CN103003722B - Light directive property control module and manufacture method, display module - Google Patents

Light directive property control module and manufacture method, display module Download PDF

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Publication number
CN103003722B
CN103003722B CN201180035097.4A CN201180035097A CN103003722B CN 103003722 B CN103003722 B CN 103003722B CN 201180035097 A CN201180035097 A CN 201180035097A CN 103003722 B CN103003722 B CN 103003722B
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China
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liquid crystal
directive property
property control
control module
base
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CN201180035097.4A
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CN103003722A (en
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徳久博昭
西川通则
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133526—Lenses, e.g. microlenses or Fresnel lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/02—Simple or compound lenses with non-spherical faces
    • G02B3/06—Simple or compound lenses with non-spherical faces with cylindrical or toric faces
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
    • G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
    • G02B30/26—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type
    • G02B30/27—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type involving lenticular arrays
    • G02B30/28—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type involving lenticular arrays involving active lenticular arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B35/00—Stereoscopic photography
    • G03B35/18—Stereoscopic photography by simultaneous viewing
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
    • H04N13/30—Image reproducers
    • H04N13/302—Image reproducers for viewing without the aid of special glasses, i.e. using autostereoscopic displays
    • H04N13/305—Image reproducers for viewing without the aid of special glasses, i.e. using autostereoscopic displays using lenticular lenses, e.g. arrangements of cylindrical lenses
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
    • H04N13/30—Image reproducers
    • H04N13/356—Image reproducers having separate monoscopic and stereoscopic modes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/29—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the position or the direction of light beams, i.e. deflection

Abstract

The present invention is a kind of light directive property control module, and it comprises: transparency carrier; Lens jacket, subtend is disposed in the face side of this transparency carrier, has column lens array overleaf; Liquid crystal orienting film, laminated on the back side of this lens jacket, is formed by radioactivity-sensitive crystal aligning agent; Liquid crystal lens layer, is situated between every this liquid crystal orienting film laminated on the rear side of lens jacket.Also can comprise other liquid crystal orienting films, other liquid crystal orienting films described, laminated on the back side of above-mentioned liquid crystal lens layer, are formed by radioactivity-sensitive crystal aligning agent.

Description

Light directive property control module and manufacture method, display module
Technical field
The present invention relates to a kind of smooth directive property control module and manufacture method thereof, can the display module that switches of 2D/3D and crystal aligning agent.
Background technology
In recent years, as the liquid crystal indicator carrying out stereoscopic three-dimensional (3D) and show, develop a kind of automatic stereo display (autostereoscopic) module, it does not use during the vision appurtenances such as special spectacles in spectator side also can identify 3D rendering.As an example of this kind of automatic stereo display module, propose a kind of display module, it is included in longitudinal direction in two dimensional liquid crystal display panel and the array of elongated lens (lenticular) element extended abreast, can carry out the switching (with reference to patent documentation 1 and non-patent literature 1) of two dimension (2D) pattern and three-dimensional (3D stereo display) pattern.
Above-mentioned can 2D/3D switch display module in, said lens element is generally formed by liquid crystal, but in order to ensure display formedness, the homogeneity of the orientation of this liquid crystal must be improved.Therefore, at formation liquid crystal orienting film around the formation space of liquid crystal before, after (rubbing) process of carrying out rubbing, form liquid crystal, improve the regiospecific of liquid crystal therefrom.
Friction treatment is carried out usually in the following way: the friction cloth that the outer peripheral face being used in roller attaches, and one side makes this roller rotate one side and makes friction cloth and liquid crystal orienting film surface contact, rubs to the face forming liquid crystal orienting film.If carry out this kind of friction treatment for the fine concavo-convex face that has as matrix lens etc., then the direction processed easily becomes heterogeneity.Therefore, the homogeneity of the orientation of formed liquid crystal cannot be improved, the undesirable condition that the resolution of the rewarding display of its result tool etc. reduce.
Prior art document
Patent documentation
Patent documentation 1: Jap.P. spy table 2009-528565 publication
Non-patent literature
Non-patent literature 1:IDW, the 11st volume, the 1495th page of-1496 pages, 2004
Summary of the invention
The problem that invention solves
The present invention forms to eliminate undesirable condition as above.That is, fundamental purpose of the present invention be to provide a kind of liquid crystal lens layer by comprising orientation homogeneity excellence and can obtain the good display such as resolution light directive property control module and comprise this light directive property control module can the display module that switches of 2D/3D.And other objects of the present invention are the manufacture method providing this kind of light directive property control module.
The means of dealing with problems
In order to the invention solving above-mentioned problem is a kind of light directive property control module, it comprises:
Transparency carrier;
Lens jacket, subtend is disposed in the face side of this transparency carrier, has column lens array overleaf;
Liquid crystal orienting film, laminated on the back side of this lens jacket, is formed by radioactivity-sensitive crystal aligning agent;
Liquid crystal lens layer, is situated between every this liquid crystal orienting film laminated on the rear side of lens jacket.
Smooth directive property control module of the present invention comprises above-mentioned formation, and lamination has lens jacket and the orientation liquid crystal lens layer on certain orientation.Owing to passing through the direction of vibration of polarisation of this unit and the alignment direction angulation of the liquid crystal of liquid crystal lens layer, the refractive index of liquid crystal changes.That is can form as follows: relative to the polarisation vibrated in the prescribed direction, lens jacket is identical with the refractive index of liquid crystal lens layer, relative to the polarisation with the vibration plane different from it, lens jacket is different from the refractive index of liquid crystal lens layer.Therefore, according to this light directive property control module, by make light merely through or reflect in liquid crystal lens layer, the directive property of changeable light.And as this light directive property control module, above-mentioned liquid crystal orienting film is formed by radioactivity-sensitive crystal aligning agent, therefore with the liquid crystal orienting film implementing friction treatment before Comparatively speaking, the orientation homogeneity of alignment film is excellent.Thus, in this light directive property control module, the orientation homogeneity of the liquid crystal lens layer formed every this liquid crystal orienting film that is situated between uprises.Its result, the display module of changeable 2 meta schemas and 3 meta schemas that comprise this light directive property control module can improve its formedness shown.
In this light directive property control module, also can comprise other liquid crystal orienting films, other liquid crystal orienting films described, laminated on the back side of above-mentioned liquid crystal lens layer, are formed by radioactivity-sensitive crystal aligning agent.Except the face side of liquid crystal lens layer, the side also liquid crystal orienting film that formed by radioactivity-sensitive crystal aligning agent of lamination, can further improve the orientation homogeneity of the liquid crystal of the liquid crystal lens layer in this light directive property control module thus overleaf.Its result, can further improve comprise this light directive property control module can the formedness of expression of display module that switches of 2D/3D.
Also a pair transparent electrode layer of the side, two sides laminated on above-mentioned liquid crystal lens layer can be comprised in this light directive property control module.According to this light directive property control module, by being included in a pair transparent electrode layer of side, the two sides institute lamination of above-mentioned liquid crystal lens layer, by the presence or absence that the voltage of this transparency electrode interlayer applies, the regiospecific of the liquid crystal of liquid crystal lens layer is changed, changeable smooth directive property thus.
Also can comprise in this light directive property control module the liquid crystal layer be overlapped on above-mentioned transparency carrier, with a pair transparent electrode layer of side, two sides being disposed in this liquid crystal layer.Above-mentioned liquid crystal layer and the combination of a pair transparent electrode layer of side, two sides being disposed in this liquid crystal, the presence or absence applied by the voltage of this pair transparency electrode interlayer and the orientation of the liquid crystal layer of those transparency electrode interlayers is changed, thus form the liquid crystal shutter that can change the anglec of rotation of the plane of polarisation of the polarisation of advance.Therefore, this light directive property control module is by comprising this liquid crystal shutter further, thus the presence or absence applied by the voltage of this pair transparency electrode interlayer and switches light directive property.
Above-mentioned radioactivity-sensitive crystal aligning agent also can have the polysiloxane (hereinafter sometimes referred to " [A] light regiospecific polysiloxane ") of light regiospecific base containing [A].In the liquid crystal orienting film obtained by irradiating radioactive ray to the film formed by the above-mentioned crystal aligning agent containing [A] light regiospecific polysiloxane, the regiospecific of the molecule forming alignment film can be improved.Its result, the orientation homogeneity of the liquid crystal lens layer formed every this liquid crystal orienting film that is situated between improves.
Above-mentioned smooth regiospecific base preferably has the base of cinnamic acid structure.Have using the base of the cinnamic acid or derivatives thereof cinnamic acid structure that is basic framework as light regiospecific base by using, in the polysiloxane of above-mentioned crystal aligning agent, the transfiguration of lead-in light regiospecific base is easy, and the liquid crystal orienting film that kind crystal aligning agent is formed thus has light orientation performance high further.Its result, can make the orientation homogeneity of the liquid crystal lens layer in this light directive property control module uprise further.
The above-mentioned base with cinnamic acid structure can be at least a kind of base being selected from the group be made up of the base of the compound be derived from represented by following formula (1) and the base of compound that is derived from represented by formula (2).
[changing 1]
(in formula (1), R 1penylene, biphenylene, terphenyl support or cyclohexalene.Part or all of hydrogen atom of the support of this penylene, biphenylene, terphenyl and cyclohexalene also can be by the carbon number also can with fluorine atom 1 ~ 10 alkyl or carbon number be 1 ~ 10 alkoxy, fluorine atom or cyano group replace.R 2singly-bound, carbon number be 1 ~ 3 alkane two base, oxygen atom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-.A is the integer of 0 ~ 3.Wherein, when a is more than 2, multiple R 1and R 2can distinguish identical also can be different.R 3fluorine atom or cyano group.B is the integer of 0 ~ 4.
In formula (2), R 4penylene or cyclohexalene.The hydrogen atom of this penylene and cyclohexalene part or all also can by carbon number be 1 ~ 10 chain or the alkyl of ring-type, carbon number be 1 ~ 10 chain or the alkoxy of ring-type, fluorine atom or cyano group replace.R 5singly-bound, carbon number be 1 ~ 3 alkane two base, oxygen atom, sulphur atom or-NH-.C is the integer of 1 ~ 3.Wherein, when c is more than 2, multiple R 4and R 5can distinguish identical also can be different.R 6fluorine atom or cyano group.D is the integer of 0 ~ 4.R 7oxygen atom ,-COO-or-OCO-.R 8it is the thick cyclic group of the aromatic series base of divalent, the ester ring type base of divalent, the hetero ring type base of divalent or divalent.R 9singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*.* the bond position with carboxyl is represented.F and g is respectively the integer of 1 ~ 10.E is the integer of 0 ~ 3.Wherein, when e is more than 2, multiple R 7and R 8can distinguish identical also can be different)
By using the above-mentioned base being derived from specific cinnamic acid derivative as the above-mentioned base with cinnamic acid structure, the light orientation performance of the liquid crystal orienting film of gained can be made to improve further, and its result can make the orientation homogeneity of the liquid crystal lens layer in this light directive property control module improve further.
The polysiloxane that [A] has a light regiospecific base preferably have epoxy radicals polysiloxane, with the reaction product of at least a kind of compound being selected from the group that the compound represented by above-mentioned formula (1) and the compound represented by above-mentioned formula (2) are formed.In this light directive property control module, by utilizing the reactivity had between the polysiloxane of epoxy radicals and specific cinnamic acid derivative, the side chain radical being derived from the specific cinnamic acid derivative with light regiospecific base easily can be imported in as the polysiloxane of main chain.
Preferred above-mentioned crystal aligning agent has containing [C] the one kind or two or more structure being selected from the group be made up of the tert-butyl ester structure of the ketal ester structure of the acetal ester structure of carboxylic acid, carboxylic acid, the 1-alkyl-cycloalkyl ester structure of carboxylic acid and carboxylic acid further, has the compound (hereinafter sometimes referred to " [C] compound containing ester structure ") of this structure multiple when this structure is a kind.Because above-mentioned crystal aligning agent contains [C] compound containing ester structure, therefore in calcining step (drying afterwards), acid is produced, promote the crosslinked of [A] polysiloxane due to produced acid, its result can improve the thermotolerance of the light directive property control module of gained.
Preferred above-mentioned crystal aligning agent is selected from least a kind of polymkeric substance (hereinafter sometimes referred to " [B] other polymkeric substance ") of the group be made up of polyamic acid, polyimide, ethene unsaturated polymerizable compound thing and the polysiloxane of not having light regiospecific base further containing [B].Owing to containing other polymkeric substance in above-mentioned crystal aligning agent, even if therefore reduce the content of the light regiospecific polysiloxane in above-mentioned crystal aligning agent, light regiospecific polysiloxane is also partial to liquid crystal alignment layer surface and exists, therefore can improve the light orientation performance of liquid crystal orienting film, its result can maintain the orientation homogeneity of the liquid crystal of liquid crystal lens jacket higher.Therefore, can reduce the content of light regiospecific polysiloxane in above-mentioned crystal aligning agent that manufacturing cost is high, its result can lower the manufacturing cost of this light directive property control module.
Of the present invention can 2D/3D switch display module comprise:
Display panel;
This light directive property control module.
This can comprise the above-mentioned smooth directive property control module of the orientation homogeneity excellence of the liquid crystal of liquid crystal lens layer, with therefore can reducing the display quality of two dimension and three-dimensional hardly for spectator provides good display by display module of switching of 2D/3D.
The manufacture method of smooth directive property control module of the present invention is the manufacture method comprising the following light directive property control module formed: transparency carrier; Lens jacket, subtend is disposed in the face side of this transparency carrier, has column lens array overleaf; Liquid crystal orienting film, laminated on the back side of this lens jacket; Liquid crystal lens layer, is situated between every this liquid crystal orienting film laminated on the rear side of lens jacket;
The method comprises following steps:
(1) at the backsize radioactivity-sensitive crystal aligning agent of lens jacket, the step of film is formed;
(2) step of liquid crystal orienting film is formed by irradiating radioactive ray to above-mentioned film; And
(3) between this liquid crystal orienting film and transparency carrier, form the step of liquid crystal lens layer.
And preferably above-mentioned (3) step comprises following steps:
(3-1) make this liquid crystal orienting film and transparency carrier subtend arrange, form the step in the space clamped by this liquid crystal orienting film and this transparency carrier; And
(3-2) filling liquid crystal material within this space, forms the step of liquid crystal lens layer.
Further more preferably (3-2) step comprises following steps:
(3-2-1) step of polymerizable liquid crystal is sucked in this space; And
(3-2-2) make this polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
And preferably above-mentioned (3) step comprises following steps:
(3-1 '), at the rear side coating of liquid crystalline material of this liquid crystal orienting film, forms the step of liquid crystal lens layer; And
(3-2 ') arranges the step of transparency carrier in the rear side of this liquid crystal lens layer.
More preferably above-mentioned (3-1 ') step comprises following steps further:
(3-1 '-1) is in the step of the rear side coating polymerizable liquid crystal of this liquid crystal orienting film; And
(3-1 '-2) make this polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
Manufacturing method according to the invention, efficiency can manufacture the light directive property control module of the orientation homogeneity excellence of liquid crystal lens layer well, and can promote the attenuating of productive raising and manufacturing cost.
Crystal aligning agent of the present invention is can the liquid crystal lens layer orientation crystal aligning agent of display module that switches of 2D/3D, it is characterized in that:
There is radioactivity-sensitive.
According to crystal aligning agent of the present invention, can improve can the regiospecific of liquid crystal orienting film of institute's lamination on the liquid crystal lens layer of the light directive property control module of display module that switches of 2D/3D, and its result can improve the orientation homogeneity of liquid crystal lens layer.
The effect of invention
Utilize smooth directive property control module of the present invention, the orientation homogeneity of liquid crystal lens layer can be made to improve, its result can improve use it can the display precision such as resolution of display module that switches of 2D/3D.
Accompanying drawing explanation
Fig. 1 is the sectional view of the light directive property control module of the 1st example of the present invention.
Fig. 2 is the sectional view of the light directive property control module of the 2nd example of the present invention.
Fig. 3 is the sectional view of the light directive property control module of the 3rd example of the present invention.
Fig. 4 is the sectional view of the light directive property control module of the 4th example of the present invention.
Fig. 5 be the 1st example of the present invention can 2D/3D switch display module sectional view.
Fig. 6 be the 2nd example of the present invention can 2D/3D switch display module sectional view.
Fig. 7 be the 3rd example of the present invention can 2D/3D switch display module sectional view.
Fig. 8 be the 4th example of the present invention can 2D/3D switch display module sectional view.
The explanation of symbol
1: light directive property control module (the 1st example)
2: light directive property control module (the 2nd example)
3: light directive property control module (the 3rd example)
4: light directive property control module (the 4th example)
11,12: transparency carrier
13: lens jacket
14: liquid crystal lens layer
15,16: liquid crystal orienting film
21,51,52: switch transparency carrier
22,23,26,27,28,53,54: transparent electrode layer
24,55: switching Liquid Crystal layer
25: switch transparent electrode substrate
31: display panel
41: liquid crystal switch cell
61: incident light polarization element
62: emergent light polarization element
71: can 2D/3D switch display module (the 1st example)
72: can 2D/3D switch display module (the 2nd example)
73: can 2D/3D switch display module (the 3rd example)
74: can 2D/3D switch display module (the 4th example)
Embodiment
< light directive property control module >
First, with reference to Fig. 1, following explanation is carried out to the light directive property control module of the 1st example.Light directive property control module 1 comprises a pair transparency carrier 11,12, lens jacket 13, liquid crystal lens layer 14,2 liquid crystal orienting film 15,16.This light directive property control module 1 is the form of the situation that the extraordinary refractive index (relative in the refractive index being parallel to the polarisation that the direction of the optical axis of liquid crystal vibrates) of liquid crystal lens layer 14 is larger than the refractive index of lens jacket 13.In the light directive property control module of Fig. 1, wherein transparency carrier 12 side of a side is rear side, that is the side of light incidence from display panel, and transparency carrier 11 side of the opposing party is face side, that is the side that light penetrates to spectator.
