present invention,
The anisotropic amplification effect caused by heat in the side chain type polymeric membrane of enough present invention cannot be produced.
Even if additionally, the side chain type polymeric membrane of the present invention by heating and in mesomorphic state, if heating-up temperature is high, then
The state of side chain type polymeric membrane is close to isotropic liquid condition, it is difficult to refetched in one direction by self assembly
To.Such as, heating-up temperature is the temperature of low 10 DEG C of the upper limit of the liquid crystal temperature range with the side chain type polymeric membrane than the present invention
In the case of comparing higher temperature, it is impossible to produce in the side chain type polymeric membrane of enough present invention by heat cause each
Heterotropic amplification effect.
As it has been described above, in the manufacture method of the liquid crystal orientation film of the present invention, in order to efficiently in side chain type polymeric membrane
Introduce anisotropy, on the basis of the liquid crystal temperature range of this side chain type polymeric membrane, determine suitable heating-up temperature.And
As it has been described above, the temperature of the heating after polarized UV rays being irradiated is set to the liquid crystal temperature range than this side chain type polymeric membrane
The temperature of lower limit for height 10 DEG C be lower limit, with the temperature of lower than the upper limit of liquid crystal temperature range 10 DEG C as the upper limit in the range of temperature
Degree.It is thus possible, for instance in the case of the liquid crystal temperature range of the side chain type polymeric membrane of the present invention is 100 DEG C～200 DEG C, polarization purple
The temperature of the heating after outside line irradiation is preferably 110 DEG C～190 DEG C.Thereby, can give the side chain type polymeric membrane of the present invention with
Bigger anisotropy.
Above the orientation process in the manufacture method of the liquid crystal orientation film of the present invention is illustrated, then to this
The manufacture method of bright liquid crystal orientation film illustrates.
The manufacture method of the liquid crystal orientation film of the present invention includes following [I]～the operation of [III] or following in the following order
[I]～the operation of [IV].Can manufacture and introduce anisotropic liquid crystal orientation film with high efficiency.
[I] forms the operation of the photosensitive side chain type polymeric membrane that can embody liquid crystal liquid crystal property on substrate；
[II] side chain type polymeric membrane to obtaining in operation [I] irradiates the operation of polarized UV rays；
The operation of [III] side chain type polymeric membrane heating to irradiating through polarized UV rays in operation [II]；
Illuminated described ultraviolet, the side chain type polymeric membrane that is then passed through heating are irradiated unpolarized ultraviolet by [IV]
Operation.
Hereinafter, to [I] included by the manufacture method of the liquid crystal orientation film of the present invention～the operation of [III] or following [1]
～each operation of the operation of [IV] illustrates.
In operation [I], substrate forms the side chain type polymeric membrane of the present invention.Substrate is not particularly limited.Such as, remove
Outside glass substrate, it is possible to use the transparency carriers such as plastic base such as acrylic acid substrate and polycarbonate substrate.In view of gained liquid
The application of brilliant alignment films, from the viewpoint of the simplification of the manufacturing process of liquid crystal display cells, it is possible to use be formed with liquid crystal
The substrate of ITO (Indium Tin Oxide: the tin indium oxide) electrode etc. driven.Furthermore, it is contemplated that reflective liquid crystal shows
Application in element, it is possible to use the opaque substrate such as silicon wafer, electrode now can also use the reflection light such as aluminum
Material.
In the case of the side chain type polymeric membrane of the present invention is in being dissolved in the solution shape of required solvent, the film on substrate is formed
Carry out by being coated with the side chain type polymeric membrane The of this solution shape.Being not particularly limited coating process, industrial circle is usual
Use the method being coated by silk screen printing, hectographic printing, flexographic printing or ink-jet method etc..As other coating process,
There are dip coating, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying process etc., can be used these according to purpose
Method.
