CN102311739B - The manufacture method of liquid crystal aligning agent, liquid crystal display device and liquid crystal display device - Google Patents

The manufacture method of liquid crystal aligning agent, liquid crystal display device and liquid crystal display device Download PDF

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CN102311739B
CN102311739B CN201110189182.8A CN201110189182A CN102311739B CN 102311739 B CN102311739 B CN 102311739B CN 201110189182 A CN201110189182 A CN 201110189182A CN 102311739 B CN102311739 B CN 102311739B
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liquid crystal
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organopolysiloxane
carbonatoms
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CN102311739A (en
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吉泽纯司
角谷宪一
清水成夫
谏山纯
片桐宽
秋池利之
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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

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Abstract

The present invention relates to the manufacture method of a kind of liquid crystal aligning agent, liquid crystal display device and liquid crystal display device.The invention provides a kind of liquid crystal aligning agent, can give vertical orientated property the excellent liquid crystal aligning agent also simultaneously with the liquid crystal orientation film of height ultraviolet resistance.The feature of above-mentioned liquid crystal aligning agent is, containing organopolysiloxane, this organopolysiloxane possesses the group containing polymerizability carbon-to-carbon double bond, the group that the described group containing polymerizability carbon-to-carbon double bond represents with following formula (A) for representative, in formula (A), R is hydrogen atom or methyl, X iand X iIbe respectively Isosorbide-5-Nitrae-phenylene, methylene radical, ethylene, propylene or trimethylene, a, b, c and d are respectively 0 or 1, wherein c be 0 and d is 1 time, X iIfor Isosorbide-5-Nitrae-phenylene, when b is 0, d is 0.

Description

The manufacture method of liquid crystal aligning agent, liquid crystal display device and liquid crystal display device
Technical field
The present invention relates to the manufacture method of liquid crystal aligning agent, liquid crystal display device and liquid crystal display device.In more detail, the liquid crystal aligning agent that vertical orientated property excellence can be provided also simultaneously to have the liquid crystal orientation film of the ultraviolet resistance of height is related to.
Background technology
As liquid crystal display device, except using with TN (twisted-nematic) type, STN (supertwist is to row) type etc. for except the liquid crystal display device with the horizontal alignment pattern of the heterotropic nematic liquid crystal of positive dielectric of representative, known VA (vertical orientated) the type liquid crystal display device also having use to have vertical (arranged vertically) alignment mode of the heterotropic nematic liquid crystal of negative dielectric.
This liquid crystal display device possesses the liquid crystal orientation film with making liquid crystal molecule orientation function in a certain direction.As the material forming this liquid crystal orientation film, there will be a known polyamic acid, polyimide, polymeric amide, polyester, organopolysiloxane etc., the liquid crystal orientation film be particularly made up of polyamic acid or polyimide, due to its thermotolerance, physical strength, excellent etc. with the affinity of liquid crystal molecule, be preferably used (patent documentation 1 ~ 3) all the time.
In addition, in patent documentation 4, disclose containing make 3 officials can and 4 officials can the mixture of hydrolysable silanes compound carry out under the existence of oxalic acid and alcohol should, and the liquid crystal aligning agent of the organopolysiloxane obtained, and the vertical orientated property of the liquid crystal orientation film formed by described liquid crystal aligning agent and excellent heat resistance.
Liquid crystal display device is in progress significantly in recent years, can carry out the high-quality display of fine display and animation responsiveness excellence at a high speed, except televisor, be widely used in vehicle-mounted type display unit, game machine, pocket animation player etc. as everyone knows.In addition, along with the display carrying out high briliancy, the situation of liquid crystal display device as above outdoor use by day adds, liquid crystal display device and possess its liquid crystal orientation film thus, will be exposed in the ultraviolet of not advised high strength under using state in the past for a long time.Therefore, as in the past known liquid crystal aligning mould material, do not have the ultraviolet resistance that can adapt to current using state, the ultraviolet resistance of liquid crystal orientation film need to improve.