Above-mentioned a pair transparency carrier 11,12 subtend arranges, and the face side of the transparency carrier 12 of a side wherein arranges substantially in parallel the transparency carrier 11 of the opposing party.Lens jacket 13 is had at the back side lamination of this transparency carrier 11.Lens jacket 13 has the column lens array of matrix overleaf.Become the mode in a direction with the crest line direction of this lens pillar layer 13 and formed.Liquid crystal orienting film 15 is laminated on the matrix column lens array face at the back side of lens jacket 13, and liquid crystal orienting film 16 is laminated on the surface of the wherein transparency carrier 12 of a side.Liquid crystal lens layer 14 is formed between above-mentioned 2 liquid crystal orienting films 15,16.
2 liquid crystal orienting films that the back side of said lens layer 13 and the surface of transparency carrier 12 are formed respectively have LCD alignment ability by irradiating radioactive ray in same direction, that is all have the LCD alignment ability in z direction.
Above-mentioned liquid crystal lens layer 14 comprises the liquid crystal of filling between above-mentioned 2 liquid crystal alignment layers 15,16, and its result liquid crystal lens layer 14 has in its surface contrary column lens array concavo-convex with lens jacket 13.The liquid crystal of this liquid crystal lens layer 14 along with the LCD alignment ability of above-mentioned liquid crystal orienting film 15,16 orientation on z direction.Therefore, as the refractive index of liquid crystal lens layer 14, high for the polarisation that direction of vibration is z direction, on the other hand, low for the polarisation that direction of vibration is x direction, and there is the refractive index roughly equal with lens jacket 13.
Light directive property control module 1 due to the alignment direction of the liquid crystal forming liquid crystal lens layer 14 be z direction, therefore when the direction of vibration of the polarisation being incident to light directive property control module 1 is z direction, liquid crystal lens layer 14 is different from the refractive index of lens jacket 13, the refractive index of liquid crystal lens layer 14 is larger, therefore liquid crystal lens layer 14 and lens jacket 13 combination as have liquid crystal lens layer 14 shape lens pillar and play function, light directive property control module 1 provides the light directive property function of refractive.On the other hand, when the direction of the polarisation being incident to light directive property control module 1 is x direction, liquid crystal lens layer 14 is substantially identical with the refractive index of lens jacket 13, therefore in liquid crystal lens layer 14 combination with lens jacket 13, light do not reflect and merely through, light directive property control module 1 provides the light directive property function of infiltration type.In addition, as the LCD alignment ability that above-mentioned 2 liquid crystal orienting films have, except z direction, also can be x direction, preferably z direction.
With reference to Fig. 2, following explanation is carried out to the light directive property control module 2 of the 2nd example of the present invention.Light directive property control module 2 comprises a pair transparency carrier 11,12, lens jacket 13, liquid crystal lens layer 14,2 liquid crystal orienting films 15,16, transparency carrier (switch transparency carrier) 21, a pair transparent electrode layer (switch transparency electrode) 22,23, liquid crystal layer (switching Liquid Crystal layer) 24.Switch transparency carrier 21, pair of switches transparent electrode layer 22,23 and switching Liquid Crystal layer 24 be combined through the presence or absence that the voltage between pair of switches transparent electrode layer 22,23 applies, the alignment direction of the liquid crystal of formation switching Liquid Crystal layer 24 is changed, being rotated in " liquid crystal shutter " that change between 0 ° and 90 ° and playing function therefrom as rotatory polarization.That is light directive property control module 2 has the formation being attached with liquid crystal shutter in the formation of the light directive property control module 1 of the 1st example.In fig. 2, identical to the light directive property control module 1 with the 1st example formation is accompanied by same numbering and omits the description.In addition, in this manual, also the transparency carrier of formation liquid crystal shutter, transparent electrode layer and liquid crystal layer are called switch transparency carrier, switch transparent electrode layer and switching Liquid Crystal layer.
In light directive property control module 2, arrange switch transparency carrier 21 in the face side subtend of transparency carrier 11.The gap that interval is certain on the face of the respective subtend of transparency carrier 11 and switch transparency carrier 21 and configure a pair transparent electrode layer 22,23, arranges switching Liquid Crystal layer 24 between these a pair transparency conducting layers 22,23.
Light directive property control module 2 is except the formation of light directive property control module 1, also the formation of above-mentioned liquid crystal shutter is comprised, therefore by the presence or absence that the voltage between transparent electrode layer 22,23 applies, switch in the mode that the polarisation being incident to the direction of vibration desired by liquid crystal lens layer 14 penetrates from light directive property control module 2.That is, utilize light directive property control module 2, make after the refracting light incident of z direction polarisation by liquid crystal lens layer 14 and lens jacket 13, it is made to penetrate to desired direction polarisation by liquid crystal shutter, and make incident light to x direction polarisation merely through rear by liquid crystal lens layer 14 and lens jacket 13, make it penetrate to desired direction polarisation by liquid crystal shutter.Therefore, utilize light directive property control module 2, for the emergent light with desired direction of vibration, the light directive property function of changeable infiltration type and refractive.
With reference to Fig. 3, following explanation is carried out to the light directive property control module 3 of the 3rd example of the present invention.Light directive property control module 3 comprises a pair transparency carrier 11,12, lens jacket 13, liquid crystal lens layer 14,2 liquid crystal orienting film 15,16, switch transparent electrode substrate 25, transparent electrode layer 26, switching Liquid Crystal layer 24.Switch transparent electrode substrate 25 is the substrates having transparent electrode layer at the rear side lamination of transparency carrier.That is light directive property control module 3 has the formation being attached with the liquid crystal shutter of switch transparent electrode substrate 25, transparent electrode layer 26 and switching Liquid Crystal layer 24 in the formation of the light directive property control module 1 of the 1st example.In figure 3, identical to the light directive property control module 1 with the 1st example formation is accompanied by same numbering and omits the description.
Light directive property control module 3 has following formation: between the transparency carrier 12 of the liquid crystal orienting film 16 in the light directive property control module 1 of the 1st example and wherein a side, be configured with switch transparent electrode substrate 25, switching Liquid Crystal layer 24 and transparent electrode layer 26 in turn.Those switch transparent electrode substrates 25 and transparent electrode layer 26 and between those clamped switching Liquid Crystal layer 24 play function as liquid crystal shutter as described above.Therefore, light directive property control module 3 in the same manner as the light directive property control module 2 of the 2nd example by presence or absence that the voltage between switch transparent electrode substrate 25 and transparent electrode layer 26 applies, for the emergent light with desired direction of vibration, switch the light directive property function of infiltration type and refractive.That is, utilize light directive property control module 3, the incident light of polarisation on specific direction is on x-z plane made to become the polarisation in z direction by liquid crystal shutter, it is made to reflect rear injection by liquid crystal lens layer 14 and lens jacket 13, and, make the incident light of polarisation on specific direction on x-z plane become the polarisation in x direction by liquid crystal shutter, make by liquid crystal lens layer 14 and lens jacket 13 its merely through and penetrate.
With reference to Fig. 4, following explanation is carried out to the light directive property control module 4 of the 4th example of the present invention.Light directive property control module 4 comprises a pair transparency carrier 11,12, lens jacket 13, liquid crystal lens layer 14,2 liquid crystal orienting film 15,16, a pair transparent electrode layer 27,28.That is light directive property control module 4 has the formation being attached with a pair transparency conducting layer 27,28 in the formation of the light directive property control module 1 of the 1st example.In the diagram, identical to the light directive property control module 1 with the 1st example formation is accompanied by same numbering and omits the description.
In light directive property control module 4, on a pair transparency carrier 11,12, in the side, face of its subtend, lamination has transparent electrode layer 27,28 respectively.And the back side lamination of the transparent electrode layer 27 of a side has lens jacket 13 wherein.And, there is liquid crystal orienting film 16 at the surface area layer of the transparent electrode layer 28 of the opposing party.In light directive property control module 4, the presence or absence applied by the voltage between a pair transparent electrode layer 27,28, the alignment direction change of the liquid crystal of the liquid crystal lens layer 14 that formation can be made therebetween configured.Therefore, utilize light directive property control module 4, for the incident light of the direction of vibration of regulation, the lens function that switchable liquid crystal lens jacket 14 produces with the combination of lens jacket 13, thus the light directive property function of changeable penetrating type and refractive.
As above-mentioned transparency carrier 11,12, include, for example the transparency carrier etc. of the plastic basis material such as addition polymer, aromatic polyether comprising the glass baseplate such as float glass, soda-lime glass, cellulose triacetate (triacetyl cellulose, TAC), the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethylmethacrylate, polycarbonate, cyclic olefin and hydride thereof, cyclic olefin.
As the material forming lens jacket 13, preferably the ordinary refraction index of its refractive index and liquid crystal lens layer 14 is equal extent, the acryl (acryl) such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide, polymethylmethacrylate can be used aptly, the resins such as polycarbonate, Polyvinylchloride, polyolefin.
In addition, also the back side of above-mentioned transparency carrier can be set to the lens shape of convex or concavity, make transparency carrier integrated with lens jacket.
< liquid crystal orienting film >
In the light directive property control module of above-mentioned any example, all there is liquid crystal orienting film 15,16.The alignment direction that liquid crystal orienting film has the liquid crystal formed being adjacent limits, thus improves the function of regiospecific.In the present invention, need be the liquid crystal orienting film formed by radioactivity-sensitive crystal aligning agent at the liquid crystal orienting film 15 of the back side institute lamination of the surface of liquid crystal lens layer 14 that is lens jacket 13.Radioactivity-sensitive crystal aligning agent uses the polarisation of the direction of vibration of regulation to replace common friction treatment and improves the regiospecific that alignment film forms molecule, improves the material of LCD alignment performance.By using radioactivity-sensitive crystal aligning agent, even if for the fine convex-concave surface etc. at the lens jacket back side being difficult to carry out friction treatment, also can form the liquid crystal orienting film of regiospecific excellence, its result can make the orientation homogeneity of the liquid crystal lens layer of gained improve.
And, about at first-class the formed liquid crystal orienting film 16 of the rear side of liquid crystal lens layer 14 that is the surface of transparency carrier 12, also preferably to be formed by radioactivity-sensitive crystal aligning agent.The liquid crystal orienting film of the back side institute lamination of liquid crystal lens layer 14 also can further improve the orientation homogeneity of liquid crystal lens layer 14 owing to being formed by radioactivity-sensitive crystal aligning agent, its result can further improve comprise this light directive property control module can the display precision such as resolution of display module that switches of 2D/3D.
< radioactivity-sensitive crystal aligning agent >
Liquid crystal orienting film 15 is formed by radioactivity-sensitive crystal aligning agent (below also referred to as " crystal aligning agent ").Owing to being formed by radioactivity-sensitive crystal aligning agent, even if be therefore considered to the fine convex-concave surface being formed at lens jacket, be difficult to the liquid crystal orienting film 15 being improved regiospecific by friction treatment, also can improve the regiospecific that alignment film forms molecule, its result can make the orientation homogeneity of the liquid crystal lens layer 14 of gained improve.Therefore, can improving further by the display precision such as the resolution of display module that switches of 2D/3D of this light directive property control module can be made to comprise.Liquid crystal orienting film 16 also can be formed by radioactivity-sensitive crystal aligning agent.If any one of a pair liquid crystal orienting film 15,16 of side, the two sides institute lamination of liquid crystal lens layer 14 all uses radioactivity-sensitive crystal aligning agent, and utilize same polarisation radioactive ray to make its orientation, alignment film on two films of then a pair liquid crystal orienting film 15,16 forms the alignment direction of molecule can be consistent at high level, its result can make the orientation homogeneity of the liquid crystal lens layer 14 of gained improve further, therefore and preferably.
If above-mentioned crystal aligning agent radioactivity-sensitive is then not particularly limited, various crystal aligning agent can being used, include, for example in Japanese Patent Laid-Open 9-297313 publication the described crystal aligning agent etc. of polymkeric substance containing having the molecular cell that can produce photoisomeric change/dimerization in the described crystal aligning agent containing specific polyimide resin, Japanese Patent Laid-Open 6-287453 publication.
Above-mentioned crystal aligning agent is preferably the crystal aligning agent containing the inorganic polymer with light regiospecific base.By using the crystal aligning agent containing the inorganic polymer with light regiospecific base, the liquid crystal orienting film of LCD alignment performance and excellent heat stability can be formed.
And, above-mentioned containing having in the crystal aligning agent of inorganic polymer of light regiospecific base, more preferably there is containing [A] crystal aligning agent of the polysiloxane (polyorganosiloxane) of light regiospecific base.Therefore and then can form the excellent liquid crystal orienting film of the transparency above-mentioned crystal aligning agent contains [A] light regiospecific polysiloxane, and can lower the necessary smooth exposure of orientation due to the light regiospecific of ISO.Can calcining heat be lowered, the range of choice of used substrate therefore can be made to expand, and then without the need in radiation exposure and postradiation heating steps, therefore efficiency can form liquid crystal orienting film well.
Crystal aligning agent containing [A] light regiospecific polysiloxane, preferably containing [B] other polymkeric substance, [C] compound containing ester structure, also can contain other any compositions further in the scope not undermining effect of the present invention.Below, to compound containing ester structure of [A] light regiospecific polysiloxane, [B] other polymkeric substance, [C] and arbitrarily composition described in detail.
< [A] light regiospecific polysiloxane >
[A] light regiospecific polysiloxane is being derived from lead-in light regiospecific base in the part of at least a kind being selected from the group be made up of the condensation product as the polysiloxane of main chain, its hydrolysate and hydrolysate thereof.Due to light regiospecific base, the light sensitivity of light orientation becomes good, can realize low light exposure, and the LCD alignment of liquid crystal orienting film is excellent.And owing to adopting polysiloxane as main chain, the liquid crystal orienting film therefore formed by above-mentioned crystal aligning agent has excellent chemical stability, thermal stability.
Light regiospecific base can adopt the base of the various compounds being derived from display light regiospecific, to include, for example containing azobenzene or derivatives thereof as the azobenzene (azobenzene) of basic framework containing base, have containing the base of cinnamic acid (cinnamic acid) or derivatives thereof as the cinnamic acid structure of basic framework, base is contained as the chalcone of basic framework containing chalcone (chalcone) or derivatives thereof, containing benzophenone or derivatives thereof as the benzophenone (benzophenone) of basic framework containing base, there is the cumarin (coumarin) of cumarin or derivatives thereof as basic framework containing base etc.In those light regiospecific bases, import the easiness of high orientation ability if consider, then preferably have containing the base of cinnamic acid or derivatives thereof as the cinnamic acid structure of basic framework.
If the structure with the base of cinnamic acid structure is then not particularly limited as basic framework containing cinnamic acid or derivatives thereof, preferred source is from the base of above-mentioned specific cinnamic acid derivative.In addition, R 1penylene, biphenylene, terphenyl support (terphenylene) or cyclohexalene.Part or all of the hydrogen atom of the support of this penylene, biphenylene, terphenyl and cyclohexalene also also can be had alkyl that the carbon number of fluorine atom is 1 ~ 10 or alkoxy, fluorine atom or cyano group that carbon number is 1 ~ 10 are replaced.R 2singly-bound, carbon number be 1 ~ 3 alkane two base (alkanediyl), oxygen atom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-.A is the integer of 0 ~ 3.Wherein, when a is more than 2, multiple R 1and R 2can distinguish identical also can be different.R 3fluorine atom or cyano group.B is the integer of 0 ~ 4.
Compound represented by above-mentioned formula (1) include, for example the compound represented by following formula.
[changing 2]
In those bases, R 1the penylene be preferably unsubstituted or the penylene replaced by the alkyl that fluorine atom or carbon number are 1 ~ 3.R 2be preferably singly-bound, oxygen atom or-CH 2=CH 2-.B is preferably 0 ~ 1.When being 1 ~ 3 particularly preferably in a, b is 0.
In above-mentioned formula (2), R 4penylene or cyclohexalene.The alkoxy of part or all chain that can be also 1 ~ 10 by carbon number of the hydrogen atom of this penylene or cyclohexalene or the alkyl of ring-type, chain that carbon number is 1 ~ 10 or ring-type, fluorine atom or cyano group are replaced.R 5singly-bound, carbon number be 1 ~ 3 alkane two base, oxygen atom, sulphur atom or-NH-.C is the integer of 1 ~ 3.Wherein, when c is more than 2, multiple R 4and R 5can distinguish identical also can be different.R 6fluorine atom or cyano group.D is the integer of 0 ~ 4.R 7oxygen atom ,-COO-or-OCO-.R 8it is condensed ring (condensed ring) the formula base of the aromatic series base of divalent, the ester ring type base of divalent, the hetero ring type base of divalent or divalent.R 9singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*.* the bond position with carboxyl is represented.F and g is respectively the integer of 1 ~ 10.E is the integer of 0 ~ 3.Wherein, when e is more than 2, multiple R 7and R 8can distinguish identical also can be different.
Compound represented by above-mentioned formula (2) include, for example the compound represented by following formula (2-1) ~ formula (2-2).
[changing 3]
(in formula, Q to be carbon number be 1 ~ 10 chain or the alkyl of ring-type, carbon number be 1 ~ 10 chain or the alkoxy of ring-type, fluorine atom or cyano group.F and formula (2) synonym)
The synthesis order of specific cinnamic acid derivative is not particularly limited, known method before capable of being combined and carrying out.Representational synthesis order include, for example: (i) in the basic conditions, make to have compound and the acrylic acid of the phenyl ring skeleton replaced through halogen atom, carry out in the presence of transition metal catalysts reacting and obtain the method for specific cinnamic acid derivative; (ii) in the basic conditions, the cinnamic acid that the hydrogen atom of phenyl ring is replaced through halogen atom and the compound with the phenyl ring skeleton replaced through halogen atom, carry out in the presence of transition metal catalysts reacting and make the method etc. of specific cinnamic acid derivative.