On substrate after the side chain type polymeric membrane of the present invention of coating solution shape, heating plate, heat-circulation type can be passed through
The heaters such as stove or IR (infrared ray) type stove 20 DEG C～180 DEG C, preferably make solvent evaporate at 40 DEG C～150 DEG C, thus
Obtain the side chain type polymeric membrane of the present invention.If the thickness of side chain type polymeric membrane is blocked up, then using liquid crystal orientation film
The power consumption aspect of liquid crystal display cells is unfavorable；If crossing thin, the reliability of liquid crystal display cells reduces the most sometimes, the most preferably
5nm～300nm, more preferably 10nm～100nm.
Side chain type polymeric membrane is will be formed with alternatively, it is also possible to arrange after [I] operation, before follow-up [II] operation
Substrate be cooled to the operation of room temperature.
In operation [II], the side chain type polymeric membrane obtained in operation [I] is irradiated polarized UV rays.High to side chain type
In the case of the face of molecular film irradiates polarized UV rays, across polaroid, substrate is irradiated polarized UV rays from certain orientation.
As ultraviolet used, it is possible to use the ultraviolet in the range of wavelength 100nm～400nm.Preferably according to side used
The kind of chain polymeric membrane selects suitable wavelength by wave filter etc..Such as, anti-in order to enable optionally to induce photo-crosslinking
Should, can select to use the ultraviolet in the range of wavelength 250nm～400nm.As ultraviolet, such as, can use by high pressure
The light that mercury lamp emission goes out.
About the irradiation dose of polarized UV rays, as described above, it is preferred at the side chain type polymeric membrane of the present invention used
The polarized UV rays realizing Δ Amax amount 1%～70% in the range of, more preferably in the range of 1%～50%.
In operation [III], to the side chain type polymeric membrane heating irradiated through polarized UV rays in operation [II].Heating uses
The heaters such as heating plate, heat-circulation type stove or IR (infrared ray) type stove.About the temperature of heating, as set forth above, it is possible to consider
Side chain type polymeric membrane to the present invention used embodies the temperature of liquid crystal liquid crystal property and determines.That is, after polarized UV rays is irradiated
Heating-up temperature preferably embody the liquid crystal temperature range of liquid crystal liquid crystal property with the side chain type polymeric membrane than the present invention used
The temperature of lower limit for height 10 DEG C is lower limit, with the temperature of lower than the upper limit of liquid crystal temperature range 10 DEG C as the upper limit in the range of temperature
Degree.
By including above operation, by the manufacture method of the liquid crystal orientation film of the present invention, can be high to side chain type efficiently
Molecular film introduces anisotropy.And the liquid crystal orientation film of the present invention can be manufactured efficiently.
In operation [IV], to illuminated described ultraviolet, be then passed through heating side chain type polymeric membrane irradiate unpolarized
Ultraviolet.By this operation, unreacted in [II] operation and remain, occur in [III] operation the present invention's of reorientation
Side chain type polymeric membrane crosslinks reaction, is orientated stabilisation.
Ultraviolet preferably by [IV] operation irradiates, and makes the photocrosslinking reaction base that described side chain type polymeric membrane is had
20 moles of more than % of group react.In other words, if there is no the photocrosslinking reaction base of 20 moles of more than % in [II] operation
Group left behind, then be not easy in this operation fully to realize being orientated stabilisation.Its reason is, the photoreactive group of reorientation
It is difficult to keep its state of orientation and immobilization.In the case of above formula (6), (7), if carried out this operation, then the effect of the present invention
It is not easy on the contrary to play.
Embodiment
Enumerate embodiment embodiments of the present invention are described in detail.But, the present invention is not necessarily to be construed as
It is confined to this.
<synthesis example 1>
By 4,4 '-'-biphenyl diphenol and 1,6-dibromo-hexane heats in the basic conditions, thus synthesizes 4 '-(6-bromine hexyloxy)
Biphenyl-4-phenol.Make this product react with lithium methacrylate, obtain 2-(4 '-xenol-4-base epoxide) hexoxymethyl
Acrylate.Then, 4-methoxycinnamate acyl chlorides, the compound shown in synthesis following formula (9) are added in the basic conditions.
<synthesis example 2>
1-hydroxycinnamic acid and 1-hydroxyl-6-hexanol are heated in the basic conditions, thus synthesizes 4-(the own oxygen of 6-hydroxyl
Base) cinnamic acid.Make this product react in the basic conditions with methacrylic chloride, obtain the compound shown in following formula (10).