So propose the liquid crystal display device of PSA (polymkeric substance continues to aim at) pattern in recent years.PSA pattern is by the substrate with pattern-like conducting film and the gap of a pair substrate that forms with the substrate of pattern-free conducting film, or the liquid-crystal composition of clamping containing polymerizable compound in the gap of a pair substrate be made up of with the substrate of pattern-like conducting film two panels, irradiation ultraviolet radiation under alive state is executed between conducting film, polymerizable compound is polymerized, reach thus and present tilt angle characteristic, control the technology of liquid crystal area differently-oriented directivity.If adopt this technology, just can by make conducting film have high speed that specific formation seek the expansion of angle of visibility and liquid crystal molecule response, the problem for inevitably transmitance and contrast gradient deficiency MVA profile plate can be eliminated.Wherein, for PSA pattern, in order to carry out the polymerization of above-mentioned polymerizable compound, need to carry out such as 10,000J/m 2above a large amount of uviolizings.Therefore the known unfavorable condition that may occur liquid crystal orientation film generation deterioration in uviolizing operation.
To this, in order to replace above-mentioned PSA pattern, recently also been proposed the technology (patent documentation 5) relating to new display format.The Kapton be intended that with containing the laurate structure possessing light functionality without polarisation uviolizing of this technology, the molecule utilizing the photoisomerization of above-mentioned laurate structure to cause rotates, the presenting property of tilt angle desired by imparting.Wherein, in order to give desired presenting property of tilt angle, need the ultraviolet irradiating a great deal of, activity duration when liquid crystal display device can be caused to manufacture is elongated, or due to strong ultraviolet, the electrical specification of the liquid crystal orientation film of formation, particularly voltage retention such as to suffer damage at the disadvantage.
As previously discussed, the use-pattern along with liquid crystal display device changes, the exploitation of new display format, smartens, extremely expect there is urgent countermeasure to the requirement that ultraviolet resistance in liquid crystal aligning mould material improves.
On the other hand, the manufacturing process of liquid crystal display device achieves very much progress in recent years.The large substrate conveying technology particularly adopted while substrate maximizes and liquid crystal drop add mode (One Drop Fill mode, in the art referred to as " ODF mode ") such technology obtain people and pay close attention to.ODF mode is wherein the liquid crystal of the multiple predetermined portion dropping necessary amounts on the substrate defining liquid crystal orientation film, another baseplate-laminating is neutralized again in vacuum, liquid crystal is extruded on whole of substrate after spreading simultaneously, the sealing agent being used in encapsulated liquid crystals carries out UV solidification, thus on whole of panel the method for filling liquid crystal, be the technology that significantly can shorten the operating time of liquid crystal filling work procedure compared with the vacuum injection mode of in the past carrying out.Wherein, if in the past known having in the VA type liquid crystal display device manufacture of liquid crystal orientation film adopt ODF mode, the unfavorable condition that the display that is called as " ODF is uneven " is uneven may be produced.It is believed that this phenomenon causes due to the vertical orientated restraint force deficiency of liquid crystal orientation film.
Therefore, just need to damage the various necessary performance required for liquid crystal aligning agent, the liquid crystal aligning agent of the liquid crystal orientation film not producing above-mentioned ODF inequality and the liquid crystal display device of display quality excellence can be provided.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 4-153622 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 56-91277 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-258605 publication
Patent documentation 4: Japanese Unexamined Patent Publication 9-281502 publication
Patent documentation 5: U.S. Patent Application Publication No. 2009/0325453 specification sheets
Patent documentation 6: Japanese Unexamined Patent Publication 6-222366 publication
Patent documentation 7: Japanese Unexamined Patent Publication 6-281937 publication
Patent documentation 8: Japanese Unexamined Patent Publication 5-107544 publication
Patent documentation 9: Japanese Unexamined Patent Publication 2010-97188 publication
Non-patent literature
Non-patent literature 1:T.J.Scheffer etc., J.Appl.Phys.48 roll up, 1783 pages (1977)
Non-patent literature 2:F.Nakano etc., JPN.J.Appl.Phys.19 roll up, 2013 pages (1980)
Summary of the invention
The present invention makes in view of the foregoing, its object is to provide to provide the excellent liquid crystal aligning agent also simultaneously with the liquid crystal orientation film of the ultraviolet resistance of height of particularly vertical orientated property.