As being derived from the part of at least a kind being selected from the group be made up of the condensation product of the polysiloxane, its hydrolysate and the hydrolysate thereof that contain as main chain in [A] light regiospecific polysiloxane, as long as have the part be derived from the structure that himself can import above-mentioned smooth regiospecific base, be then not particularly limited.[A] light regiospecific polysiloxane comprise be derived from be selected from plant thus polysiloxane, its hydrolysate, its hydrolysate condensation product at least a kind of group of forming part, with the base being derived from the compound showing above-mentioned smooth regiospecific.
As the structure that can import above-mentioned smooth regiospecific base, include, for example hydroxyl, epoxy radicals, amino, carboxyl, sulfydryl, ester group, amide group etc.Wherein, the easiness importing if consider and modulate, be then preferably epoxy radicals.
[A] light regiospecific polysiloxane preferably has the polysiloxane of epoxy radicals and the reaction product of above-mentioned formula (1) and/or the compound represented by formula (2).In above-mentioned crystal aligning agent, can easily import the base being derived from the specific cinnamic acid derivative with light regiospecific in as the polysiloxane of main chain by utilizing the reactivity that has between the polysiloxane of epoxy radicals and specific cinnamic acid derivative.
The polysiloxane if above-mentioned with epoxy radicals imports epoxy radicals as side chain in polysiloxane, is not particularly limited.The above-mentioned polysiloxane with epoxy radicals also can be the hydrolysate of the polysiloxane with epoxy radicals, also can be the condensation product of its hydrolysate.As the above-mentioned polysiloxane with epoxy radicals, be preferably selected from least a kind of the group be made up of the condensation product of the polysiloxane of the structural unit had represented by following formula (3), its hydrolysate and hydrolysate thereof.
[changing 4]
(in formula (3), X 1it is the 1 valency organic group with epoxy radicals.Y 1hydroxyl, carbon number be 1 ~ 10 alkoxy, carbon number be 1 ~ 20 alkyl or carbon number be the aryl of 6 ~ 20)
In addition, the hydrolytic condensate with the polysiloxane of the structural unit represented by above-mentioned formula (3) is following concept: be not merely this polysiloxane hydrolytic condensate each other, also be included in by the hydrolytic condensation of the structural unit represented by above-mentioned formula (3) and generate in the process of polysiloxane, main chain produces the hydrolytic condensate when structural unit that branch or crosslinked etc. and the polysiloxane of gained have represented by above-mentioned formula (3).
X in above-mentioned formula (3) 1if the 1 valency organic group with epoxy radicals is then not particularly limited, include, for example the base etc. comprising glycidyl, glycidoxypropyl, epoxycyclohexyl.X 1preferably with following formula (X 1-1) or formula (X 1-2) represent.
[changing 5]
(formula (X 1-1), in, A is oxygen atom or singly-bound.H is the integer of 1 ~ 3.I is the integer of 0 ~ 6.Wherein, when i is 0, A is singly-bound.
Formula (X 1-2), in, j is the integer of 1 ~ 6.
Formula (X 1-1) and formula (X 1-2) in, * represents bond key respectively)
In addition, above-mentioned formula (X 1-1) or formula (X 1-2) in the epoxy radicals represented by, preferred following formula (X 1-1-1) or formula (X 1-2-1) represented by base.
[changing 6]
(formula (X 1-1-1) or formula (X 1-2-1) in, * represents bond key)
Y in above-mentioned formula (3) 1in,
Carbon number be 1 ~ 10 alkoxy include, for example methoxyl, ethoxy etc.;
Carbon number be 1 ~ 20 alkyl include, for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base etc.;
Carbon number be 6 ~ 20 aryl include, for example phenyl etc.
What have the polysiloxane of epoxy radicals utilizes gel permeation chromatograph (Gel PermeationChromatography, GPC) and measure polystyrene conversion weight average molecular weight (Mw) be preferably 500 ~ 100,000, be more preferably 1,000 ~ 10,000, be particularly preferably 1,000 ~ 5,000.
In addition, the Mw in this instructions is the polystyrene conversion value utilizing the GPC of following specification and measure.
Tubing string: Dong Cao company manufactures, TSKgelGRCXLII
Solvent: tetrahydrofuran
Temperature: 40 DEG C
Pressure: 6.8MPa
The polysiloxane that this kind has an epoxy radicals synthesizes by such as under type: the potpourri of the silane compound preferably making to have epoxy radicals or the silane compound with epoxy radicals and other silane compounds, is hydrolyzed or hydrolytic condensation under the existence being preferably suitable organic solvent, water and catalyzer.
The above-mentioned silane compound with epoxy radicals include, for example 3-glycydoxy trimethoxy silane, 3-glycydoxy triethoxysilane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy methyldiethoxysilane, 3-glycydoxy dimethyl methoxy silane, 3-glycydoxy dimethylethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane etc.
Other silane compounds above-mentioned include, for example tetrachloro silicane, tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four different n-butoxy silane, four sec-butoxy silane, trichlorosilane, trimethoxy silane, triethoxysilane, three positive propoxy silane, three isopropoxy silane, three n-butoxy silane, three sec-butoxy silane, fluorine trichlorosilane, fluorine trimethoxy silane, fluorine triethoxysilane, fluorine three positive propoxy silane, fluorine three isopropoxy silane, fluorine three n-butoxy silane, fluorine three sec-butoxy silane, methyl trichlorosilane, methyltrimethoxy silane, methyl triethoxysilane, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, 2-(trifluoromethyl) ethyl trichlorosilane, 2-(trifluoromethyl) ethyl trimethoxy silane, 2-(trifluoromethyl) ethyl triethoxysilane, 2-(trifluoromethyl) ethyl three positive propoxy silane, 2-(trifluoromethyl) ethyl three isopropoxy silane, 2-(trifluoromethyl) ethyl three n-butoxy silane, 2-(trifluoromethyl) ethyl three sec-butoxy silane, 2-(perfluor n-hexyl) ethyl trichlorosilane, 2-(perfluor n-hexyl) ethyl trimethoxy silane, 2-(perfluor n-hexyl) ethyl triethoxysilane, 2-(perfluor n-hexyl) ethyl three positive propoxy silane, 2-(perfluor n-hexyl) ethyl three isopropoxy silane, 2-(perfluor n-hexyl) ethyl three n-butoxy silane, 2-(perfluor n-hexyl) ethyl three sec-butoxy silane, 2-(n-perfluoro-octyl) ethyl trichlorosilane, 2-(n-perfluoro-octyl) ethyl trimethoxy silane, 2-(n-perfluoro-octyl) ethyl triethoxysilane, 2-(n-perfluoro-octyl) ethyl three positive propoxy silane, 2-(n-perfluoro-octyl) ethyl three isopropoxy silane, 2-(n-perfluoro-octyl) ethyl three n-butoxy silane, 2-(n-perfluoro-octyl) ethyl three sec-butoxy silane, hydroxymethyl trichlorosilane, hydroxymethyl trimethoxy silane, hydroxyethyl trimethoxy silane, hydroxymethyl three positive propoxy silane, hydroxymethyl three isopropoxy silane, hydroxymethyl three n-butoxy silane, hydroxymethyl three sec-butoxy silane, 3-(methyl) acryloxypropyl trichlorosilane, 3-(methyl) acryloxypropyl trimethoxy silane, 3-(methyl) acryloxypropyl triethoxysilane, 3-(methyl) acryloxypropyl three positive propoxy silane, 3-(methyl) acryloxypropyl three isopropoxy silane, 3-(methyl) acryloxypropyl three n-butoxy silane, 3-(methyl) acryloxypropyl three sec-butoxy silane, 3-mercaptopropyi trichlorosilane, 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi three positive propoxy silane, 3-mercaptopropyi three isopropoxy silane, 3-mercaptopropyi three n-butoxy silane, 3-mercaptopropyi three sec-butoxy silane, mercapto methyl trimethoxy silane, mercapto methyl triethoxysilane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three positive propoxy silane, vinyl silane triisopropoxide, vinyl three n-butoxy silane, vinyl three sec-butoxy silane, allyltrichlorosilane, allyltrimethoxysilanis, allyltriethoxysilane, allyl three positive propoxy silane, allyl three isopropoxy silane, allyl three n-butoxy silane, allyl three sec-butoxy silane, phenyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, methyl two positive propoxy silane, methyl diisopropoxy silane, methyl two n-butoxy silane, methyl two sec-butoxy silane, dimethyldichlorosilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl two positive propoxy silane, dimethyl diisopropoxy silane, dimethyl two n-butoxy silane, dimethyl two sec-butoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] dichlorosilane, (methyl) [2-(n-perfluoro-octyl) ethyl] dimethoxysilane, (methyl) [2-(n-perfluoro-octyl) ethyl] diethoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two positive propoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] diisopropoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two n-butoxy silane, (methyl) [2-(n-perfluoro-octyl) ethyl] two sec-butoxy silane, (methyl) (3-mercaptopropyi) dichlorosilane, (methyl) (3-mercaptopropyi) dimethoxysilane, (methyl) (3-mercaptopropyi) diethoxy silane, (methyl) (3-mercaptopropyi) two positive propoxy silane, (methyl) (3-mercaptopropyi) diisopropoxy silane, (methyl) (3-mercaptopropyi) two n-butoxy silane, (methyl) (3-mercaptopropyi) two sec-butoxy silane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) dimethoxysilane, (methyl) (vinyl) diethoxy silane, (methyl) (vinyl) two positive propoxy silane, (methyl) (vinyl) diisopropoxy silane, (methyl) (vinyl) two n-butoxy silane, (methyl) (vinyl) two sec-butoxy silane, divinyldichlorosilane, divinyl dimethoxysilane, divinyl diethoxy silane, divinyl two positive propoxy silane, divinyl diisopropoxy silane, divinyl two n-butoxy silane, divinyl two sec-butoxy silane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, diphenyl two positive propoxy silane, diphenyl diisopropoxy silane, diphenyl two n-butoxy silane, diphenyl two sec-butoxy silane, chlorodimethylsilane, methoxyl dimethylsilane, ethoxy dimethylsilane, chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, methoxytrimethylsilane, ethoxytrimethylsilane, positive propoxy trimethyl silane, IPOTMS isopropyloxy trimethylsilane, n-butoxy trimethyl silane, sec-butoxy trimethyl silane, tert-butoxy trimethyl silane, (chlorine) (vinyl) dimethylsilane, (methoxyl) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chlorine) (methyl) diphenyl silane, (methoxyl) (methyl) diphenyl silane, (ethoxy) (methyl) diphenyl silane etc. has the silane compound etc. of 1 silicon atom.
Commercially available product include, for example:
KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (being manufactured by SHIN-ETSU HANTOTAI's chemical industry above),
GlassResin (Showa electrician manufacture);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (being manufactured by the beautiful DOW CORNING in east (Toray Dow Coming) above);
FZ3711, FZ3722 (blocking (Unicar) by the excellent Buddhist nun of Japan above to manufacture);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (being manufactured by Chisso Corporation (Chisso) above);
Methyl silicate (Methyl Silicate) MS51, methyl silicate MS56 (being manufactured by Mitsubishi Chemical above);
Silester (Ethyl Silicate) 28, ethyl silicate 40, silester 48 (being manufactured by COLCOAT company above);
The partial condensates such as GR100, GR650, GR908, GR950 (being manufactured by Showa electrician above).
In those other silane compounds, consider from the regiospecific of the liquid crystal orienting film of gained and the viewpoint of chemical stability, be preferably tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, 3-(methyl) acryloxypropyl trimethoxy silane, 3-(methyl) acryloxypropyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane, mercapto methyl trimethoxy silane, mercapto methyl triethoxysilane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
The polysiloxane with epoxy radicals used in the present invention is in order to have the side chain of light regiospecific to measure fully to import, and suppress the import volume of epoxy radicals to become superfluous and unexpected subsidiary reaction etc. that is that cause, its epoxide equivalent is preferably 100g/mol ~ 10,000g/mol, be more preferably 150g/mol ~ 1,000g/mol.Therefore, synthesize there is the polysiloxane of epoxy radicals time, preferably become the mode of above-mentioned scope with the epoxide equivalent of the polysiloxane of gained and modulate there is the silane compound of epoxy radicals and the usage ratio of other silane compounds.
Specifically, as other silane compound of this kind, for the total of the polysiloxane and other silane compounds with epoxy radicals, preferably use 0 quality % ~ 50 quality %, more preferably use 5 quality % ~ 30 quality %.
When synthesis has the polysiloxane of epoxy radicals, spendable organic solvent include, for example hydrocarbon compound, ketonic compound, ester compounds, ether compound, alcoholic compound etc.
Above-mentioned hydrocarbon compound include, for example toluene, dimethylbenzene etc.; Above-mentioned ketone include, for example methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone, methyl-n-amyl ketone, metacetone, cyclohexanone etc.; Above-mentioned ester include, for example ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol methyl ether acetate, acetic acid-3-methoxy butyl acrylate, ethyl lactate etc.; Above-mentioned ether include, for example glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, diox etc.; Above-mentioned alcohol include, for example 1-hexanol, 4-methyl-2-amylalcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether etc.Preferred non-water-soluble organic solvent in those.Those organic solvents can be used alone or two or more is used in combination.
As the use amount of organic solvent, for all silane compound 100 mass parts, be preferably 10 mass parts ~ 10,000 mass parts, is more preferably 50 mass parts ~ 1,000 mass parts.And, as the use amount of the water manufactured when there is the polysiloxane of epoxy radicals, for all silane compounds, be preferably 0.5 times mole ~ 100 times moles, be more preferably 1 times mole ~ 30 times moles.
Above-mentioned catalyzer such as can use acid, alkali metal compound, organic base, titanium compound, zirconium compounds etc.
Above-mentioned alkali metal compound include, for example NaOH, potassium hydroxide, sodium methoxide, potassium methoxide, caustic alcohol, potassium ethoxide etc.
Above-mentioned organic base include, for example:
1 grade ~ 2 grades organic amines such as ethamine, diethylamine, piperazine, piperidines, pyrrolidine, pyrroles;
3 grades of organic amines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, DMAP, diazabicyclo undecylene (diazabicycloundecene);
4 grades of organic ammonium salts such as Tetramethylammonium hydroxide etc.In those organic bases, consider then to be preferably 3 grades of organic amines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, DMAP in the aspect that stable reaction ground carries out; 4 grades of organic ammonium salts such as Tetramethylammonium hydroxide.
As the catalyzer manufactured when there is the polysiloxane of epoxy radicals, be preferably alkali metal compound or organic base.By alkali metal compound or organic base are used as catalyzer, obtain target polysiloxane with can not producing the subsidiary reactions such as the open loop of epoxy radicals with high hydrolytic condensation speed, it is excellent and preferably to become production stability.And the above-mentioned radioactivity-sensitive crystal aligning agent containing the polysiloxane with epoxy radicals using alkali metal compound or organic base to synthesize as catalyzer and the reaction product of specific cinnamic acid derivative is due to storage stability extremely excellence and just right.
Its reason as " chemistry comment (Chemical Reviews) ", the 95th volume, pointed in the 1409th page (nineteen ninety-five), be presumed as follows: if use alkali metal compound or organic base as catalyzer in hydrolysis-condensation reaction, then form disordered structure, forge piece of step type structure or cagelike structure, therefore, it is possible to obtain silanol (silanol) base containing proportional few polysiloxane.Can infer: containing of silanol base is proportional few, therefore the condensation reaction each other of silanol base is inhibited, in addition when organic semiconductor orientation constituent of the present invention contains other polymkeric substance described later, the condensation reaction of silanol base and other polymkeric substance is inhibited, and therefore becomes the result of excellent storage stability.
Catalyzer is organic base particularly preferably.The use amount of organic base is different from the reaction conditions such as kind, temperature etc. of organic base, can be suitable for setting.As the concrete use amount of organic base, such as, for all silane compounds, be preferably 0.01 times mole ~ 3 times moles, be more preferably 0.05 times mole ~ 1 times mole.
Manufacture hydrolysis when there is the polysiloxane of epoxy radicals or hydrolysis-condensation reaction to implement preferably by such as under type: the silane compound with epoxy radicals is dissolved in organic solvent with other silane compounds optionally, this solution is mixed with organic base and water, utilizes such as oil bath etc. and heat.
It is desirable to, when hydrolysis-condensation reaction, the heating-up temperature of oil bath is preferably set to less than 130 DEG C, be more preferably set to 40 DEG C ~ 100 DEG C, preferably heating 0.5 hour ~ 12 hours, more preferably heats 1 hour ~ 8 hours.In heating process, can stir mixed liquor, under also can being positioned over backflow.
Reaction terminate after, preferably with water to autoreaction liquid divide the organic solvent layer got to clean.When this cleaning, in cleaning operation change is easy to, preferably clean with the water containing a small amount of salt, the such as aqueous ammonium nitrate solution etc. of about 0.2 quality %.Carry out cleaning until the water layer after cleaning becomes neutral, thereafter optionally use the drying agent such as dead plaster, molecular sieve (molecular sieve) by after organic solvent layer in addition drying, the polysiloxane with epoxy radicals of target can be obtained except desolventizing.
In the present invention, the polysiloxane with epoxy radicals also can use commercially available product.This kind of commercially available product include, for example DMS-E01, DMS-E12, DMS-E21, EMS-32 (being manufactured by Chisso Corporation above) etc.
[A] light regiospecific polyorganosiloxane compounds also can comprise the part being derived from polysiloxane self hydrolysis with epoxy radicals and the hydrolysate produced or the part being derived from the polysiloxane hydrolytic condensate of hydrolytic condensation each other with epoxy radicals.Also modulate by the condition same with the hydrolysis of polysiloxane or condensation condition with epoxy radicals as those hydrolysates of the constituent material of above-mentioned part or hydrolytic condensate.