<synthesis example 3>
1-hydroxy benzoic acid and 1-hydroxyl-6-hexanol are heated in the basic conditions, thus synthesizes 4-(the own oxygen of 6-hydroxyl
Base) benzoic acid.Make this product react in the basic conditions with methacrylic chloride, obtain the compound shown in following formula (11).
<synthesis example 4>
Chloro-to 4-iodophenol and 6-1-hexanol is heated in the basic conditions, thus synthesizes 4-(6-hydroxyl hexyloxy) iodobenzene
Phenol.After making this product react with 2-methyl-3-butyne-2-alcohol, heat in the basic conditions, thus (6-hydroxyl is own to obtain 4-
Epoxide) Phenylacetylene. (compound A).Additionally, make 4-methoxycinnamate acyl chlorides react with 4-iodophenol by other approach, synthesize 4-
Iodophenyl-3-(4-methoxyphenyl) acrylate (compound B).Then, compound A and compound B is made in the basic conditions
Reaction, thus obtain the compound shown in following formula (12).
<synthesis example 5>
1-hydroxy benzoic acid and 1-hydroxyl-6-hexanol are heated in the basic conditions, thus synthesizes 4-(the own oxygen of 6-hydroxyl
Base) after benzoic acid, add thionyl chloride, thus obtain 4-(6-hydroxyl hexyloxy) Benzenecarbonyl chloride..Make this product and to methoxy
Base phenol reacts in the basic conditions, obtains the compound shown in following formula (13).
<synthesis example 6>
Methacrylate shown in above formula (9) is dissolved in oxolane, adds azodiisobutyronitrile (AIBN) and make
It is polymerized for reaction initiator, thus obtains polymer 1.This polymer 1 shows within the temperature range of 116 DEG C～315 DEG C
Go out liquid crystal liquid crystal property.
<synthesis example 7>
Methacrylate shown in above formula (10) is dissolved in oxolane, adds azodiisobutyronitrile (AIBN) and make
It is polymerized for reaction initiator, thus obtains polymer 2.This polymer 2 shows within the temperature range of 135 DEG C～187 DEG C
Go out liquid crystal liquid crystal property.
<synthesis example 8>
By the methacrylate shown in above formula (10) and the methacrylate shown in above formula (11) with 25 to 75 ratio
Example is dissolved in oxolane, adds azodiisobutyronitrile (AIBN) and is polymerized as reaction initiator, thus is polymerized
Thing 3.This polymer 3 demonstrates liquid crystal liquid crystal property within the temperature range of 146 DEG C～183 DEG C.
<synthesis example 9>
Methacrylate shown in above formula (12) is dissolved in oxolane, adds azodiisobutyronitrile (AIBN) and make
It is polymerized for reaction initiator, thus obtains polymer 4.This polymer 4 demonstrates within the temperature range of 66 DEG C～320 DEG C
Liquid crystal liquid crystal property.
<synthesis example 10>
Methacrylate shown in above formula (13) is dissolved in oxolane, adds azodiisobutyronitrile (AIBN) and make
It is polymerized for reaction initiator, thus obtains polymer 5.This polymer 5 shows within the temperature range of 143 DEG C～283 DEG C
Go out liquid crystal liquid crystal property.
[changing 4]
<introducing the preparation of anisotropic liquid crystal orientation film>
<embodiment 1>
Using the polymer 1 obtained in synthesis example 6, be dissolved in dichloromethane, the thickness spin with about 190nm is each at optics
On the substrate of the same sex, thus on substrate, form side chain type polymeric membrane.With this basal lamina determination ultra-violet absorption spectrum, result is
Big absorbance is 0.89 at 314nm.Side chain type polymeric membrane irradiation Glan-Taylor prism on the substrate of gained is turned
Change the ultraviolet of rectilinearly polarized light into.