According to the present invention, the problems referred to above of the present invention solve by the liquid crystal aligning agent of the organopolysiloxane containing the group possessed containing polymerizability carbon-to-carbon double bond.Wherein, this organopolysiloxane be side chain has more than one the ring structure being selected from cyclohexane ring and phenyl ring material or be not carry out by the organoalkoxysilane comprising compound that following formula (1) represents and the compound that following formula (2) represents the polysiloxane that polycondensation obtains.
R ASi(OR B) 3(1)
R CSi(OR D) 3(2)
(in formula (1), R athe alkyl of the carbonatoms 8 ~ 30 that can be replaced by fluorine atoms, R bit is the alkyl of carbonatoms 1 ~ 5;
In formula (2), R cby the alkyl that acryl or methacryloyl replace, R dthe alkyl of carbonatoms 1 ~ 5).
Liquid crystal aligning agent of the present invention can provide vertical orientated property excellent, has the liquid crystal orientation film of the ultraviolet resistance of height simultaneously.
Therefore, liquid crystal aligning agent of the present invention is except going for all the time known VA type liquid crystal display device, when being applicable to the liquid crystal display device needing the PSA pattern of strong ultraviolet radiation or upgrade display format in its manufacturing process, also can not there is liquid crystal orientation film deterioration in manufacturing process, desired display quality can be realized.
The liquid crystal orientation film formed by liquid crystal aligning agent of the present invention, there is the ultraviolet resistance of height, therefore possess the liquid crystal display device of described liquid crystal orientation film, even if under strong ultraviolet radiation condition, such as open air uses for a long time by day, and its display quality also can not deterioration.
In addition, according to the particularly preferred scheme of the present invention, if liquid crystal aligning agent of the present invention to be used for the manufacture of VA type liquid crystal display device, even if adopt in liquid crystal filling work procedure liquid crystal drop add mode (ODF mode) and also there is excellent vertical orientated restraint force, can form the liquid crystal orientation film that there will not be ODF inequality effectively, be therefore very favourable from the viewpoint of job efficiency.
Accompanying drawing explanation
Fig. 1 is the explanatory view of electrically conducting transparent film figure in the liquid crystal cell representing the nesa coating with patterning, by embodiment and comparative example manufacture.
Fig. 2 is the explanatory view of electrically conducting transparent film figure in the liquid crystal cell representing the nesa coating with patterning, by embodiment and comparative example manufacture.
Embodiment
As mentioned above, liquid crystal aligning agent of the present invention contains organopolysiloxane (hereinafter also referred to " organopolysiloxane (A) "), and it possesses the group containing polymerizability carbon-to-carbon double bond.
< organopolysiloxane (A) >
The organopolysiloxane (A) contained in liquid crystal aligning agent of the present invention possesses the group containing polymerizability carbon-to-carbon double bond.As organopolysiloxane (A), except containing except the group of polymerizability carbon-to-carbon double bond, can also possess: be selected from least one group in the group of group (hereinafter referred to as " liquid crystal aligning group ") and the epoxy group(ing) formation having and make liquid crystal molecular orientation function.
This organopolysiloxane (A) is preferably material side chain with more than one ring structures being selected from cyclohexane ring and phenyl ring.Proportional as containing of these ring structures in organopolysiloxane (A), be preferably more than 0.2mmol/g, be more preferably 0.3 ~ 6mmol/g.
As the group containing polymerizability carbon-to-carbon double bond that organopolysiloxane (A) has, such as following formula (A) can be enumerated
(in formula (A), R is hydrogen atom or methyl, X iand X iIbe respectively the alkylidene group of Isosorbide-5-Nitrae-phenylene, methylene radical or carbonatoms 2 ~ 8, Z is Sauerstoffatom ,-COO- *or-OCO- *(wherein, be with the connecting key of " * " at X iIside), a, b, c and d are respectively 0 or 1, wherein, c be 0 and d is 1 time, X iIfor Isosorbide-5-Nitrae-phenylene, when b is 0, d is 0) group etc. that represents.