The synthetic method > of < [A] light regiospecific polysiloxane
[A] light regiospecific polysiloxane used in the present invention such as synthesizes by such as under type: make above-mentioned there is epoxy radicals polysiloxane and specific cinnamic acid derivative preferably react in the presence of a catalyst.
Herein, as the use amount of specific cinnamic acid derivative, for the epoxy radicals 1 mole that polysiloxane has, be preferably 0.001 mole ~ 10 moles, be more preferably 0.01 mole ~ 5 moles, be particularly preferably 0.05 mole ~ 2 moles.
Above-mentioned catalyzer can be used as the so-called hardening accelerator of the reaction promoting organic base or epoxy compound and acid anhydrides and known compound.Above-mentioned organic base include, for example the compound identical with above-mentioned organic base.
Above-mentioned hardening accelerator include, for example:
3 grades of amine such as dimethyl benzylamine, 2,4,6-tri-(dimethylaminomethyl) phenol, cyclohexyldimethyl amine, triethanolamine;
Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1,2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-glyoxal ethyline, 1-(2-cyanoethyl)-2-n-undecane base imidazoles, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis-(hydroxymethyl) imidazoles, 1-(2-cyanoethyl)-2-phenyl-4,5-bis-[(2 '-cyanoethoxy) methyl] imidazoles, 1-(2-cyanoethyl)-2-n-undecane base imidazoles trimellitic acid salt, 1-(2-cyanoethyl)-2-phenylimidazole trimellitic acid salt, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole trimellitic acid salt, 2,4-diamido-6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine (s-triazine), 2,4-diamido-6-(2 '-n-undecane base imidazole radicals) ethyl-s-triazine, 2,4-diamido-6-[-4 '-methylimidazolyl-(1 ') of 2 '-ethyl] ethyl-s-triazine, the fulminuric acid addition product of glyoxal ethyline, the fulminuric acid addition product of 2-phenylimidazole, and the imidazolium compounds such as the fulminuric acid addition product of 2,4-diamido-6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine,
The organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;
Benzyltriphenyl phosphonium phosphonium chloride, tetra-n-butyl phosphonium bromide, first base triphenyl phosphonium bromide, second base triphenyl phosphonium bromide, normal-butyl triphenyl phosphonium bromide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, ethyl triphen guanidine-acetic acid Phosphonium, four positive fourth base Phosphonium O, 4 grades of phosphonium salts such as O-diethyl phosphorothioate, four positive fourth base Phosphonium benzotriazole salt, tetraphenylphosphoniphenolate tetraphenyl borate salts, four positive fourth base Phosphonium tetrafluoroborates, four positive fourth base Phosphonium tetraphenyl borate salts;
The Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecylene-7 or its acylate;
The organometallicss such as zinc octoate, tin octoate, diacetone aluminium complex;
4 grades of ammonium salts such as tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride;
The boron compound such as boron trifluoride, triphenyl borate;
The metal halide compounds such as zinc chloride, butter of tin (tin tetrachloride);
The high-melting-point decentralized potentiality hardening accelerators such as amine add-on type promoter such as the addition product of dicyanodiamide or amine and epoxy resin;
The microcapsule-type potentiality hardening accelerator of polymkeric substance is had at the Surface coating of the hardening accelerators such as above-mentioned imidazolium compounds, organic phosphorus compound or 4 phosphonium salts;
Amine salt type potentiality hardening accelerator;
The potentiality hardening accelerators etc. such as the hot cationic polymerization type potentiality hardening accelerator of the thermal dissociation types such as lewis acid, Bronsted acid (bronsted acid) salt.
4 grades of ammonium salts such as preferred tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride in those catalyzer.
As the use amount of catalyzer, for polysiloxane 100 mass parts with epoxy radicals, be preferably below 100 mass parts, be more preferably 0.01 mass parts ~ 100 mass parts, be particularly preferably 0.1 mass parts ~ 20 mass parts.
Temperature of reaction is preferably 0 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 150 DEG C.Reaction time is preferably 0.1 hour ~ 50 hours, is more preferably 0.5 hour ~ 20 hours.
[A] light regiospecific polysiloxane can optionally synthesize in presence of organic solvent.This organic solvent include, for example hydrocarbon compound, ether compound, ester compounds, ketonic compound, amide compound, alcoholic compound etc.In those compounds, consider from the viewpoint of the easiness of raw material and the dissolubility of product and the purifying of product, preferred ether compound, ester compounds, ketonic compound.Preferably become below more than 0.1 quality % 70 quality % with solid concentration (ratio that the quality of the composition beyond the solvent in reaction solution is shared in the gross mass of solution), more preferably become the amount of below more than 5 quality % 50 quality % and use solvent.
As mentioned above and the Mw of [A] light regiospecific polysiloxane of gained is not particularly limited, be preferably 1,000 ~ 20,000, be more preferably 3,000 ~ 15,000.By being set to this kind of molecular weight ranges, good regiospecific and the stability of liquid crystal orienting film can be guaranteed.
[A] light regiospecific polysiloxane is on the polysiloxane with epoxy radicals, imports by the open loop addition in epoxy radicals of the carboxyl of specific cinnamic acid derivative the structure being derived from specific cinnamic acid derivative.This manufacture method is easy, and can improve the Drug delivery rate of the structure being derived from specific cinnamic acid derivative, is the method be extremely suitable in this regard.
In the present invention, can in the scope not undermining effect of the present invention, a part for above-mentioned specific cinnamic acid derivative be substituted by the compound represented by following formula (4) and use.In such cases, the synthesis of [A] light regiospecific polyorganosiloxane compounds is undertaken by following mode: make to have the polysiloxane of epoxy radicals, react with the potpourri of specific cinnamic acid derivative and the compound represented by following formula (4).
[changing 7]
R 10-R 11one R 12(4)
R in above-mentioned formula (4) 10be preferably carbon number be 8 ~ 20 alkyl or alkoxy or carbon number be 4 ~ 21 fluoroalkyl or Fluoroalkyloxy.R 11be preferably singly-bound, Isosorbide-5-Nitrae-cyclohexalene or Isosorbide-5-Nitrae-penylene.R 12be preferably carboxyl.
Compound represented by above-mentioned formula (4) include, for example the compound represented by following formula (4-1) ~ formula (4-3).
[changing 8]
Compound represented by above-mentioned formula (4) can make the active site inactivation of [A] light regiospecific polysiloxane, thus the stability contributing to above-mentioned crystal aligning agent improves.In the present invention, when together using the compound represented by above-mentioned formula (4) with specific cinnamic acid derivative, as the total usage ratio of the compound represented by specific cinnamic acid derivative and above-mentioned formula (4), 0.001 mole ~ 1.5 moles are preferably for the epoxy radicals 1 mole that polysiloxane has, be more preferably 0.01 mole ~ 1 mole, be particularly preferably 0.05 mole ~ 0.9 mole.In such cases, as the use amount of the compound represented by above-mentioned formula (4), relative to the total of specific cinnamic acid derivative for be preferably below 50mol%, be more preferably below 25mol%.If the usage ratio of the compound represented by above-mentioned formula (4) is more than 50mol%, then there is the possibility of the unfavorable condition of the regiospecific reduction producing liquid crystal orienting film.
< [B] other polymkeric substance >
Above-mentioned crystal aligning agent can containing [B] other polymkeric substance as suitable compositions.[B] other polymkeric substance can enumerate at least a kind that is selected from the group be made up of polyamic acid, polyimide, ethene unsaturated polymerizable compound thing, the polysiloxane of not having light regiospecific base.When containing those [B] other polymkeric substance, in the liquid crystal orienting film formed by above-mentioned crystal aligning agent, obvious light regiospecific polysiloxane is partial near this top layer and exists.Therefore, by making the content of other polymkeric substance increase, even if reduce the content of the light regiospecific polysiloxane in above-mentioned crystal aligning agent, light regiospecific polysiloxane is also partial to alignment film surface and exists, and therefore obtains sufficient LCD alignment.Therefore, in the present invention, can reduce the content of light regiospecific polysiloxane in above-mentioned crystal aligning agent that manufacturing cost is high, its result can lower the manufacturing cost of above-mentioned crystal aligning agent.
[polyamic acid]
Polyamic acid reacts by making tetracarboxylic dianhydride and diamine compound and obtains.
Tetracarboxylic dianhydride include, for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.Those tetracarboxylic dianhydrides can be used alone or two or more combinationally used.
Aliphatics tetracarboxylic dianhydride include, for example ethylene-dimalonic acid dianhydride etc.
Alicyclic tetracarboxylic acid dianhydride include, for example 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone etc.
Aromatic tetracarboxylic acid's dianhydride include, for example pyromellitic acid anhydride etc., also can enumerate tetracarboxylic dianhydride described in No. 2010-97188, Japanese Patent Laid-Open in addition.
In those tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydrides.
As 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1, the use amount of 2,3,4-cyclobutanetetracarboxylic dianhydride, for all tetracarboxylic dianhydrides, be preferably more than 10mol%, be more preferably more than 20mol%, particularly preferably only comprise 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
As diamine compound, include, for example aliphatic diamine, ester ring type diamines, aromatic diamine, diamido organosiloxane etc.Those diamine compounds can be used alone or two or more combinationally used.
Aliphatic diamine include, for example m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine etc.
Ester ring type diamines include, for example Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 1,3-two (amino methyl) cyclohexanes etc.
Aromatic diamine include, for example p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7-diamino-fluorene (2,7-diamonefluorene), 4,4 '-diaminodiphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to penylene diisopropylidene) dianiline, 4,4 '-(a penylene diisopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-biphenylamine, N, N '-bis-(4-aminophenyl)-N, N '-dimethylbenzidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-diaminobenzene, cholestane base oxygen base-2,4-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base, 3,5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid lanostane base ester, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) cyclohexane of 1,1-, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzene methylamine, 3-aminobenzene methylamine and the diamine compound etc. represented by following formula (A-1).
[changing 9]
(in formula (A-1), X ito be carbon number be 1 ~ 3 alkyl, *-O-, *-COO-or *-OCO-.Wherein, with bond key and the diamino-phenyl bond of *.R is 0 or 1.S is the integer of 0 ~ 2.T is the integer of 1 ~ 20)
Diamido organosiloxane include, for example two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., also can enumerate diamines described in No. 2010-97188, Japanese Patent Laid-Open in addition.
As the tetracarboxylic dianhydride of synthetic reaction and the usage ratio of diamine compound that are provided to polyamic acid, for amino 1 equivalent contained in diamine compound, the anhydride group of tetracarboxylic dianhydride is preferably 0.2 equivalent ~ 2 equivalent, is more preferably 0.3 equivalent ~ 1.2 equivalent.
Synthetic reaction is preferably carried out in organic solvent.Temperature of reaction is preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.Reaction time is preferably 0.5 hour ~ 24 hours, is more preferably 2 hours ~ 12 hours.
As organic solvent, if then there is no particular restriction for the organic solvent of the polyamic acid synthesized by solubilized, include, for example METHYLPYRROLIDONE (NMP), N, N-dimethyl acetamide, N, the non-proton class polar solvents such as dinethylformamide, N, N-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; The phenol solvents such as metacresol, xylenols, phenol, halogenated phenols.
As the use amount (a) of organic solvent, for the total (a+b) of tetracarboxylic dianhydride and the total amount (b) of diamine compound and the use amount (a) of organic solvent, be preferably 0.1 quality % ~ 50 quality %, be more preferably 5 quality % ~ 30 quality %.
After reaction, the polyamic acid solution of gained directly can be supplied to the modulation of crystal aligning agent, also by being supplied to the modulation of crystal aligning agent after polyamic acid contained in reaction solution segregation, the modulation of crystal aligning agent can after also can carrying out purifying to emanated polyamic acid, be supplied to.As the isolation process of polyamic acid, include, for example following method: reaction solution is injected into the precipitate of gained in a large amount of poor solvents and under reduced pressure carries out dry method; By the method etc. that reaction solution decompression distillation removes by evaporator.As the purification process of polyamic acid, the method that can be listed below: emanated polyamic acid is dissolved in organic solvent again, the method making it separate out with poor solvent; Carry out 1 time or repeatedly by the method for evaporator by the step of the decompression distillation such as organic solvent removing.
[polyimide]
Polyimide is by manufacturing as under type: to above-mentioned polyamic acid the amic acid structure that has carry out dehydration closed-loop and imidizate.Polyimide can be using the complete acid imide compound of the amic acid structure fully dehydrating closed loop had as the polyamic acid of its precursor, also can be only a part of dehydration closed-loop of amic acid structure, thus amic acid structure and imide ring structure the part acid imide compound of depositing.
As the synthetic method of polyimide, include, for example method (hereinafter sometimes referred to " method (i) ") that (i) heat polyamic acid, polyamic acid is dissolved in organic solvent by (ii), dewatering agent and dehydration closed-loop catalyzer is added, the method that the method (hereinafter sometimes referred to " method (ii) ") etc. optionally carrying out heating utilizes the dehydration closed-loop of polyamic acid to react in this solution.
As the temperature of reaction in method (i), be preferably 50 DEG C ~ 200 DEG C, be more preferably 60 DEG C ~ 170 DEG C.If temperature of reaction is less than 50 DEG C, then dehydration closed-loop reaction is also carried out deficiently, if temperature of reaction is more than 200 DEG C, then and the phenomenon that the molecular weight that there is the polyimide of gained reduces.Reaction time is preferably 0.5 hour ~ 48 hours, is more preferably 2 hours ~ 20 hours.
The polyimide of gained directly can be supplied to the modulation of crystal aligning agent in method (i), be supplied to after polyimide also can be made to emanate crystal aligning agent modulation or after purifying is carried out to emanated polyimide or be supplied to the modulation of crystal aligning agent after purifying is carried out to the polyimide of gained.
Dewatering agent in method (ii) include, for example the acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.
As the use amount of dewatering agent, can be suitable for according to desired acid imide rate selecting, for 1 mole, the amic acid structure of polyamic acid, be preferably 0.01 mole ~ 20 moles.
Dehydration closed-loop catalyzer in method (ii) include, for example pyridine, collidine, two picolins, triethylamine etc.
As the use amount of dehydration closed-loop catalyzer, for contained dewatering agent 1 mole, be preferably 0.01 mole ~ 10 moles.In addition, the content of above-mentioned dewatering agent and dehydration closed-loop agent more can improve acid imide rate more at most.
As the organic solvent used in method (ii), include, for example the organic solvent etc. identical with the illustrative organic solvent as the organic solvent used in the synthesis of polyamic acid.
Temperature of reaction in method (ii) is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction time is preferably 0.5 hour ~ 20 hours, is more preferably 1 hour ~ 8 hours.By making reaction conditions be above-mentioned scope, carry out while dehydration closed-loop sufficient reacting can be made, and the suitable molecular weight of polyimide of gained can be made.
The reaction solution containing polyimide is obtained in method (ii).This reaction solution directly can be supplied to the modulation of crystal aligning agent, also be supplied to the modulation of crystal aligning agent after can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, be supplied to the modulation of crystal aligning agent or after purifying is carried out to emanated polyimide, be supplied to the modulation of crystal aligning agent after polyimide also can be made to emanate.The method removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution include, for example the method etc. of solvent displacement.The isolation process of polyimide and purification process include, for example with as the isolation process of polyamic acid and purification process and the identical method etc. of illustrative method.
[ethene unsaturated polymerizable compound thing]
Ethene unsaturated polymerizable compound thing as [B] other polymkeric substance obtains by using known method to make known ethene unsaturated polymerizable compound.Such as obtain (by by this copolymerization, the multipolymer of gained is called " (B1) multipolymer " sometimes below) by making polymerizable unsaturated compound (hereinafter sometimes referred to " (b2) the unsaturated compound ") copolymerization beyond (a) ethene unsaturated compound containing epoxy radicals (hereinafter sometimes referred to " (a) unsaturated compound ") and (b1) ethene unsaturated carboxylic acid and/or the unsaturated polybasic acid anhydride of polymerism (hereinafter sometimes referred to " (b1) unsaturated compound ") and (a) unsaturated compound and (b1) unsaturated compound.
A () unsaturated compound include, for example (methyl) glycidyl acrylate, α-ethylacrylate glycidyl esters, α-n-pro-pyl glycidyl acrylate, α-n-butyl glycidyl esters, (methyl) acrylic acid-3,4-epoxybutyl ester, α-ethylacrylate-3,4-epoxybutyl ester, (methyl) acrylic acid-6,7-epoxy heptyl ester, α-ethylacrylate-6,7-epoxy heptyl ester etc.
(b1) unsaturated compound include, for example:
The unsaturated carboxylic acid classes such as (methyl) acrylic acid, crotonic acid, α-ethylacrylate, α-n-pro-pyl acrylic acid, α-n-butyl, maleic acid, fumaric acid, citraconic acid (citraconic acid), mesaconic acid (mesaconic acid), itaconic acid (itaconic acid);
The unsaturated polybasic acid anhydride class such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrabydrophthalic anhydride etc.
(b2) unsaturated compound include, for example:
(methyl) hydroxyalkyl acrylates classes such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester;
(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester is (below by three ring [5.2.1.0 2,6] decane-8-base is called " bicyclopentyl "), (methyl) acrylate ring type ester class such as (methyl) acrylic acid 2-bicyclopentyl oxygen base ethyl ester, (methyl) isobornyl acrylate;
(methyl) benzyl acrylate classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
The unsaturated dicarboxylic diester classes such as diethyl maleate, DEF, diethyl itaconate;
The unsaturated dicarbonyl imides derivants such as N-phenylmaleimide, N-benzyl maleimide, N-N-cyclohexylmaleimide, N-succinimide (succinimidyl) base-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide;
The acrylonitrile compounds such as (methyl) vinyl cyanide, α-chloro-acrylonitrile, vinylidene dinitrile;
The unsaturated acyl amines such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide;
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to aromatic ethenyl compounds such as methoxy styrenes;
The indene derivative classes such as indenes, 1-methyl indenes;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene equiconjugate diolefinic compounds, also can enumerate vinyl chloride, vinylidene chloride, vinyl acetate etc. in addition.