Measure ultra-violet absorption spectrum with the side chain type polymeric membrane on the substrate obtained as mentioned above, evaluate Δ A, this Δ A
The ultraviolet absorbance in the direction that the polarization direction of the polarized UV rays being side chain type polymeric membrane and irradiate is parallel and with photograph
The difference of the ultraviolet absorbance in the direction that the polarization direction of the polarized UV rays penetrated is vertical.Irradiate and be scaled with wavelength 365nm
During the polarized UV rays of 4500mJ, Δ A is 0.2 at 314nm to the maximum, irradiates the polarized UV rays of 650mJ so that Δ A reaches
0.065 (having the difference of 32% relative to maximum), is then heated to 155 DEG C by this substrate, and making side chain type polymeric membrane is liquid crystal
Phase, keeps 5 minutes with this state.It is then cooled to room temperature, obtains having in film, introduce anisotropic side chain type high score
The substrate of sub-film.Δ A now is amplified to 1.8, and the degree of orientation is 0.73.Then, anisotropic side chain type is introduced to having
The substrate of polymeric membrane irradiates the unpolarized ultraviolet being scaled 1500mJ with wavelength 365nm, thus obtains having liquid crystal aligning
The substrate of film.
<embodiment 2>
Except using in synthesis example 6 polymer 1 obtained, the irradiation dose of polarized UV rays to be, (Δ A reaches Δ A to 500mJ
The irradiation dose of the 25% of big value) beyond, carry out polarized UV rays similarly to Example 1 and irradiate and heat treatment subsequently.Its knot
Fruit is that the Δ A before and after heat treatment is amplified to 1.85 from 0.05, and the degree of orientation now is 0.74 at 314nm.Then with embodiment
1 similarly irradiates unpolarized ultraviolet, obtains the substrate with liquid crystal orientation film.
<embodiment 3>
Except the polymer obtained in synthesis example 72 being dissolved in oxolane, with the thickness spin of about 150nm at optics
On isotropic substrate, the irradiation dose of polarized UV rays be 5mJ (Δ A reach Δ A maximum 10% irradiation dose), subsequently
Heat treatment be at 165 DEG C beyond 5 minutes, carry out polarized UV rays similarly to Example 1 and irradiate and heat treatment subsequently.Its
Result is, the Δ A before and after heat treatment is amplified to 1.6 from 0.03, and the degree of orientation now is 0.72 at 314nm.Then with enforcement
Example 1 similarly irradiates the unpolarized ultraviolet of 1000mJ, obtains the substrate with liquid crystal orientation film.
<embodiment 4>
Except using in synthesis example 8 polymer 3 obtained, the irradiation dose of polarized UV rays to be, (Δ A reaches Δ A to 20mJ
The irradiation dose of the 40% of big value) beyond, carry out polarized UV rays similarly to Example 3 and irradiate and heat treatment subsequently.Its knot
Fruit is that the Δ A before and after heat treatment is amplified to 1.6 from 0.12, and the degree of orientation now is 0.62 at 314nm.Then with embodiment 1
Similarly irradiate the unpolarized ultraviolet of 1000mJ, obtain the substrate with liquid crystal orientation film.
<embodiment 5>
Except the polymer obtained in synthesis example 94 being dissolved in dichloromethane, with the thickness spin of about 220nm at optics
Form side chain type polymeric membrane on substrate on isotropic substrate, the irradiation dose of polarized UV rays is that (Δ A reaches 300mJ
To Δ A maximum 29% irradiation dose), heat treatment subsequently be at 200 DEG C beyond 5 minutes, carry out similarly to Example 1
Polarized UV rays is irradiated and heat treatment subsequently.As a result of which it is, the Δ A before and after heat treatment is amplified to 1.4 from 0.04, taking now
It is 0.62 at 294nm to degree.Irradiate the unpolarized ultraviolet of 5000mJ the most similarly to Example 1, obtain that there is liquid crystal
The substrate of alignment films.