As the object lesson of the group that above-mentioned formula (A) represents, such as vinyl can be enumerated, allyl group, to styryl, (methyl) acryloyloxymethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group, 4-((methyl) acryloxy) butyl, 5-((methyl) acryloxy) amyl group, 6-((methyl) acryloxy) hexyl, 7-((methyl) acryloxy) heptyl, 8-((methyl) acryloxy) octyl group, 9-((methyl) acryloxy) nonyl, 10-((methyl) acryloxy) decyl, 4-(2-((methyl) acryloxy) ethyl) phenyl, 2-((4-(methyl) acryloxy) phenyl) ethyl, 4-((methyl) acryloyloxymethyl) phenyl, 4-(methyl) acryloxy phenyl methyl, 4-(3-((methyl) acryloxy) propyl group) phenyl, 3-(4-(methyl) acryloxy phenyl) propyl group, 4-((methyl) acryloyl-oxy ylmethoxy) phenyl, 4-(2-((methyl) acryloxy) oxyethyl group) phenyl, 4-(3-((methyl) acryloxy) propoxy-) phenyl, (methyl) acryloyl-oxy ylmethoxymethyl, 2-((methyl) acryloyl-oxy ylmethoxy) ethyl, 2-(2-((methyl) acryloxy) oxyethyl group) ethyl, 2-(2-(2-((methyl) acryloxy) oxyethyl group) oxyethyl group) ethyl, 3-(3-((methyl) acryloxy) propoxy-) propyl group, acryloyloxymethyl, 6-{ [6-(acryloxy) caproyl] oxygen } hexyl etc.Can enumerate in these groups vinyl, allyl group, to styryl, (methyl) acryloyloxymethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group and 6-{ [6-(acryloxy) caproyl] oxygen hexyl is as preferred group.
Group base Z in above-mentioned formula (A) is preferably Sauerstoffatom.
For the organopolysiloxane contained in liquid crystal aligning agent of the present invention (A), group containing polymerizability carbon-to-carbon double bond is preferably the group that above-mentioned formula (A) represents, be more preferably more than one the group be selected from above-mentioned illustrative concrete group, it is relative to the 1mol Siliciumatom contained in organopolysiloxane (A), preferably in the ratio of 0.01 ~ 0.60mol, more preferably in the ratio of 0.02 ~ 0.50mol, the preferred ratio in 0.02 ~ 0.30mol contains further.
For organopolysiloxane (A), as the liquid crystal aligning base that can optionally have, such as following formula (D ') can be enumerated
(formula (D ') in, R ifor the fluoroalkyl of the alkyl of carbonatoms 1 ~ 40, carbonatoms 1 ~ 40, cyano group or fluorine atom or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton;
Z ifor singly-bound, *-O-, *-COO-or *-OCO-(wherein, is with the connecting key of " * " at R iside),
R iIfor cyclohexylidene or phenylene, wherein this cyclohexylidene or phenylene can be replaced by the alkyl of cyano group, fluorine atom, trifluoromethyl or carbonatoms 1 ~ 3,
N1 is 1 or 2, when wherein n1 is 2, and two R iIcan be the same or different, n2 is 0 or 1;
Z iIfor singly-bound, *-O-, *-COO-or *-OCO-(wherein, is with the connecting key of " * " at R iside.)，
N3 is the integer of 0 ~ 2, and n4 is 0 or 1) group etc. that represents.
As the R in above-mentioned formula (D ') ithe alkyl of carbonatoms 1 ~ 40, specifically, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl, dodecyl, hexadecyl, stearyl etc. can be enumerated;
As the fluoroalkyl of carbonatoms 1 ~ 40, specifically, such as trifluoromethylpropyl, trifluoromethylbutyl, trifluoromethyl hexyl, trifluoromethyl decyl, pentafluoroethyl group propyl group, pentafluoroethyl group butyl, pentafluoroethyl group octyl group, 3 can be enumerated, 3,4,4,5,5,5-seven fluorine amyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl group, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-17 fluorine decyl etc.;
As the above-mentioned alkyl with 17 ~ 51 of steroid skeleton, such as 3-cholestane base, 3-cholesteryl, 3-lanostane base, 3-cholestane base, 3-pregnane base, 3-androstane alkyl, 3-female steroid alkyl etc. can be enumerated respectively.
R in above-mentioned formula (D ') iIcyclohexylidene and phenylene be preferably Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylene respectively, as in above-mentioned formula (D ')-(R iI) n1the divalent group of-expression, when n1 is 1, can enumerates such as Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene etc. and, as preferred group, when n1 is 2, can enumerate such as 4,4 '-biphenylene, 4,4 '-Ya dicyclohexyl, following formula
(in above-mentioned formula, the connecting key of band " * " is at R iside) group that represents etc. is as preferred group.