In (B1) multipolymer, as the containing ratio of structural unit being derived from (a) unsaturated compound, for all structural units, be preferably 10 quality % ~ 70 quality %, be more preferably 20 quality % ~ 60 quality %; As the total containing ratio of structural unit being derived from (b1) unsaturated compound, for all structural units, be preferably 5 quality % ~ 40 quality %, be more preferably 10 quality % ~ 30 quality %; As the containing ratio of structural unit being derived from (b2) unsaturated compound, for all structural units, be preferably 10 quality % ~ 70 quality %, be more preferably 20 quality % ~ 50 quality %.
(B1) multipolymer can make each unsaturated compound under the existence of suitable solvent and polymerization initiators, is synthesized by such as free radical polymerization.Organic solvent include, for example the organic solvent etc. identical with the illustrative organic solvent as the organic solvent used in the synthesis of polyamic acid.
Polymerization initiators include, for example:
2,2 '-azobis isobutyronitrile, 2,2 '-azo is two-(2,4-methyl pentane nitrile), 2, and 2 '-azo is two-azo-compound such as (4-methoxyl-2,4-methyl pentane nitrile);
The organic peroxide such as benzoyl peroxide, lauroyl peroxide, the peroxidating pivalic acid tert-butyl ester (t-butyl peroxypivalate), 1,1 '-bis--(t-butylperoxy) cyclohexane;
Hydrogen peroxide;
Comprise the oxidation-reduction type initiator etc. of those superoxide and reductive agent.Those polymerization initiators can be used alone or two or more is used in combination.
The polysiloxane of light regiospecific base [do not have]
Above-mentioned crystal aligning agent also can further containing the polysiloxane of not having a light regiospecific base as [B] other polymkeric substance except [A] light regiospecific polysiloxane.The polysiloxane of light regiospecific base of not having preferably is selected from least a kind of the group be made up of the condensation product of the polysiloxane of the structural unit had represented by following formula (5), its hydrolysate and hydrolysate.In addition, when above-mentioned crystal aligning agent comprise do not have the polysiloxane of light regiospecific base, if major part and [A] light regiospecific polysiloxane of polysiloxane of light regiospecific base of not having has an independent existence, then its part also can be used as and the condensation product of [A] light regiospecific polysiloxane and existing.
[changing 10]
In above-mentioned formula (5), X 2hydroxyl, halogen atom, carbon number be 1 ~ 20 alkyl, carbon number be 1 ~ 6 alkoxy or carbon number be the aryl of 6 ~ 20.Y 2to be hydroxyl or carbon number be 1 ~ 10 alkoxy.
Carbon number be 1 ~ 20 alkyl include, for example the methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc. of straight-chain or branch-like.
Carbon number be 1 ~ 6 alkoxy include, for example methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy etc.
Carbon number be 6 ~ 20 aryl include, for example phenyl, naphthyl etc.
The polysiloxane of light regiospecific base of not having such as can synthesize in the following way: will be selected from least a kind of silane compound (hereinafter sometimes referred to " raw silicon hydride compounds ") of the group be made up of alkoxysilane compound containing trialkylsilyl group in molecular structure and silane halide compound, is preferably hydrolyzed or hydrolytic condensation in suitable organic solvent, under the existence of water and catalyzer.
Raw silicon hydride compounds include, for example:
Tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four different n-butoxy silane, four sec-butoxy silane, four tert-butoxy silane, tetrachloro silicane etc.;
Methyltrimethoxy silane, methyl triethoxysilane, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three tert-butoxy silane, methyl triple phenoxyl silane, methyl trichlorosilane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three positive propoxy silane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, ethyl three sec-butoxy silane, ethyl three tert-butoxy silane, ethyl trichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl trichlorosilane etc.,
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane etc.;
Trimethylmethoxysilane, trimethylethoxysilane, trimethyl chlorosilane etc.
Preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylmethoxysilane or trimethylethoxysilane in those raw silicon hydride compounds.
Synthesize do not have the polysiloxane of light regiospecific base time, the organic solvent that can at random use include, for example alcoholic compound, ketonic compound, amide compound, ester compounds or other aprotic compounds.Those compounds can be used alone or two or more combinationally used.
As the amount of the water used when synthesizing and not having the polysiloxane of light regiospecific base, for the total 1 mole of the alkoxy had relative to raw silicon hydride compounds and halogen atom, be preferably 0.01 mole ~ 100 moles, be more preferably 0.1 mole ~ 30 moles, be particularly preferably 1 mole ~ 1.5 moles.
As synthesize do not have the polysiloxane of light regiospecific base time spendable catalyzer, include, for example meal chelate compounds, organic acid, mineral acid, organic base, alkali metal compound, alkaline earth metal compound, ammonia etc.Those compounds can be used alone or two or more combinationally used.
As the use amount of catalyzer, for raw silicon hydride compounds 100 mass parts, be preferably 0.001 mass parts ~ 10 mass parts, be more preferably 0.001 mass parts ~ 1 mass parts.
As the water added when synthesizing and not having the polysiloxane of light regiospecific base, can to make an addition to intermittently or continuously in the silane compound as raw material or silane compound to be dissolved in the solution in organic solvent.Catalyzer can to make an addition in advance in the silane compound as raw material or to be dissolved in by silane compound in the solution in organic solvent, and it also can be made to be dissolved or dispersed in advance in added water.
As synthesizing temperature of reaction when not having the polysiloxane of light regiospecific base, being preferably 0 DEG C ~ 100 DEG C, being more preferably 15 DEG C ~ 80 DEG C.Reaction time is preferably 0.5 hour ~ 24 hours, is more preferably 1 hour ~ 8 hours.
When above-mentioned crystal aligning agent contains [B] other polymkeric substance, proportional as containing of [B] other polymkeric substance, different because of the kind of [B] other polymkeric substance, 10 are preferably for [A] light regiospecific polysiloxane 100 mass parts, below 000 mass parts, be more preferably 5, below 000 mass parts, be more preferably 2 further, below 000 mass parts.
The compound > of < [C] containing ester structure
Above-mentioned crystal aligning agent can to form the excellent liquid crystal orienting film such as thermotolerance by comprising [C] containing the compound of ester structure.And by containing [C] compound containing ester structure in above-mentioned crystal aligning agent, becoming and can calcine liquid crystal orienting film at lower temperatures, the range of choice therefore forming the substrate of liquid crystal orienting film becomes large.
[C] compound containing ester structure has to be selected from the one kind or two or more of the group that is made up of the tert-butyl ester structure of the ketal ester structure of the acetal ester of carboxylic acid (acetalester) structure, carboxylic acid, the 1-alkyl-cycloalkyl ester structure of carboxylic acid and carboxylic acid in molecule, and have the compound of this structure multiple when this structure is a kind.That is [C] compound containing ester structure can be the compound of the structure of the identical type had in more than 2 those structures, also can be the compound merging the different types of structure had in more than 2 those structures.The above-mentioned base comprising the acetal ester structure of carboxylic acid can enumerate following formula (C-1) and the base represented by formula (C-2).
[changing 11]
(in formula (C-1), R 13and R 14the alkyl, the carbon number that are independently 1 ~ 20 for carbon number be 3 ~ 10 ester ring type base, carbon number be 6 ~ 10 aryl or carbon number be the aralkyl of 7 ~ 10.
In formula (C-2), n1 is the integer of 2 ~ 10)
R in above-mentioned formula (C-1) 13in, carbon number be 1 ~ 20 alkyl be preferably methyl, carbon number be 3 ~ 10 ester ring type base be preferably cyclohexyl, carbon number be 6 ~ 10 aryl be preferably phenyl, carbon number be 7 ~ 10 aralkyl be preferably benzyl.R 14carbon number be 1 ~ 20 alkyl be preferably the alkyl that carbon number is 1 ~ 6, carbon number be 3 ~ 10 ester ring type base be preferably the ester ring type base that carbon number is 6 ~ 10, carbon number be 6 ~ 10 aryl be preferably phenyl, carbon number be 7 ~ 10 aralkyl be preferably benzyl or 2-phenylethyl.N1 in formula (C-2) is preferably 3 or 4.
Base represented by above-mentioned formula (C-1) include, for example 1-methoxyethoxycarbonyl, 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-n-butoxy ethoxy carbonyl, 1-isobutoxy ethoxy carbonyl, 1-sec-butoxy ethoxy carbonyl, 1-tert-butoxyethoxy carbonyl, 1-cyclohexyloxy ethoxy carbonyl, 1-norborny oxygen base oxethyl carbonyl, 1-phenoxy group carbonyl, (cyclohexyl) (methoxyl) methoxycarbonyl, (cyclohexyl) (cyclohexyloxy) methoxycarbonyl, (cyclohexyl) (phenoxy group) methoxycarbonyl, (cyclohexyl) (benzyloxy) methoxycarbonyl, (phenyl) (methoxyl) methoxycarbonyl, (phenyl) (cyclohexyloxy) methoxycarbonyl, (phenyl) (phenoxy group) methoxycarbonyl, (phenyl) (benzyloxy) methoxycarbonyl, (benzyl) (methoxyl) methoxycarbonyl, (benzyl) (cyclohexyloxy) methoxycarbonyl, (benzyl) (phenoxy group) methoxycarbonyl, (benzyl) (benzyloxy) methoxycarbonyl etc.
Base represented by above-mentioned formula (C-2) include, for example 2-tetrahydrofuran base oxygen base carbonyl, 2-THP trtrahydropyranyl oxygen base carbonyl etc.
Preferred 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-cyclohexyloxy ethoxy carbonyl, 2-tetrahydrofuran base oxygen base carbonyl, 2-THP trtrahydropyranyl oxygen base carbonyl in those bases.
The above-mentioned base comprising the ketal ester structure of carboxylic acid include, for example the base represented by following formula (C-3) ~ formula (C-5).
[changing 12]
(in formula (C-3), R 15to be carbon number be 1 ~ 12 alkyl.R 16and R 17the alkyl, the carbon number that are independently 1 ~ 12 for carbon number be 3 ~ 20 ester ring type base, carbon number be 6 ~ 20 aryl or carbon number be the aralkyl of 7 ~ 20.
In formula (C-4), R 18to be carbon number be 1 ~ 12 alkyl.N2 is the integer of 2 ~ 8.
In formula (C-5), R 19to be carbon number be 1 ~ 12 alkyl.N3 is the integer of 2 ~ 8)
R in above-mentioned formula (C-3) 15carbon number be 1 ~ 12 alkyl be preferably methyl, R 16in carbon number be 1 ~ 12 alkyl be preferably methyl, carbon number be 3 ~ 20 ester ring type base be preferably cyclohexyl, carbon number be 6 ~ 20 aryl be preferably phenyl, carbon number be 7 ~ 20 aralkyl be preferably benzyl.R 17in carbon number be 7 ~ 20 alkyl be preferably the alkyl that carbon number is 1 ~ 6.Carbon number be 3 ~ 20 ester ring type base be preferably the ester ring type base that carbon number is 6 ~ 10.Carbon number be 6 ~ 20 aryl be preferably phenyl.Carbon number be 7 ~ 20 aralkyl be preferably benzyl or 2-phenylethyl.R in formula (C-4) 18carbon number be 1 ~ 12 alkyl be preferably methyl.N2 is preferably 3 or 4.R in formula (C-5) 19carbon number be 1 ~ 12 alkyl be preferably methyl.N3 is preferably 3 or 4.
Base represented by above-mentioned formula (C-3) include, for example 1-methyl isophthalic acid-methoxyethoxycarbonyl, 1-methyl isophthalic acid-positive propoxy ethoxy carbonyl, 1-methyl isophthalic acid-n-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-isobutoxy ethoxy carbonyl, 1-methyl isophthalic acid-sec-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-tert-butoxyethoxy carbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxy carbonyl, 1-methyl isophthalic acid-norborny oxygen base oxethyl carbonyl, 1-methyl isophthalic acid-phenoxy group carbonyl, 1-methyl isophthalic acid-Benzyloxyethoxy carbonyl, 1-methyl isophthalic acid-phenoxy group carbonyl, 1-cyclohexyl-1-methoxyethoxycarbonyl, 1-cyclohexyl-1-cyclohexyloxy ethoxy carbonyl, 1-cyclohexyl-1-phenoxy group carbonyl, 1-phenyl-1-methoxyethoxycarbonyl, 1-phenyl-1-ethoxy ethoxy carbonyl, 1-phenyl-1-phenoxy group carbonyl, 1-phenyl-1-Benzyloxyethoxy carbonyl, 1-benzyl-1-methoxyethoxycarbonyl, 1-benzyl-1-cyclohexyloxy ethoxy carbonyl, 1-benzyl-1-phenoxy group carbonyl, 1-benzyl-1-Benzyloxyethoxy carbonyl etc.
Base represented by above-mentioned formula (C-4) include, for example 2-(2-methyltetrahydrofuran base) oxygen base carbonyl, 2-(2-methyl THP trtrahydropyranyl) oxygen base carbonyl etc.
Base represented by above-mentioned formula (C-5) include, for example 1-methoxyl cyclopentyloxy carbonyl, 1-methoxycyclohexyl oxygen base carbonyl etc.
Preferred 1-methyl isophthalic acid-methoxyethoxycarbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxy carbonyl in those bases.
The above-mentioned base comprising the 1-alkyl-cycloalkyl ester structure of carboxylic acid include, for example the base represented by following formula (C-6).
[changing 13]
(in formula (C-6), R 20to be carbon number be 1 ~ 12 alkyl.N4 is the integer of 1 ~ 8)
R in above-mentioned formula (C-6) 20carbon number be 1 ~ 12 alkyl be preferably the alkyl that carbon number is 1 ~ 10.
Base represented by above-mentioned formula (C-6) include, for example 1-methyl ring propoxycarbonyl, 1-methyl cyclobutoxycarbonyl, 1-methylcyclopentoxy carbonyl, 1-methyl cyclohexane oxygen base carbonyl, 1-methyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-ethyl cyclobutoxycarbonyl, 1-ethyl cyclopentyloxy carbonyl, 1-cyclohexyl oxygen base carbonyl, 1-ethyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) propyl group ring propoxycarbonyl, 1-(different) propyl group cyclobutoxycarbonyl, 1-(different) propyl group ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) butyl cyclobutoxycarbonyl, 1-(different) butyl cyclopentyloxy carbonyl, 1-(different) butylcyclohexyl oxygen base carbonyl, 1-(different) butyl ring oxygen in heptan base carbonyl, 1-(different) butyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) amyl group ring oxygen in heptan base carbonyl, 1-(different) amyl group ring carbonyl octyloxy, 1-(different) hexyl ring propoxycarbonyl, 1-(different) hexyl cyclobutoxycarbonyl, 1-(different) hexyl cyclopentyloxy carbonyl, 1-(different) hexyl cyclohexyloxy carbonyl, 1-(different) hexyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) hexyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) octyl group ring propoxycarbonyl, 1-(different) octyl group cyclobutoxycarbonyl, 1-(different) octyl group cyclopentyloxy carbonyl, 1-(different) octyl group cyclohexyloxy carbonyl, 1-(different) octyl group ring oxygen in heptan base carbonyl, 1-(different) octyl group ring carbonyl octyloxy, 1-(different) octyl group ring oxygen in last of the ten Heavenly stems base carbonyl etc.
The above-mentioned base comprising the tert-butyl ester structure of carboxylic acid is tert-butoxycarbonyl.
[C] compound containing ester structure in the present invention is preferably the compound represented by following formula (C).
T nR (C)
(in formula (C), T is the base represented by any formula or the tert-butoxycarbonyl of above-mentioned formula (C-1) ~ formula (C-6), be from n be 2 and R is singly-bound or n be 2 ~ 10 integer and R is carbon number be 3 ~ 10 heterogeneous ring compound except the n valency base of dehydrogenation and gained or carbon number be 1 ~ 18 n valency alkyl.)
N is preferably 2 or 3.
As the R in above-mentioned formula (C), singly-bound can be enumerated when n is 2, carbon number be 1 ~ 12 alkane two base, 1,2-penylene, 1,3-penylene, Isosorbide-5-Nitrae-penylene, 2,6-naphthyls, 5-sodium sulfo group-1,3-penylene, 5-4-butyl-phosphonium sulfo group-1,3-penylene etc.
When n is 3, above-mentioned R can enumerate base, benzene-1,3,5-tri-base etc. represented by following formula.
[changing 14]
Above-mentioned alkane two base is preferably straight-chain.
[C] represented by above-mentioned formula (C) compound containing ester structure is by vitochemical conventional method or vitochemical conventional method combined aptly and synthesize.
Such as, compound (wherein, the R of the base of the T in above-mentioned formula (C) represented by above-mentioned formula (C-1) 13for phenyl situation except) synthesize by such as under type: preferably under the existence of phosphoric acid catalyst, to compound R-(COOH) n(wherein, R and n respectively with above-mentioned formula (C) synonym) and compound R 14-O-CH=R 13 '(wherein, R 14with above-mentioned formula (C-1) synonym.R 13 'the R in above-mentioned formula (C-1) 13carbon removing hydrogen atom and the base of gained) carry out addition.
The compound of the base of the T in above-mentioned formula (C) represented by above-mentioned formula (C-2) synthesizes by such as under type: preferably under the existence of Catalyzed by p-Toluenesulfonic Acid agent, to compound R-(COOH) n(wherein, R and n and above-mentioned formula (C) synonym) and the compound represented by following formula carry out addition.