<embodiment 6>
Except the polymer obtained in synthesis example 10 5 being dissolved in dichloromethane, with the thickness spin of about 220nm at optics
Form side chain type polymeric membrane on substrate on isotropic substrate, the irradiation dose of polarized UV rays is that (Δ A reaches 1000mJ
To Δ A maximum 49% irradiation dose), heat treatment subsequently be at 180 DEG C beyond 5 minutes, carry out similarly to Example 1
Polarized UV rays is irradiated and heat treatment subsequently.As a result of which it is, Δ A before and after obtaining having heat treatment from 0.07 being amplified to 1.7,
The degree of orientation now is the substrate of the liquid crystal orientation film of 0.72 at 262nm.
<comparative example 1>
Using the polymer 1 obtained in synthesis example 6, be dissolved in dichloromethane, the thickness spin with about 190nm is each at optics
On substrate, side chain type polymeric membrane is formed on the substrate of the same sex.With this basal lamina determination ultra-violet absorption spectrum, result is maximum
Absorbance is 0.89 at 314nm.To the side chain type polymeric membrane irradiation Glan on the substrate of gained-Taylor prism conversion
Be in line the ultraviolet of polarized light.
Measure ultra-violet absorption spectrum with the side chain type polymeric membrane on the substrate obtained as mentioned above, evaluate Δ A, this Δ A
The ultraviolet absorbance in the direction that the polarization direction of the polarized UV rays being side chain type polymeric membrane and irradiate is parallel and with photograph
The difference of the ultraviolet absorbance in the direction that the polarization direction of the polarized UV rays penetrated is vertical.Irradiate and be scaled with wavelength 365nm
During the polarized UV rays of 4500mJ, Δ A is 0.2 at 314nm to the maximum, irradiates the polarized UV rays of 650mJ so that Δ A reaches
0.065 (having the difference of 32% relative to maximum), is then heated to 155 DEG C by this substrate, and making side chain type polymeric membrane is liquid crystal
Phase, keeps 5 minutes with this state.It is then cooled to room temperature, obtains having in film, introduce anisotropic liquid crystal orientation film
Substrate.Δ A now is amplified to 1.8, and the degree of orientation is 0.73.
<comparative example 2>
Except the polymer obtained in synthesis example 61 being dissolved in dichloromethane, with the thickness spin of about 190nm at optics
Form side chain type polymeric membrane on substrate on isotropic substrate, the irradiation dose of polarized UV rays is that (Δ A reaches 4500mJ
Irradiation dose to maximum) beyond, carry out polarized UV rays in the same manner as comparative example 1 and irradiate and heat treatment subsequently, obtain to
Film introduces anisotropic liquid crystal orientation film.Now, the Δ A before and after heat treatment does not changes, and is still 0.07, the degree of orientation
Also it is 0.12 at 314nm, unconfirmed to Δ A with the amplification of the degree of orientation.
<comparative example 3>
Except the polymer obtained in synthesis example 72 being dissolved in oxolane, with the thickness spin of about 150nm at optics
Form side chain type polymeric membrane on substrate on isotropic substrate, the irradiation dose of polarized UV rays is that (Δ A reaches 900mJ
Irradiation dose to maximum), heat treatment subsequently be beyond 165 DEG C, carry out in the same manner as comparative example 1 polarized UV rays irradiate and
Heat treatment subsequently, obtains introducing anisotropic liquid crystal orientation film in film.Now, the Δ A before and after heat treatment does not occurs
Change, is still 0.07, and the degree of orientation is also 0.12 at 314nm, unconfirmed to Δ A with the amplification of the degree of orientation.
<comparative example 4>
Except the polymer obtained in synthesis example 72 being dissolved in oxolane, with the thickness spin of about 150nm at optics
Form side chain type polymeric membrane on substrate on isotropic substrate, the irradiation dose of polarized UV rays is that (Δ A reaches 5mJ
The irradiation dose of the 10% of Δ A maximum), heat treatment subsequently be 200 DEG C, more than the liquid crystal temperature range of polymer 2 beyond,
Carry out polarized UV rays irradiation and heat treatment subsequently in the same manner as comparative example 1, obtain liquid crystal orientation film.Now, before heat treatment
After Δ A be reduced to 0 from 0.07, orientation is also 0 at 314nm, and the anisotropy in macromolecule membrane disappears.