N3 in above-mentioned formula (D ') is preferably 2.
N2 in preferred above-mentioned formula (D ') is 1, or n2 is 0 and R ifor having the alkyl of the carbonatoms 17 ~ 51 of steroid skeleton.
Because organopolysiloxane (A) has the group that such above-mentioned formula (D ') represents, the film formed by the liquid crystal aligning agent containing it has given play to good liquid crystal aligning ability, is preferred.
Ratio is there is as liquid crystal aligning base in organopolysiloxane (A), relative to the 1mol Siliciumatom contained in organopolysiloxane (A), be preferably the ratio of below 0.7mol, be more preferably the ratio of below 0.5mol, be particularly preferably the ratio of 0.1 ~ 0.5mol.
In addition, owing to having epoxy group(ing) in organopolysiloxane (A), the film formed by the liquid crystal aligning agent containing it has tough mechanical characteristics, and the various excellent performance such as thermotolerance, photostabilization is preferred.
Ratio is there is as organopolysiloxane (A) epoxy group, relative to the 1mol Siliciumatom contained in organopolysiloxane (A), be preferably the ratio of below 0.7mol, be more preferably the ratio of below 0.5mol, be particularly preferably the ratio of 0.1 ~ 0.5mol.
About organopolysiloxane (A), be preferably 500 ~ 1 by gel permeation chromatography and through the weight-average molecular weight of polystyrene conversion, 000,000, be more preferably 1,000 ~ 100,000, more preferably 1,000 ~ 50,000.
The manufacturing process > of < organopolysiloxane (A)
As this organopolysiloxane (A), as long as have feature as described above, can manufacture by any method, the polysiloxane that the organoalkoxysilane of the compound wherein preferably represented by the compound represented containing following formula (1) and following formula (2) carries out polycondensation and obtains.
R ASi(OR B) 3(1)
R CSi(OR D) 3(2)
(in formula (1), R athe alkyl of the carbonatoms 8 ~ 30 that can be replaced by fluorine atoms, R bto be carbonatoms be 1 ~ 5 alkyl;
In formula (2), R cby the alkyl that acryl or methacryloyl replace, R dto be carbonatoms be 1 ~ 5 alkyl).
As the organopolysiloxane in the present invention, if the polysiloxane using the organoalkoxysilane of the compound represented by the compound represented containing above-mentioned formula (1) and above-mentioned formula (2) to carry out polycondensation and obtain, in the manufacture of VA type liquid crystal display device, adopting the unfavorable condition that ODF inequality can occur during ODF mode, is therefore not preferred.Its reason is also unclear, but can infer that its cause is that the affinity of liquid crystal orientation film and the liquid crystal molecule formed by aforesaid method is not enough, the special component thus in liquid crystal compound at element memory uneven.
The operation that organopolysiloxane (A) can carry out polycondensation by the mixture such as had containing the group of polymerizability carbon-to-carbon double bond and the silane compound (hereinafter referred to as " silane compound (a1) ") of alkoxyl group or silane compound (a1) and other alkoxysilane compound containing trialkylsilyl group in molecular structure (hereinafter referred to as " silane compound (a2) ") manufactures (manufacturing process 1).
Herein, except silane compound (a1), also use silane compound (a2), and use the silane compound (hereinafter referred to as " silane compound (a2-1) ") with epoxy group(ing) and alkoxyl group as in silane compound (a2) at least partially, first manufacture and have containing the group of polymerizability carbon-to-carbon double bond and the organopolysiloxane of alkoxyl group (hereinafter referred to as " precursor organopolysiloxane (A i) "); then make its with containing being with the carboxylic acid of the compound of liquid crystal aligning group and carboxyl (hereinafter referred to as " carboxylic acid (1-1) ") to react, thus can obtain having the organopolysiloxane (A) (manufacturing process 2) containing both the group of polymerizability carbon-to-carbon double bond and liquid crystal aligning base.