[changing 15]
(in formula, n1 and above-mentioned formula (C-2) synonym)
As the content of [C] compound containing ester structure in above-mentioned crystal aligning agent, if the thermotolerance etc. required by considering and determining, then be not particularly limited, for [A] light regiospecific polysiloxane 100 mass parts, [C] compound containing ester structure is preferably 0.1 mass parts ~ 50 mass parts, be more preferably 1 mass parts ~ 20 mass parts, be particularly preferably 2 mass parts ~ 10 mass parts.
Other any composition > of <
Above-mentioned crystal aligning agent than that described above, can contain rigidizer, hardening catalyst, hardening accelerator, the compound (hereinafter sometimes referred to " epoxy compound ") in molecule with at least one epoxy radicals, functional silanes compound, surfactant, light sensitizer etc. in the scope not undermining effect of the present invention.Below those other any composition is described in detail.
[rigidizer, hardening catalyst and hardening accelerator]
The cross-linking reaction that can make [A] light regiospecific polysiloxane more firmly for the purpose of and containing rigidizer and hardening catalyst in above-mentioned crystal aligning agent.And, can promote in above-mentioned crystal aligning agent, to contain above-mentioned hardening accelerator for the purpose of the sclerous reaction involved by rigidizer.
As rigidizer, can use generally as curable composition (described curable composition contains the hardening compound with epoxy radicals or the compound with epoxy radicals) sclerosis with and the rigidizer that uses, include, for example polyamine, polybasic acid anhydride, polybasic carboxylic acid etc.
Polybasic acid anhydride include, for example the acid anhydrides and other polybasic acid anhydrides etc. of cyclohexane tricarboxylic acid.Cyclohexane front three acid anhydrides include, for example cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-acid anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-acid anhydrides etc.
Other polybasic acid anhydrides include, for example 4-methyl tetrahydrophthalic anhydride, methyl Na Dike acid (nadic acid) acid anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, compound represented by following formula (6), and usual used tetracarboxylic dianhydride in the synthesis of polyamic acid, also α-terpinene (α-terpinene) can be enumerated in addition, alloocimene (allo-ocimene) etc. has the ester ring type compound of conjugated double bond and Diels-Alder reaction (Diels-Alder reaction) product of maleic anhydride and those hydride etc.
[changing 16]
(in formula (6), p is the integer of 1 ~ 20)
Hardening catalyst include, for example diazo salt, Iodonium salt, sulfosalt, aluminium-alcohol salt, aluminium chelate compound etc.Commercially available product can enumerate AMERICURE (BF 4) (diazo salt that ACC manufactures), ULTRASET (BF 4, PF 6) (diazo salt that rising sun electrochemical industry manufactures), UVE series (GE Zao Iodonium salt), Photoinitiator 2074 ((C 6f 6) 4b) (Rhone-Poulenc (Rhone-Poulenc) Zao processed Iodonium salt), CYRACUREUVI-6974, CYRACURE UVI-6990 (being the sulfosalt of UCC manufacture above), UVI-508, UVI-509 (being the sulfosalt of GE manufacture above), OPTOMER SP-150, OPTOMER SP-170 (sulfosalt that rising sun electrochemical industry manufactures), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (being the sulfosalt that three new chemical industry manufacture above), IRUGACURE 261 (metallocene compound that vapour Ba-Jia Ji (Ciba-geigy) manufactures), aluminium chelate compound A (W) (manufacture of refining is ground in river) etc.Those hardening catalysts can be also can be potpourri of more than two kinds separately.
As the usage ratio of hardening catalyst, for [A] light regiospecific polysiloxane 100 mass parts, be preferably below 20 mass parts, be more preferably below 10 mass parts.When above-mentioned crystal aligning agent contains hardening catalyst, as it containing proportional, for total 100 mass parts of above-mentioned [A] light regiospecific polysiloxane and [B] other polymkeric substance at random to use, be preferably below 30 mass parts, be more preferably below 20 mass parts.
In those hardening catalysts, preferred sulfosalt, aluminium chelate compound, more preferably comprise 6 antimony fluorides, 6 and fluoridize the compound as negative ion kind such as phosphorus in sulfosalt.As those sulfosalts, include, for example the lithium antimonic salt of aminomethyl phenyl dimethyl disulfide, the lithium antimonic salt of ethylphenyl dimethyl disulfide, the hexafluorophosphate etc. of aminomethyl phenyl dimethyl disulfide.Those sulfosalts can be also can be potpourri of more than two kinds separately.The commercially available product of those sulfosalts can enumerate San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (above by three new chemical industry manufactures), UVI-6990, UVI-6992, UVI-6974 (being manufactured by Union Carbide Corporation (Union Carbide Corporation) above), Adeka Optomer SP-150, AdekaOptomer SP-170, Adeka Opton CP-66, Adeka Opton CP-77 (being manufactured by rising sun electrochemical industry above), IRGACURE 261 (vapour Ba-Jia Ji (Ciba-geigy) manufacture) etc.
Hardening accelerator include, for example:
Imidazolium compounds;
4 grades of phosphorus compounds;
4 grades of amines;
As 1,8-diazabicyclo [5.4.0] undecylene-7 or the such Diazabicycloalkene of its acylate;
As the organometallics zinc octoate, tin octoate, diacetone aluminium complex;
As the boron compound boron trifluoride, boric acid triphenyl ester; Metal halide compound as zinc chloride, butter of tin;
The high-melting-point decentralized potentiality hardening accelerators such as the amine add-on type promoter as the addition product of dicyanodiamide, amine and epoxy resin;
The Surface coating of 4 Ji phosphonium salts etc. has the microcapsule-type potentiality hardening accelerator of polymkeric substance;
Amine salt type potentiality hardening accelerator;
The hot cationic polymerization type potentiality hardening accelerator etc. of the thermal dissociation type as lewis acid, Bronsted hydrochlorate.
As the usage ratio of hardening accelerator, for [A] light regiospecific polysiloxane 100 mass parts, be preferably below 10 mass parts.
When above-mentioned crystal aligning agent contains rigidizer and hardening catalyst, as it containing proportional, for total 100 mass parts of above-mentioned [A] light regiospecific polysiloxane and [B] other polymkeric substance at random to use, be preferably below 10 mass parts, be more preferably below 1 mass parts.
[epoxy compound]
For the purpose of the adherence (adhesion) that can improve the substrate surface for formed liquid crystal orienting film further in above-mentioned crystal aligning agent containing epoxy compound.
Epoxy compound include, for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidyl ether, 1, 3, 5, 6-four glycidyl group-2, 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzene methanamine, N, N-diglycidyl-aminomethyl cyclohexane etc.
As epoxy compound containing proportional, for total 100 mass parts of [A] light regiospecific polysiloxane and [B] other polymkeric substance at random contained, be preferably below 40 mass parts, be more preferably 0.1 mass parts ~ 30 mass parts.In addition, when above-mentioned crystal aligning agent contains epoxy compound, can also efficiency to produce well for the purpose of cross-linking reaction and with base catalysts such as 1 benzyl 2 methyl imidazoles.
[functional silanes compound]
Above-mentioned functional silanes compound can make the adherence for the substrate surface of formed liquid crystal orienting film rise to object and use.
Functional silanes compound include, for example 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-tri-ethoxy silylpropyl three ethylene triamine, N-trimethoxysilylpropyl three ethylene triamine, 10-trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (oxygen base the ethylene)-3-TSL 8330 of N-, two (oxygen base the ethylene)-APTES of N-, 3-glycydoxy trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, tetracarboxylic dianhydride and the reactant etc. with amino silane compound, also can enumerate tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. Sho 63-291922 publication and the reactant etc. with amino silane compound in addition.
As functional silanes compound containing proportional, for total 100 mass parts of [A] light regiospecific polysiloxane and [B] other polymkeric substance at random contained, be preferably below 50 mass parts, be more preferably below 20 mass parts.
[surfactant]
Surfactant such as can enumerate non-ionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, silicone surfactant, polyalkylene oxide surfactant, fluorochemical surfactant etc.
As the usage ratio of surfactant, for overall 100 mass parts of above-mentioned crystal aligning agent, be preferably below 10 mass parts, be more preferably below 1 mass parts.
[light sensitizer]
The light sensitizing agent that can contain in above-mentioned crystal aligning agent be have select free carboxyl group, hydroxyl ,-SH ,-NCO ,-NHR (wherein, R to be hydrogen atom or carbon number be 1 ~ 6 alkyl) ,-CH=CH 2and SO 2at least a kind of base of the group that Cl is formed and the compound of light sensitizing structure.By making the potpourri of the above-mentioned polysiloxane and specific cinnamic acid derivative and the agent of light sensitizing with epoxy radicals react, thus [A] light regiospecific polysiloxane contained in above-mentioned crystal aligning agent is made to have the photosensitive structure (cinnamic acid structure) being derived from specific cinnamic acid derivative and the light sensitizing structure being derived from the agent of light sensitizing concurrently.This light sensitizing structure has following function: penetrate due to illumination and excite, thus this excitation energy being imparted to the photosensitive structure closely connect in polymkeric substance.This excited state can be singlet, also can be triplet, but in view of long-life or efficient energy trasfer, is preferably triplet.The light optimal wavelength that above-mentioned smooth sensitizing structure absorbs is ultraviolet or the luminous ray of the scope of 150nm ~ 600nm.The short light of the above-mentioned lower limit of wavelength ratio cannot operate by common optical system, therefore cannot be suitably used in light orientation method.On the other hand, the energy of the light of the above-mentioned upper limit for length of wavelength ratio is little, and is difficult to the excited state of bringing out above-mentioned smooth sensitizing structure.
This light sensitizing structure include, for example acetophenone structure, benzophenone structural, anthraquinone ring, biphenyl structural, carbazole structure, nitroaryl structure, fluorene structured, naphthalene structure, anthracene structure, acridine structure, indole structure etc., and those can be used alone or two or more are combinationally used.Those light sensitizing structures refer to comprise and remove 1 ~ 4 hydrogen atoms and the structure of the base of gained from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitro benzene, naphthalene, fluorenes, anthracene, acridine or indoles respectively.Herein, acetophenone structure, carbazole structure and indole structure preferably comprise the structure of in the hydrogen atom that has of phenyl ring of removing acetophenone, carbazole or indoles 1 ~ 4 and the base of gained separately.Preferably be selected from least a kind of the group be made up of acetophenone structure, benzophenone structural, anthraquinone ring, biphenyl structural, carbazole structure, nitroaryl structure and naphthalene structure in those light sensitizing structures, be particularly preferably at least a kind that is selected from the group be made up of acetophenone structure, benzophenone structural and nitroaryl structure.
The agent of light sensitizing preferably has the compound of carboxyl and light sensitizing structure, and preferred compound include, for example the compound etc. represented by following formula (H-1) ~ formula (H-10).
[changing 17]
(in formula, q is the integer of 1 ~ 6)
The light regiospecific polyorganosiloxane compounds used in the present invention also synthesizes by such as under type: except the polysiloxane having epoxy radicals except above-mentioned and specific cinnamic acid derivative, the agent of combined light sensitizing, preferably in the presence of a catalyst, preferably react in organic solvent.
In such cases, as the use amount of specific cinnamic acid derivative, relative to have epoxy radicals polysiloxane silicon atom 1 mole for, be preferably 0.001 mole ~ 10 moles, be more preferably 0.01 mole ~ 5 moles, be particularly preferably 0.05 mole ~ 2 moles.As the use amount of light sensitizing agent, relative to have epoxy radicals polysiloxane silicon atom 1 mole for, be preferably 0.0001 mole ~ 0.5 mole, be more preferably 0.0005 mole ~ 0.2 mole, be particularly preferably 0.001 mole ~ 0.1 mole.
The modulator approach > of < crystal aligning agent
Above-mentioned crystal aligning agent as described above such as containing [A] light regiospecific polysiloxane, and optionally containing suitable composition, other any compositions, can preferably be modulated to the solution shape constituent of each component dissolves in organic solvent.
As organic solvent, preferred dissolution [A] light regiospecific polysiloxane and other compositions at random used, and the organic solvent do not reacted with those compositions.As the organic solvent that preferably can use in above-mentioned crystal aligning agent, different from the kind of other polymkeric substance that contains arbitrarily.
Contain [A] light regiospecific polysiloxane and preferred organic solvent when [B] other polymkeric substance as above-mentioned crystal aligning agent, the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid can be enumerated.Those organic solvents can be used alone or two or more combinationally used.
The preferred solvent used in modulation as above-mentioned crystal aligning agent, according to whether using other polymkeric substance and kind thereof, can obtain the one kind or two or more combination of above-mentioned organic solvent.This kind of solvent is in following preferred solid concentration, and each composition contained in crystal aligning agent is not separated out, and the surface tension of crystal aligning agent becomes the solvent of the scope of 25mN/m ~ 40mN/m.
The solid concentration of above-mentioned crystal aligning agent, that is the ratio shared in the gross mass of crystal aligning agent of the quality of all the components beyond desolventizing in above-mentioned crystal aligning agent can be considered viscosity, volatility etc. and select, and is preferably 1 quality % ~ 10 quality %.If solid concentration is less than 1 quality %, then the thickness that there is the liquid crystal orienting film formed by above-mentioned crystal aligning agent becomes too small and cannot obtain the situation of good liquid crystal orienting film.On the other hand, if solid concentration is more than 10 quality %, then the thickness that there is film becomes excessive and cannot obtain the situation of good liquid crystal orienting film, and the viscosity that there is crystal aligning agent increases and causes the situation of coating characteristics deficiency.The method adopted when the scope of preferred solid concentration is because being coated on crystal aligning agent on substrate and different.Such as the scope of solid concentration when utilizing spin-coating method, be preferably 1.5 quality % ~ 4.5 quality %.When utilizing print process, preferably solid concentration being set to the scope of 3 quality % ~ 9 quality %, therefrom solution viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink-jet method, preferably solid concentration being set to the scope of 1 quality % ~ 5 quality %, therefrom solution viscosity being set to the scope of 3mPas ~ 15mPas.
As temperature during the above-mentioned crystal aligning agent of modulation, be preferably 0 DEG C ~ 200 DEG C, be more preferably 0 DEG C ~ 40 DEG C.
The manufacture method > of < light directive property control module
Smooth directive property control module of the present invention such as can manufacture as described below.The manufacture method of smooth directive property control module of the present invention is the manufacture method comprising the following light directive property control module formed: transparency carrier; Lens jacket, subtend is disposed in the face side of this transparency carrier, has column lens array overleaf; Liquid crystal orienting film, laminated on the back side of this lens jacket; Liquid crystal lens layer, is situated between every this liquid crystal orienting film laminated on the rear side of lens jacket;
The method comprises following steps:
(1) at the backsize radioactivity-sensitive crystal aligning agent of lens jacket, the step of film is formed;
(2) step of liquid crystal orienting film is formed by irradiating radioactive ray to above-mentioned film; And
(3) between this liquid crystal orienting film and transparency carrier, form the step of liquid crystal lens layer.
In (1) step and (2) step, form liquid crystal orienting film by radioactivity-sensitive crystal aligning agent.
The formation method > of < liquid crystal orienting film
In this light directive property control module, the method forming liquid crystal orienting film 15,16 include, for example on the face being formed with column lens array at the back side of lens jacket 13 and on the surface of transparency carrier 12, form the film of radioactivity-sensitive liquid crystal orienting film, next utilizes light orientation method and gives the method for this film LCD alignment ability.
Liquid crystal orienting film can utilize above-mentioned crystal aligning agent, such as, manufactured by following method.Such as by the coating process that spraying process, slot coated method, rolling method, spin-coating method, print process, ink-jet method, vapour deposition method etc. are suitable, above-mentioned crystal aligning agent is coated on substrate.Secondly, carry out preheating (preliminary drying) to this coated face, next carries out rear baking and forms film.As preliminary drying condition, such as, at 40 DEG C ~ 120 DEG C, carry out 0.1 minute ~ 5 minutes.As rear baking condition, be preferably 120 DEG C ~ 300 DEG C, be more preferably 130 DEG C ~ 220 DEG C, be preferably 5 minutes ~ 200 minutes, be more preferably 10 minutes ~ 100 minutes.The thickness of the film after rear baking is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.
When being coated with above-mentioned crystal aligning agent, in order to the adherence of each layer and film that make formation film is good further, also functional silanes compound, titanate esters etc. can be coated with in advance on substrate.
Secondly, by irradiating the radioactive ray of linear polarization or part polarisation to above-mentioned film or giving LCD alignment ability without the radioactive ray of polarisation.As radioactive ray, such as, can use the ultraviolet comprising the light that wavelength is 150nm ~ 800nm and luminous ray, but preferably comprise the ultraviolet that wavelength is the light of 300nm ~ 400nm.When used radioactive ray linear polarization or part polarisation, irradiate and can carry out from the direction perpendicular to real estate, also can carry out from vergence direction to give tilt angle, and also those can be combined and carry out.When irradiating the radioactive ray without polarisation, direction of illumination is necessary for vergence direction.In addition, " tilt angle " in this instructions refers to the angle that liquid crystal molecule tilts from the direction parallel with real estate.
As used light source, include, for example Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, Metal halogen lamp, argon resonance lamp, xenon lamp, excimer laser mercury-xenon lamp (Hg-Xe lamp) etc.The ultraviolet of above-mentioned preferred wavelength region may is by obtaining above-mentioned light source and mechanism also such as such as wave filter, diffraction grating etc. etc.
As the exposure of radioactive ray, be preferably 1J/m 2above and less than 10,000J/m 2, be more preferably 10J/m 2~ 3,000J/m 2.In addition, when giving LCD alignment ability when utilizing light orientation method to the film formed by crystal aligning agent known before, required 10,000J/m 2above radiation exposure amount, if but use above-mentioned crystal aligning agent, even if then light orientation method time radiation exposure amount be 3,000J/m 2below, be 1,000J/m furthermore 2below, also can give good LCD alignment ability, thus contribute to the manufacturing cost of cutting down liquid crystal display cells.