<preparation of liquid crystal cell and evaluation>
<embodiment 7>
With the substrate with liquid crystal orientation film made in two pieces of embodiments 1 by Merck Amada Co., Ltd. (メ Le Network ジ
ャ パ Application) the liquid crystal ZLI-4792 that makes clamps, and obtains antiparallel type liquid crystal cell.Gained liquid crystal is observed brilliant under cross Nicols
Born of the same parents, result observes the uniform liquid crystal aligning that No yield point is bad.Additionally, make two pieces to introduce anisotropic liquid with this
The ito substrate of brilliant alignment films, presss from both sides liquid crystal ZLI-4792 between which, then with a pair linear polarization sheet by gained liquid crystal cell
Clamp, thus make the TN that thickness is 6 μm (Twisted Nematic: twisted-nematic) the type liquid crystal display cells of liquid crystal.This TN
In type liquid crystal display cells, by ITO electrode is applied voltage, can confirm that the driving of liquid crystal.Confirm that liquid crystal display cells exists
The most it is not orientated defect on whole, confirms the change in orientation of uniform liquid crystal by applying voltage.Use present embodiment
Liquid crystal orientation film, can be made into the liquid crystal display cells of present embodiment.Evaluation result is summarized in table 1.
<embodiment 8>
Use the substrate with liquid crystal orientation film made in two pieces of embodiments 2, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<embodiment 9>
Use the substrate with liquid crystal orientation film made in two pieces of embodiments 3, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<embodiment 10>
Use the substrate with liquid crystal orientation film made in two pieces of embodiments 4, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<embodiment 11>
Use the substrate with liquid crystal orientation film made in two pieces of embodiments 5, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<embodiment 12>
Use the substrate with liquid crystal orientation film made in two pieces of embodiments 6, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<comparative example 5>
Use the substrate with liquid crystal orientation film made in two pieces of comparative examples 1, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<comparative example 6>
Use the substrate with liquid crystal orientation film made in two pieces of comparative examples 2, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<comparative example 7>
Use the substrate with liquid crystal orientation film made in two pieces of comparative examples 3, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
<comparative example 8>
Use the substrate with liquid crystal orientation film made in two pieces of comparative examples 4, by method system similarly to Example 7
Become liquid crystal cell.Result is shown in table 1.
From above evaluation result, use the manufacture method of the liquid crystal orientation film of the present invention, shine with less ultraviolet
The liquid crystal orientation film of the present invention that the amount of penetrating prepares can provide liquid crystal display cells.
[table 1]
| Embodiment and comparative example | The orientation of liquid crystal |
| Embodiment 7 | Well |
| Embodiment 8 | Well |
| Embodiment 9 | Well |
| Embodiment 10 | Well |
| Embodiment 11 | Well |
| Embodiment 12 | Well |
| Comparative example 5 | It is orientated defect in a large number |
| Comparative example 6 | No yield point |
| Comparative example 7 | No yield point |
| Comparative example 8 | No yield point |
The probability utilized in industry
The manufacture method of the present invention can be used for realizing the manufacture of the liquid crystal orientation film of high efficiency orientation process.
It addition, here quote the explanation of the Japanese patent application 2011-260180 filed an application November 29 in 2011
All the elements of book, claims, accompanying drawing and summary are as the announcement of description of the invention.
The explanation of symbol
1 side chain type polymeric membrane
2,2a side chain
3 side chain type polymeric membranes
4,4a side chain
5 side chain type polymeric membranes
6,6a side chain
7 side chain type polymeric membranes
8,8a side chain
Claims (12)
1. a manufacture method for liquid crystal orientation film, comprising:
[I] embodies the work of the photosensitive side chain type polymeric membrane of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate
Sequence；
Described side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And
The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；
It is characterized in that, the ultraviolet irradiation amount of [II] operation reaches 1%～the 70% of the ultraviolet irradiation amount of maximum at Δ A
In the range of, Δ A is the ultraviolet in parallel direction, the polarization direction with described polarized UV rays of described side chain type polymeric membrane
The UV absorbance in the direction that absorbance is vertical with the polarization direction with described polarized UV rays of described side chain type polymeric membrane
The difference of degree.
2. the manufacture method of liquid crystal orientation film as claimed in claim 1, it is characterised in that the ultraviolet irradiation amount of [II] operation
Reach in the range of the 1%～50% of maximum ultraviolet irradiation amount at described Δ A.
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 [III] operation
It it is the temperature of the lower limit for height 10 DEG C of the temperature range embodying liquid crystal liquid crystal property than described side chain type polymeric membrane～than this temperature range
Low 10 DEG C of the upper limit temperature in the range of temperature.
4. the manufacture method of liquid crystal orientation film as claimed in claim 1 or 2, it is characterised in that described in embody liquid crystal liquid crystal property
Photonasty group contained in photosensitive side chain type macromolecule be diphenyl diimide, cinnamic acid, cinnamate, chalcone derivative, perfume (or spice)
Legumin, tolan, phenol benzoate or derivatives thereof.
5. a manufacture method for liquid crystal orientation film, comprising:
[I] embodies the side chain type polymeric membrane of the photocrosslinking reaction of liquid crystal liquid crystal property within the temperature range of being formed at regulation on substrate
Operation；
Described photocrosslinking reaction side chain type polymeric membrane is irradiated the operation of polarized UV rays by [II]；And
The operation of [III] side chain type polymeric membrane heating to irradiating through described ultraviolet；
[IV] is to illuminated described ultraviolet, the work of the side chain type polymeric membrane unpolarized ultraviolet of irradiation being then passed through heating
Sequence；
It is characterized in that, the ultraviolet irradiation amount of [II] operation reaches 1%～the 70% of the ultraviolet irradiation amount of maximum at Δ A
In the range of, Δ A is the ultraviolet in parallel direction, the polarization direction with described polarized UV rays of described side chain type polymeric membrane
The UV absorbance in the direction that absorbance is vertical with the polarization direction with described polarized UV rays of described side chain type polymeric membrane
The difference of degree.
6. the manufacture method of liquid crystal orientation film as claimed in claim 5, it is characterised in that the ultraviolet irradiation amount of [II] operation
Reach in the range of the 1%～50% of maximum ultraviolet irradiation amount at described Δ A.
7. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that the heating-up temperature of [III] operation
It it is the temperature of the lower limit for height 10 DEG C of the temperature range embodying liquid crystal liquid crystal property than described side chain type polymeric membrane～than this temperature range
Low 10 DEG C of the upper limit temperature in the range of temperature.
8. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that by the ultraviolet of [IV] operation
Line irradiates, and 20 moles of more than % of the photocrosslinking reaction group that described side chain type polymeric membrane is had react.
9. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that described in embody liquid crystal liquid crystal property
Photonasty group contained in the side chain type macromolecule of photocrosslinking reaction be cinnamic acid, cinnamate, chalcone derivative, coumarin, two
Phenylacetylene or derivatives thereof.
10. the manufacture method of the liquid crystal orientation film as described in claim 5 or 6, it is characterised in that described side chain type polymeric membrane
Being the structure including main chain and side chain, described main chain is constituted by selected from least one of hydrocarbon, acrylate and methacrylate,
Described side chain represents with at least one in following formula (1)～(7)；
[changing 1]
In formula (1), A1、B1Separately represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-, Y1It it is choosing
From at least one group of the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, key on these groups
The hydrogen atom closed can be separately by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl
Replace；X1Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-, l1 represents the integer of 1～12, m1 table
Showing the integer of 1～3, n1 represents the integer of 1～12；In formula (2), A2、B2、D1Separately represent singly-bound ,-O-,-CH2-、-