In (3) step, between liquid crystal orienting film 15 and transparency carrier 12, (between liquid crystal orienting film 15,16) forms liquid crystal lens layer.As the method for carrying out (3) step, include, for example: (A) forms space by engaging between liquid crystal orienting film 15 with transparency carrier 12, forming the method for liquid crystal lens layer 14 at this space filling liquid crystal material; (B) adjoin with liquid crystal orienting film 15 and after using liquid crystal material to form liquid crystal lens layer 14, arrange the method etc. of transparency carrier 12.
When said method (A), (3) step comprises:
(3-1) make this liquid crystal orienting film and transparency carrier subtend arrange, formed by the step in the space of those clampings; And
(3-2) filling liquid crystal material within this space, forms the step of liquid crystal lens layer.
In above-mentioned (3-1) step, engaging by making liquid crystal orienting film 15 arrange with transparency carrier 12 subtend, being formed at the space clamped by (between liquid crystal orienting film 15,16) between liquid crystal orienting film 15 and transparency carrier 12.
As the method that lens jacket 13 is engaged with transparency carrier 12 grade, be not particularly limited, the method etc. of the method using solid, the method using sticker, heat-sealing (heat seal) method, use Excimer UV light (UV) can be enumerated.Above-mentioned solid can use acrylic compounds solid etc. aptly.
In above-mentioned (3-2) step, filling liquid crystal material in the space between liquid crystal orienting film 15,16, forms liquid crystal lens layer 14.
As above-mentioned liquid crystal material, aqueous high molecule liquid crystal, polymerizable liquid crystal, non-polymerization liquid crystal etc. can be enumerated.When using polymerizable liquid crystal as liquid crystal material, as described later, polymerizable liquid crystal must be made to be polymerized.
As the method for filling liquid crystal material, include, for example: reduced pressure in the space between liquid crystal orienting film 15,16 and absorb the method for liquid crystal material; Space between liquid crystal orienting film 15,16 be impregnated in liquid crystal material, utilize capillarity etc. and the method for filling liquid crystal material; Liquid crystal material is injected into the method etc. in the space between liquid crystal orienting film 15,16.
When said method (B), (3) step comprises:
(3-1 '), at the rear side coating of liquid crystalline material of this liquid crystal orienting film, forms the step of liquid crystal lens layer; And
(3-2 ') arranges the step of transparency carrier in the rear side of this liquid crystal lens layer.
In above-mentioned (3-1 '), at the rear side coating of liquid crystalline material of liquid crystal orienting film 15, form liquid crystal lens layer 14.This liquid crystal material include, for example the example etc. of the liquid crystal material used in above-mentioned (3-1) step.
As the method for rear side liquid crystal material being coated liquid crystal orienting film 15, include, for example use transfer pipet and drip method, use the method for hairbrush, utilize the method for spraying, utilize the method etc. of roller coat.
In above-mentioned (3-2 '), arrange transparency carrier 12 in the rear side of above-mentioned formed liquid crystal lens layer 14, such as, make lens jacket 13 engage with transparency carrier 12.The method of this joint include, for example the example etc. of the method engaged with transparency carrier 12 by the lens jacket 13 in above-mentioned (3-1 ') step.
In above-mentioned (3-2) step and (3-1 ') step, when using polymeric materials as liquid crystal material, by heating and/or irradiate the radioactive ray etc. of non-polarized, polymerizable liquid crystal is polymerized.That is, in such cases,
Above-mentioned (3-2) step comprises:
(3-2-1) step of polymerizable liquid crystal is sucked in this space; And
(3-2-2) make this polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
And above-mentioned (3-1 ') step comprises:
(3-1 '-1) is in the step of the rear side coating polymerizable liquid crystal of this liquid crystal orienting film; And
(3-1 '-2) make this polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
As above-mentioned polymerizable liquid crystal, if the compound be polymerized by heating or irradiation radioactive ray, be then not particularly limited.Such as can be if " can UV sclerosis liquid crystal (UV curable liquid crystal) and its application " be (with reference to liquid crystal, 3rd volume, No. 1,1999,34th page ~ the 42nd page) in described nematic liquid crystal compound, also can be the potpourri with multiple compounds.And, also can comprise known photopolymerization initiator or thermal polymerization initiator.Those polymerizable liquid crystal compounds or its potpourri are dissolvable in water in suitable solvent and use.In addition, also can using by adding chiral agent etc. and the liquid crystal of the twisted nematic orientation reversed in a direction perpendicular to a substrate or cholesteric crystal (cholestricliquid crystal), also can use discotic mesogenic (discotic liquid crystal).
As temperature when heating polymerizable liquid crystal, select can obtain excellent fit to temperature.Such as when the polymerizable liquid crystal, the RMS03-013C that use Merck & Co., Inc. (Merck) to manufacture, select in the scope of 40 DEG C ~ 80 DEG C.
As radioactive ray when above-mentioned irradiation radioactive ray, include, for example the ultraviolet etc. of non-polarized.As the exposure of radioactive ray, be preferably 1,000J/m 2~ less than 100,000J/m 2, be more preferably 10,000J/m 2~ 50,000J/m 2.
The polymerization of above-mentioned polymerizable liquid crystal can be carried out under air, also can carry out under the inert gas environments such as nitrogen, can select the condition be applicable to according to the polymerism base of used polymerizable liquid crystal or initiating agent.
Described above and in the light directive property control module of gained, can the high orientation state of homogeneity and make polymerizable liquid crystal immobilization.Therefore, the light directive property control module of gained due to the orientation homogeneity of liquid crystal lens layer excellent, what therefore comprise this light directive property control module can improve the display precisions such as resolution by the display module that switches of 2D/3D.
< can 2D/3D switch display module >
The present invention also comprises aptly: comprise this light directive property control module can 2D/3D switch display module.
With reference to Fig. 5, following can being illustrated by the display module 71 that switches of 2D/3D of light directive property control module 1 to comprising the 1st example of the present invention.Can 2D/3D switch display module 71 comprise above-mentioned smooth directive property control module 1, display panel 31, liquid crystal switch cell 41.Display panel 31, except the common display device (display panel body) utilizing liquid crystal etc., also comprises incident light polarization element 61 and emergent light polarization element 62.
Display panel 31 (display panel body) is configured at the rear side (opposition side of spectator) of above-mentioned smooth directive property control module 1, is provided with incident light polarization element 61 in display panel body rear side.Display panel 31 uses usually in liquid crystal indicator, such as, comprise the liquid crystal panel that can carry out following control: make light from the backlight set by rear side, pixel by pixel through.
Liquid crystal switch cell 41 is configured at the face side (spectator side) of light directive property control module 1.And liquid crystal switch cell 41 comprises: the pair of switches transparency carrier 51,52 of subtend configuration, with the inner side abutment of those transparency carriers and a pair transparent electrode layer 53,54 that subtend configures, the switching Liquid Crystal layer 55 clamped by the inner side of those transparency conducting layers.
Above-mentioned liquid crystal switch cell 41 makes being rotated between 0 ° and 90 ° of rotatory polarization switch by the presence or absence of the voltage applying between a pair transparent electrode layer 53,54.
Incident light polarization element 61 is configured in the mode only making the polarisation that direction of vibration is x direction pass through.And, configure emergent light polarization element 62 in the mode only making the polarisation that direction of vibration is x direction pass through.In addition, emergent light polarization element 62 is configured at the spectator side of above-mentioned liquid crystal switch cell 41.
This can 2D/3D switch display module there is above-mentioned formation, therefore under alive situation not being executed to a pair transparent electrode layer 53,54 of liquid crystal switch cell 41, in liquid crystal switch cell 41, there is no the rotation of plane of polarisation, be therefore incident upon penetrating from emergent light polarization element 62 at the polarisation of x direction vibration of light directive property control module 1 from display panel 31.For this polarisation, light directive property control module 1 plays the light directive property of infiltration type, and therefore this display module can be used as 2D display use.And, under alive situation is executed to a pair transparent electrode layer 53,54 of liquid crystal switch cell 41, plane of polarisation half-twist can be made in liquid crystal switch cell 41.Therefore, penetrating from emergent light polarization element 62 at the polarisation of z direction vibration of light directive property control module 1 is incident upon from display panel 31.For this polarisation, light directive property control module 1 plays the light directive property of refractive, and therefore this display module can be used as 3D display use.As mentioned above, utilize can 2D/3D switch display module 71 can switch respectively display 2D and 3D display.
With reference to Fig. 6, following can being illustrated by the display module 72 that switches of 2D/3D of light directive property control module 2 to comprising the 2nd example of the present invention.Can 2D/3D switch display module 72 comprise above-mentioned light directive property control module 2, display panel 31.Display panel body is disposed in the rear side of light directive property control module 2, and the incident light polarization element 61 as a part for display panel is disposed in the rear side of display panel body, and emergent light polarization element 62 is disposed in the face side of light directive property control module 2.In addition, when prosign, the description thereof will be omitted.
With reference to Fig. 7, following can being illustrated by the display module 73 that switches of 2D/3D of light directive property control module 3 to comprising the 3rd example of the present invention.Can 2D/3D switch display module 73 comprise above-mentioned light directive property control module 3, display panel 31.Display panel 31 is disposed in the rear side of light directive property control module 3.Incident light polarization element 61 contained in display panel 31, emergent light polarization element 62 are disposed in rear side and the face side of display panel 31 (display panel body) respectively.
With reference to Fig. 8, following can being illustrated by the display module 74 that switches of 2D/3D of light directive property control module 4 to comprising the 4th example of the present invention.Can 2D/3D switch display module 74 comprise above-mentioned smooth directive property control module 4, display panel 31.Display panel 31 is disposed in the rear side of light directive property control module 4.Incident light polarization element 61 contained in display panel 31 is disposed in the rear side of display panel 31 (display panel body).
At above-mentioned 2nd, the 3rd and the 4th example can in the display module 72,73 and 74 that switches of 2D/3D, the presence or absence that also can be applied by the voltage of a pair transparency electrode interlayer in the same manner as the situation of the 1st example and switch respectively and show 2D and 3D and show.
According to those can 2D/3D switch display module 71 ~ 74, there is the light directive property control module 1,2,3 or 4 of the orientation homogeneity excellence of the liquid crystal of liquid crystal lens layer, with therefore can reducing the two dimension of display panel and the display quality of three-dimensional hardly for spectator provides good display.
In addition, smooth directive property control module of the present invention is not limited to above-mentioned example, such as, as lens jacket, according to the formation refractive index of material of lens jacket and the magnitude relationship of the extraordinary refractive index of liquid crystal lens layer, convex type lens layer can be used and replaces matrix lens jacket.And, of the present invention can 2D/3D switch display module be not limited to above-mentioned example, such as, as display panel, also can use plasma scope replace liquid crystal display.
Example
Below, by example, the present invention is added a concrete explanation further, but the present invention does not limit by those examples.In addition, optionally repeatedly can carry out the starting compound of synthesis scale (scale) shown in following synthesis example and the synthesis of polymkeric substance and guarantee starting compound used in the following examples and the necessary amounts of polymkeric substance.
< has the synthesis > of the polysiloxane of epoxy radicals
[synthesis example 1]
In the reaction vessel with stirring machine, thermometer, tap funnel and reflux condensing tube, load 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS) 100.0g, methyl isobutyl ketone 500g and triethylamine 10.0g and at room temperature mix.Secondly, utilize tap funnel with 30 minutes after dripping deionized water 100g, one side mixes under reflux, and one side carries out the reaction of 6 hours at 80 DEG C.After reaction terminates, take out organic layer, clean with the aqueous ammonium nitrate solution of 0.2 quality %, until the water after cleaning becomes neutral, then under reduced pressure by solvent and water distillation removing, the polysiloxane with epoxy radicals of the transparency liquid as thickness is obtained therefrom.
The polysiloxane having epoxy radicals for this carries out 1h-NMR analyzes, and result is the peak value obtained as theoretical strength near chemical shift (δ)=3.2ppm based on epoxy radicals, confirms the subsidiary reaction not producing epoxy radicals in the reaction.The Mw with the polysiloxane of epoxy radicals of gained is 2,200, and epoxide equivalent is 186g/mol.
The synthesis > of the specific cinnamic acid derivative of <
The synthetic reaction of specific cinnamic acid derivative is all carried out in inert environments.
[synthesis example 2]
In the there-necked flask of 300mL with condenser pipe, 4-flurophenyl boronic acid 6.5g, 4-bromo-cinnamic acid 10g, tetrakis triphenylphosphine palladium 2.7g, sodium carbonate 4g, tetrahydrofuran 80mL, pure water 39mL are mixed.Then reaction solution is carried out at 80 DEG C 8 hours add thermal agitation, with TLC confirm reaction terminate.After reaction solution is cooled to room temperature, be injected in 1N-aqueous hydrochloric acid solution 200mL, isolated by filtration separates out solid.Make the dissolution of solid of gained in ethyl acetate, sequentially carry out separatory cleaning with 1N-aqueous hydrochloric acid solution 100mL, pure water 100mL, saturated aqueous common salt 100mL.Secondly, with anhydrous magnesium sulfate, drying is carried out to organic layer, by solvent distillation removing.Vacuum drying is carried out to the solid of gained, obtains compound (specific cinnamic acid derivative (the K-1)) 9g represented by following formula (K-1).
[changing 18]
[synthesis example 3]
In the there-necked flask of 200mL with condenser pipe, 4-vinyl biphenyl 9.5g, 4-bromo-cinnamic acid 10g, acid chloride 0.099g, three (2-tolyl) phosphine 0.54g, triethylamine 18g, dimethyl acetamide 80mL are mixed.This solution is carried out at 120 DEG C 3 hours add thermal agitation, after confirming that reaction terminates with TLC, reaction solution is cooled to room temperature.After isolated by filtration sediment, filtrate is injected in 1N aqueous hydrochloric acid solution 500mL, reclaims sediment.With dimethyl acetamide, ethanol 1: 1 solution, recrystallization is carried out to those sediments, obtain compound (specific cinnamic acid derivative (the K-2)) 11g represented by following formula (K-2) therefrom.
[changing 19]
The synthesis > of < [A] light regiospecific polysiloxane
[synthesis example 4]
In the there-necked flask of 100mL, load specific cinnamic acid derivative (K-1) 3g and quarternary ammonium salt (San-Apro manufacture, the UCAT 18X) 0.10g of gained in the polysiloxane 9.3g with epoxy radicals, the methyl isobutyl ketone 26g of gained in synthesis example 1, synthesis example 2, at 80 DEG C, carry out the stirring of 12 hours.After reaction terminates, precipitate again with methyl alcohol, precipitate dissolves is obtained solution in ethyl acetate, after 3 washings are carried out to this solution, by solvent distillation removing, obtain [A] light regiospecific polysiloxane (S-1) 6.3g as white powder therefrom.The weight average molecular weight Mw of light regiospecific polyorganosiloxane compounds (S-1) is 3,500.
[synthesis example 5]
Use specific cinnamic acid derivative (K-2) 3g of gained in synthesis example 2, operate in the same manner as synthesis example 4 in addition, obtain the white powder 7.0g of [A] light regiospecific polysiloxane (S-2).The weight average molecular weight Mw of light regiospecific polyorganosiloxane compounds (S-2) is 4,900.
The synthesis > of < [B] other polymkeric substance
[synthesis example 6]
Two to 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 22.4g (0.1 mole) and cyclohexane (methyl amine) 14.23g (0.1 mole) is dissolved in NMP 329.3g, at 60 DEG C, carries out the reaction of 6 hours.Secondly, reaction mixture is injected in excessive methyl alcohol, reaction product is precipitated.With methyl alcohol, sediment is cleaned, under reduced pressure, carry out the drying of 15 hours at 40 DEG C, obtain polyamic acid (PA-2) 32g thus.
Get this (PA-2) 17.5g, add NMP 232.5g, pyridine 3.8g and acetic anhydride 4.9g wherein, at 120 DEG C, carry out the reaction of 4 hours and carry out imidizate.Secondly, reaction mixture is injected in excessive methyl alcohol, reaction product is precipitated.With methyl alcohol, sediment is cleaned, under reduced pressure carry out the drying of 15 hours, obtain polyimide (PI-1) 15g thus.
[synthesis example 7]
2 are loaded, two (2,4-methyl pentane nitrile) 5 mass parts of 2 '-azo and diethylene glycol methyl ethyl ether (DEGME) 200 mass parts in the flask with condenser pipe and stirring machine.Then load glycidyl methacrylate 40 mass parts, styrene 10 mass parts, methacrylic acid 30 mass parts and N-cyclohexylmaleimide 20 mass parts and after carrying out nitrogen displacement, slowly start to stir.Make solution temperature rise to 70 DEG C, this temperature kept 5 hours and obtain the polymer solution comprising the multipolymer (MA-1) of poly-(methyl) acrylate.The solid concentration of the polymer solution of gained is 33.1 quality %.The number average molecular weight of the polymkeric substance of gained is 7,000.
The synthesis > of < [C] compound containing ester structure
The compound (C-1-1) synthesized containing ester structure according to following flow process.
[changing 20]
[synthesis example 8]
Load trimesic acid 21g, n-butyl vinyl ether 60g and phosphoric acid 0.09g having recirculatory pipe, in the there-necked flask of 500mL that temperature takes into account nitrogen ingress pipe, react under within 30 hours at 50 DEG C, stirring.After reaction terminates, for the organic layer adding hexane 500mL and gained in the reactive mixture, carry out 2 separatory cleanings with 1M sodium hydrate aqueous solution in turn and carry out 3 separatory cleanings with water.Thereafter, in organic layer, distillation is except desolventizing, obtains compound (C-1-1) 50g containing ester structure as colourless transparent liquid therefrom.