COO-,-OCO-,-CONH-or NH-CO-, Y2Selected from phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8
At least one group of cyclic hydrocarbon, on these groups, the hydrogen atom of bonding can be separately by-NO2,-CN ,-C=C
(CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl replace；X2Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=
C-,-C ≡ C-or C6H4-, R1Represent hydrogen atom or the alkyl of carbon number 1～6；L2 represents the integer of 1～12, m2 represent 1～3 whole
Number, n2 represents the integer of 1～12；In formula (3), A3Represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-,
X3Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-, R2Represent hydrogen atom or the alkane of carbon number 1～6
Base；L3 represents the integer of 1～12, and m3 represents the integer of 1～3；In formula (4), l4 represents the integer of 1～12；In formula (5), A4Table
Show singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-, X4Expression-COO-, Y3It is selected from phenyl ring, naphthalene nucleus and connection
At least one group of phenyl ring, on these groups, the hydrogen atom of bonding can be separately by-NO2,-CN ,-C=C (CN)2、-
C=CH-CN, halogen group, alkyl or alkoxyl replace；L5 represents the integer of 1～12, and m4 represents the integer of 1～3；Formula (6)
In, A5Represent singly-bound ,-O-,-CH2-,-COO-,-OCO-,-CONH-or NH-CO-, R3Represent selected from hydrogen atom ,-NO2、-CN、-
C=C (CN)2,-C=CH-CN, halogen group, at least one group of alkoxyl of the alkyl of carbon number 1～6 and carbon number 1～6；
L6 represents the integer of 1～12；On phenyl ring in formula (6), the hydrogen atom of bonding can be separately by-NO2,-CN ,-C=C
(CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl replace；In formula (7), A6Represent singly-bound ,-O-,-CH2-、-COO-、-
OCO-,-CONH-or NH-CO-, B3Represent singly-bound ,-COO-,-OCO-,-N=N-,-C=C-,-C ≡ C-or C6H4-；W1It it is choosing
From at least one group of the cyclic hydrocarbon of phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5～8, key on these groups
The hydrogen atom closed can be separately by-NO2,-CN ,-C=C (CN)2,-C=CH-CN, halogen group, alkyl or alkoxyl
Replace；L7 represents the integer of 1～12, and m5, m6 represent the integer of 1～3 respectively.
11. 1 kinds of liquid crystal orientation films, it is characterised in that by the liquid crystal orientation film according to any one of claim 1～10
Manufacture method and make.
12. 1 kinds of liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011260180 | 2011-11-29 | ||
| JP2011-260180 | 2011-11-29 | ||
| PCT/JP2012/080977 WO2013081066A1 (en) | 2011-11-29 | 2012-11-29 | Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103959152A CN103959152A (en) | 2014-07-30 |
| CN103959152B true CN103959152B (en) | 2016-11-30 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1576909A (en) * | 2003-07-15 | 2005-02-09 | 柯尼卡美能达精密光学株式会社 | Optical compensation film, polarizing plate and liquid crystal display |
| CN1652927A (en) * | 2002-05-21 | 2005-08-10 | 新日本石油株式会社 | Transferring laminate |
| JP2007304215A (en) * | 2006-05-09 | 2007-11-22 | Hayashi Telempu Co Ltd | Photo-alignment material and method for manufacturing optical element and liquid crystal alignment film |
| CN101408638A (en) * | 2007-01-30 | 2009-04-15 | 新日本石油株式会社 | Process for producing a liquid crystal film and laminate film for optical device |
| CN101781570A (en) * | 2009-01-16 | 2010-07-21 | 富士胶片株式会社 | Liquid crystalline composition and light absorption anisotropic film, a polarizing element and a liquid crystal display device, each employing the same |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1652927A (en) * | 2002-05-21 | 2005-08-10 | 新日本石油株式会社 | Transferring laminate |
| CN1576909A (en) * | 2003-07-15 | 2005-02-09 | 柯尼卡美能达精密光学株式会社 | Optical compensation film, polarizing plate and liquid crystal display |
| JP2007304215A (en) * | 2006-05-09 | 2007-11-22 | Hayashi Telempu Co Ltd | Photo-alignment material and method for manufacturing optical element and liquid crystal alignment film |
| CN101408638A (en) * | 2007-01-30 | 2009-04-15 | 新日本石油株式会社 | Process for producing a liquid crystal film and laminate film for optical device |
| CN101781570A (en) * | 2009-01-16 | 2010-07-21 | 富士胶片株式会社 | Liquid crystalline composition and light absorption anisotropic film, a polarizing element and a liquid crystal display device, each employing the same |
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