The modulation > of < crystal aligning agent
[example 1]
Get containing the solution as the polyimide (PI-1) of gained in the synthesis example 6 of [B] other polymkeric substance, its amount is scaled wherein contained polyimide (PI-1) and is equivalent to 1,000 mass parts, add [A] light regiospecific polysiloxane (S-1) 100 mass parts of gained in synthesis example 4 wherein, further mixing NMP and diethylene glycol methyl ethyl ether (DEGME), make the solution that solvent composition is NMP: DEGME=90: 10 (mass ratioes), solid concentration is 4.0 quality %.Be that the filtrator of 1 μm filters this solution with aperture, the crystal aligning agent (A-1) of modulation example 1 therefrom.
[example 2]
Get the solution of the multipolymer (MA-1) containing poly-(methyl) acrylate as gained in the synthesis example 7 of [B] other polymkeric substance, the multipolymer (MA-1) that its amount is scaled wherein contained poly-(methyl) acrylate is equivalent to 1, 000 mass parts, add [A] light regiospecific polysiloxane (S-2) 100 mass parts of gained in synthesis example 5 wherein, further mixing NMP and ethylene glycol monobutyl ether (EGMB), making solvent composition is NMP: EGMB=50: 50 (mass ratioes), solid concentration is the solution of 4.0 quality %.Be that the filtrator of 1 μm filters this solution with aperture, the crystal aligning agent (A-2) of modulation example 2 therefrom.
[example 3]
In example 1, add (C-1-1) 50 mass parts of gained in the synthesis example 8 as [C] compound containing ester structure further, carry out and the crystal aligning agent (A-3) of modulation example 3 in the same manner as example 1 in addition.
The manufacture > of < light directive property control module
Use the crystal aligning agent modulated in above-mentioned example, utilize following method and manufacture light directive property control module.
[example 4]
Then there is at the one side of transparent glass substrate (a) the polymethylmethacrylate substrate of matrix lens shape, utilize spraying process and on its matrix face, be coated with the crystal aligning agent (A-1) modulated in above-mentioned example 1, the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, then to carried out in case nitrogen displacement baking oven in, at 150 DEG C, carry out the rear baking of 30 minutes and form the film that thickness is 0.1 μm.Secondly, use Hg-Xe lamp and Glan-Taylor prism (Glen-Taylor prism), from substrate normal, this film coated surface is vertically irradiated to the polarisation ultraviolet 300J/m of the open-wire line comprising 313nm 2, thus form liquid crystal orienting film.And, in the one side of transparent glass substrate (b), except using rolling method, utilize method similar to the above and form same liquid crystal orienting film.
Use aperture is, after the filtrator of 0.2 μm filters polymerizable liquid crystal (Merck & Co., Inc.'s manufacture, RMS03-013C), use transfer pipet to be dripped the recess being formed with liquid crystal orienting film being filled in above-mentioned matrix lens shape substrate.Secondly, after the hot plate of 60 DEG C carries out the baking of 1 minute, use Hg-Xe lamp and the non-polarized ultraviolet 30,000J/m comprising the open-wire line of 365nm is irradiated to polymerizable liquid crystal face of filling 2, form liquid crystal.
Be formed this liquid crystal matrix lens shape substrate liquid crystal side face on, overlapping above-mentioned liquid crystal orienting film forms the face of the liquid crystal orienting film side of transparent glass substrate, then both is engaged, and manufactures the light directive property control module of example 4.
[example 5]
In example 4, liquid-crystal switching element (I) is used (to be clamped with twisted nematic (Twisted Nematic, TN) type liquid crystal a pair ITO (tin indium oxide) transparent electrode layer two outside be bonded to a pair transparent glass substrate) replacement transparent glass substrate (a), then matrix lens shape substrate on the transparent glass substrate of a side wherein, carries out in addition and manufactures the light directive property control module of example 5 in the same manner as example 4.
[example 6]
In example 4, use liquid-crystal switching element (II) (being bonded to one piece of transparent glass substrate in the outside of a wherein side of a pair ito transparent electrode layer being clamped with twisted nematic liquid crystal) replacement transparent glass substrate (b), liquid crystal alignment layer is formed on the surface of this ito transparent electrode layer, and use (A-2) that modulate in above-mentioned example 2 to replace (A-1) and as crystal aligning agent, carry out in the same manner as example 4 in addition and manufacture the light directive property control module of example 6.
[example 7]
In example 4, pair of engaging is used to have the transparent glass substrate of ITO electrode layer to replace transparent glass substrate (a) and transparent glass substrate (b), form liquid crystal orienting films in all ITO electrode layer sides of two substrates, carry out in the same manner as example 4 in addition and manufacture the light directive property control module of example 7.
[example 8]
In example 7, (A-3) that modulate in above-mentioned example 3 is used to replace (A-1) and as crystal aligning agent, and use non-polymerization liquid crystal (Merck & Co., Inc. manufactures, MLC-7028) to replace polymerizable liquid crystal, carry out in the same manner as example 7 in addition and manufacture the light directive property control module of example 8.
[example 9]
The one side of transparent glass substrate (c) then has the polymethylmethacrylate substrate of matrix lens shape, utilize spraying process on its matrix face, be coated with the crystal aligning agent (A-3) modulated in above-mentioned example 3, the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, then to having carried out in the baking oven (oven) of nitrogen displacement in case, having carried out the rear baking of 30 minutes and form the film of thickness 0.1 μm at 150 DEG C.Secondly, use Hg-Xe lamp and Glan-Taylor prism, from substrate normal, this film coated surface is vertically irradiated to the polarisation ultraviolet 300J/m of the open-wire line comprising 313nm 2, thus form liquid crystal orienting film.And, in the one side of transparent glass substrate (d), except using rolling method, utilize method similar to the above and form same liquid crystal orienting film.
The face being formed with the recess side of liquid crystal orienting film of above-mentioned matrix lens shape substrate and above-mentioned liquid crystal orienting film are formed the face of the liquid crystal orienting film side of transparent glass substrate overlapping after, both are engaged.Secondly, in the cavity between aforesaid substrate, above-mentioned polymerizable liquid crystal is injected in decompression.Thereafter, use Hg-Xe lamp, form transparent glass substrate side from liquid crystal orienting film and irradiate the non-polarized ultraviolet 30,000J/m comprising the open-wire line of 365nm 2and form liquid crystal, manufacture the light directive property control module of example 9 therefrom.
[comparative example 1]
Then there is in a face of transparent glass substrate (a) the polymethylmethacrylate substrate of matrix lens shape, utilize spraying process coating of liquid crystalline orientation agent on this matrix face (JSR manufacture, AL3046), after the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, to carried out in case nitrogen displacement baking oven in, at 150 DEG C, carry out the rear baking of 30 minutes and form the film that thickness is 0.1 μm.Secondly, one side makes the roller rotation one being wound with nylon cloth in periphery rub in the face of this film coated surface, carries out friction treatment therefrom.In the one side of transparent glass substrate (b), use rolling method and after being coated with, carry out friction treatment, utilize method similar to the above in addition and form same liquid crystal alignment layer.Thereafter, utilize the method same with example 4 and manufacture the light directive property control module of comparative example 1.
[comparative example 2 ~ comparative example 6]
In example 5 ~ example 9, the liquid crystal alignment layer utilizing the method same with comparative example 1 to be formed to have carried out friction treatment and replace being formed on the substrate with matrix lens shape and on glass substrate or on ITO electrode layer liquid crystal orienting film, carries out in addition and manufactures the light directive property control module of comparative example 2 ~ comparative example 6 respectively in the same manner as comparative example 1.
[evaluation of LCD alignment homogeneity]
For light directive property control module manufactured in example 4 ~ example 9 and comparative example 1 ~ comparative example 6, with the following section of polarized light microscope observing, this section utilizes the center by its thickness direction, and liquid crystal lens layer carries out cutting off and grinding and obtain by the plane vertical with thickness direction.When thinking that the homogeneity of LCD alignment is high, LCD alignment homogeneity being evaluated as " A ", when thinking that the homogeneity of LCD alignment is low, LCD alignment homogeneity being evaluated as " B ".Evaluation result is shown in following table 1.
< can the manufacture > of display module that switches of 2D/3D
[example 10]
The light directive property control module of example 4, display panel, liquid crystal switch cell (I) are bonded with each other according to the arrangement shown in Fig. 5, therefrom manufacture example 10 can 2D/3D switch display module.
[example 11]
The light directive property control module of example 5, above-mentioned display panel are bonded with each other according to the arrangement shown in Fig. 6, therefrom manufacture example 11 can 2D/3D switch display module.
[example 12]
The light directive property control module of example 6, above-mentioned display panel are bonded with each other according to the arrangement shown in Fig. 7, therefrom manufacture example 12 can 2D/3D switch display module.
[example 13]
The light directive property control module of example 7, above-mentioned display panel are bonded with each other according to the arrangement shown in Fig. 8, therefrom manufacture example 13 can 2D/3D switch display module.
[example 14]
The light directive property control module of example 8, above-mentioned display panel are bonded with each other according to the arrangement shown in Fig. 8, therefrom manufacture example 14 can 2D/3D switch display module.
[example 15]
The light directive property control module of example 9, above-mentioned display panel are bonded with each other according to the arrangement shown in Fig. 5, therefrom manufacture example 15 can 2D/3D switch display module.
[comparative example 7 ~ comparative example 12]
In example 10 ~ example 15, use the light directive property control module of comparative example 1 ~ comparative example 6 to replace the light directive property control module of example 4 ~ example 9, carry out in the same manner as example 10 ~ example 15 respectively in addition and manufacture comparative example 7 ~ comparative example 12 can the display module that switches of 2D/3D.
[can 2D/3D switch the evaluation of display formedness of display module]
For manufactured in example 10 ~ example 15 and comparative example 7 ~ comparative example 12 can the display module that switches of 2D/3D, the formedness of the display in visual valuation two-dimensional model.Being evaluated as " A " when not finding to show discontinuous part, being evaluated as " B " when finding the discontinuous part of display.Evaluation result is shown in Table 1.
[table 1]
Result according to table 1: the orientation with the liquid crystal of the liquid crystal lens layer of the light directive property control module of liquid crystal orienting film is homogeneous, comprise this kind of light directive property control module can the display of display module that switches of 2D/3D good.Known on the other hand: not there is the liquid crystal orienting film formed by radioactivity-sensitive crystal aligning agent, the homogeneity with the LCD alignment of the light directive property control module of the liquid crystal orienting film implementing friction treatment is low, comprise this kind of light directive property control module can the display of display module that switches of 2D/3D bad.
Utilizability in industry
The homogeneity of LCD alignment can be provided good according to the present invention, though in the 2 d mode also can the light directive property control module that excellently shows of resolution and manufacture method thereof and comprise this light directive property control module can the display module that switches of 2D/3D.

Claims (15)

1. a light directive property control module, it comprises:
Transparency carrier;
Lens jacket, subtend is disposed in the face side of described transparency carrier, has column lens array overleaf;
Liquid crystal orienting film, laminated on the back side of described lens jacket, is formed by radioactivity-sensitive crystal aligning agent;
Liquid crystal lens layer, to be situated between every described liquid crystal orienting film laminated on the rear side of lens jacket, has in its surface contrary column lens array concavo-convex with described lens jacket,
The described liquid crystal orienting film of a pair is consistent with the alignment direction of described liquid crystal lens layer,
The combination of described liquid crystal lens layer and described lens jacket as have described liquid crystal lens layer shape lens pillar and play function,
Relative to the polarisation vibrated in the prescribed direction, described lens jacket is identical with the refractive index of described liquid crystal lens layer, the light directive property function of infiltration type is provided, relative to the polarisation with the vibration plane different from it, described lens jacket is different from the refractive index of described liquid crystal lens layer, provides the light directive property function of refractive.
2. smooth directive property control module according to claim 1, is characterized in that:
It comprises a pair transparent electrode layer of the side, two sides laminated on described liquid crystal lens layer.
3. smooth directive property control module according to claim 1, is characterized in that:
It comprises the liquid crystal layer be overlapped on described transparency carrier, is disposed in a pair transparent electrode layer of the side, two sides of described liquid crystal layer.
4. smooth directive property control module according to claim 1, is characterized in that:
Described radioactivity-sensitive crystal aligning agent contains the polysiloxane that [A] has light regiospecific base.
5. smooth directive property control module according to claim 4, is characterized in that:
Described smooth regiospecific base is the base with cinnamic acid structure.
6. smooth directive property control module according to claim 5, is characterized in that:
The described base with cinnamic acid structure is at least a kind of base being selected from the group be made up of the base of the compound be derived from represented by following formula (1) and the base of compound that is derived from represented by formula (2);
[changing 1]
In formula (1), R 1penylene, biphenylene, terphenyl support or cyclohexalene; Part or all of hydrogen atom of the support of described penylene, biphenylene, terphenyl and cyclohexalene also can be by the carbon number also can with fluorine atom 1 ~ 10 alkyl or carbon number be 1 ~ 10 alkoxy, fluorine atom or cyano group replace; R 2singly-bound, carbon number be 1 ~ 3 alkane two base, oxygen atom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-; A is the integer of 0 ~ 3; Wherein, when a is more than 2, multiple R 1and R 2can distinguish identical also can be different; R 3fluorine atom or cyano group; B is the integer of 0 ~ 4;
In formula (2), R 4penylene or cyclohexalene; The hydrogen atom of described penylene and cyclohexalene part or all also can by carbon number be 1 ~ 10 chain or the alkyl of ring-type, carbon number be 1 ~ 10 chain or the alkoxy of ring-type, fluorine atom or cyano group replace; R 5singly-bound, carbon number be 1 ~ 3 alkane two base, oxygen atom, sulphur atom or-NH-; C is the integer of 1 ~ 3; Wherein, when c is more than 2, multiple R 4and R 5can distinguish identical also can be different; R 6fluorine atom or cyano group; D is the integer of 0 ~ 4; R 7oxygen atom ,-COO-or-OCO-; R 8it is the thick cyclic group of the aromatic series base of divalent, the ester ring type base of divalent, the hetero ring type base of divalent or divalent; R 9singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*; * the bond position with carboxyl is represented; F and g is respectively the integer of 1 ~ 10; E is the integer of 0 ~ 3; Wherein, when e is more than 2, multiple R 7and R 8can distinguish identical also can be different.
7. smooth directive property control module according to claim 6, is characterized in that:
The polysiloxane that [A] has a light regiospecific base be have epoxy radicals polysiloxane, with the reaction product of at least a kind of compound being selected from the group that the compound represented by described formula (1) and the compound represented by described formula (2) are formed.
8. smooth directive property control module according to claim 4, is characterized in that:
Described radioactivity-sensitive crystal aligning agent has containing [C] the one kind or two or more structure being selected from the group be made up of the tert-butyl ester structure of the ketal ester structure of the acetal ester structure of carboxylic acid, carboxylic acid, the 1-alkyl-cycloalkyl ester structure of carboxylic acid and carboxylic acid further, has the compound of multiple described structure when described structure is a kind.
9. smooth directive property control module according to claim 4, is characterized in that:
Described radioactivity-sensitive crystal aligning agent is selected from least a kind of polymkeric substance of the group be made up of polyamic acid, polyimide, ethene unsaturated polymerizable compound thing and the polysiloxane of not having light regiospecific base further containing [B].
10. can 2D/3D switch a display module, it comprises:
Display panel;
Smooth directive property control module according to claim 2.
The manufacture method of 11. 1 kinds of light directive property control modules, it is the manufacture method comprising the following light directive property control module formed: transparency carrier; Lens jacket, subtend is disposed in the face side of described transparency carrier, has column lens array overleaf; Liquid crystal orienting film, laminated on the back side of described lens jacket; Liquid crystal lens layer, to be situated between every described liquid crystal orienting film laminated on the rear side of lens jacket, has in its surface contrary column lens array concavo-convex with described lens jacket,
The described liquid crystal orienting film of a pair is consistent with the alignment direction of described liquid crystal lens layer,
The combination of described liquid crystal lens layer and described lens jacket as have described liquid crystal lens layer shape lens pillar and play function,
Relative to the polarisation vibrated in the prescribed direction, described lens jacket is identical with the refractive index of described liquid crystal lens layer, the light directive property function of infiltration type is provided, relative to the polarisation with the vibration plane different from it, described lens jacket is different from the refractive index of described liquid crystal lens layer, provides the light directive property function of infiltration type;
Described method comprises following steps:
(1) at the backsize radioactivity-sensitive crystal aligning agent of lens jacket, the step of film is formed;
(2) step of liquid crystal orienting film is formed by irradiating radioactive ray to described film; And
(3) between described liquid crystal orienting film and transparency carrier, form the step of liquid crystal lens layer.
The manufacture method of 12. smooth directive property control modules according to claim 11, is characterized in that:
Described (3) step comprises following steps:
(3-1) make described liquid crystal orienting film and transparency carrier subtend arrange, form the step in the space clamped by described liquid crystal orienting film and described transparency carrier; And
(3-2) filling liquid crystal material in described space, forms the step of liquid crystal lens layer.
The manufacture method of 13. smooth directive property control modules according to claim 12, is characterized in that:
(3-2) step comprises following steps:
(3-2-1) step of polymerizable liquid crystal is sucked in described space; And
(3-2-2) make described polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
The manufacture method of 14. smooth directive property control modules according to claim 11, is characterized in that:
Described (3) step comprises following steps:
(3-1') at the rear side coating of liquid crystalline material of described liquid crystal orienting film, the step of liquid crystal lens layer is formed; And
(3-2') step of transparency carrier is arranged in the rear side of described liquid crystal lens layer.
The manufacture method of 15. smooth directive property control modules according to claim 14, is characterized in that:
Described (3-1') step comprises following steps:
(3-1'-1) in the step of the rear side coating polymerizable liquid crystal of described liquid crystal orienting film; And
(3-1'-2) make described polymerizable liquid crystal be polymerized and form the step of liquid crystal lens layer.
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