In addition, make silane compound (a1) or silane compound (a1) and silane compound (a2) and mixture carry out polycondensation, first manufacture the organopolysiloxane of the group had containing polymerizability carbon-to-carbon double bond (hereinafter referred to as " precursor organopolysiloxane (A iI) "); then make it react with at least one nucleophilic compound (wherein this nucleophilic compound comprises the nucleophilic compound (hereinafter referred to as " nucleophilic compound (1) ") with liquid crystal aligning base) being selected from amine and mercaptan, thus also can obtain having the organopolysiloxane (A) (manufacturing process 3) containing both the group of polymerizability carbon-to-carbon double bond and liquid crystal aligning base.
Organopolysiloxane (A) can also carry out polycondensation by the mixture of silane compound (a2-1) or silane compound (a2-1) and the silane compound beyond it (a2) (hereinafter referred to as " silane compound (a2-2) "), and first manufacture has the organopolysiloxane of epoxy group(ing) (hereinafter referred to as " precursor organopolysiloxane (A iII) "), then make the operation of itself and carboxylic acid reaction carry out manufacturing (manufacturing process 4), this carboxylic acid contains the compound (hereinafter referred to as " carboxylic acid (1-2) ") of group and the carboxyl possessed containing polymerizability carbon-to-carbon double bond.Herein, as carboxylic acid, by also with carboxylic acid (1-2) and carboxylic acid (1-1), the organopolysiloxane (A) (manufacturing process 5) also except the group except containing polymerizability carbon-to-carbon double bond with liquid crystal aligning group can be obtained.
Or mode manufactures precursor organopolysiloxane (A as described above iII), then itself and the carboxylic acid reaction containing carboxylic acid (1-2) is made, and then react with nucleophilic compound (1), thus also can obtain the organopolysiloxane (A) (manufacturing process 6) also except the group except containing polymerizability carbon-to-carbon double bond with liquid crystal aligning group.
In either case, as silane compound (a2), also can be used together beyond silane compound (a2-1) belong to silane compound (a2) and without carbonatoms 8 ~ 30 alkyl and fluoridize the silane compound (hereinafter referred to as " silane compound (a2-2) ") of any group in alkyl.
If gathered above manufacture method, following table can be organized into such.
< silane compound >
Containing C=C: have the group of carbon-carbon double key and the silane compound (silane compound (a1)) of alkoxyl group
Containing epoxy group(ing): the silane compound (silane compound (a2-1)) with epoxy group(ing) and alkoxyl group
Other: alkoxysilane compound containing trialkylsilyl group in molecular structure other than the above (a2-2)
< carboxylic acid >
Carboxylic acid containing liquid crystal aligning group: the compound (carboxylic acid (1-1)) with liquid crystal aligning group and carboxyl
Carboxylic acid containing C=C: the compound (carboxylic acid (1-2)) with group containing polymerizability carbon-to-carbon double bond and carboxyl
< nucleophilic compound >
There is the nucleophilic compound of liquid crystal aligning group: the nucleophilic compound (nucleophilic compound (1)) with liquid crystal aligning group
Next coming in order are described above-mentioned manufacturing process 1 ~ 6.
[silane compound as raw material uses]
As above-mentioned silane compound (a1), such as following formula (a1) can be enumerated
(in formula (a1), R, X i, X iI, Z, a, b, c and d be identical with the implication in above-mentioned formula (A) respectively, R 1for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, e is the integer of 1 ~ 3) compound etc. that represents.
As the R in above-mentioned formula (a1) 1the alkyl of carbonatoms 1 ~ 12, be preferably the alkyl of carbonatoms 1 ~ 4, as its object lesson, such as, can enumerate methyl, ethyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl etc., preferable methyl, ethyl or n-propyl, particularly preferably ethyl.As the aryl of carbonatoms 6 ~ 12, such as, phenyl, p-methylphenyl etc. can be enumerated.
E in above-mentioned formula (a1) is preferably 1 or 2, is particularly preferably 1.
As the object lesson of silane compound (a1), such as vinyltrimethoxy silane can be enumerated, vinyltriethoxysilane, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyl three n-butoxy silane, vinyl three isobutoxy silane, vinyl three tert-butoxy silane, allyltrimethoxysilanis, allyltriethoxysilane, allyl group tripropoxy silane, allyl group three isopropoxy silane, allyl group three n-butoxy silane, allyl group three isobutoxy silane, allyl group three tert-butoxy silane, to styryl Trimethoxy silane, to styryl triethoxyl silane, to styryl tripropoxy silane, to styryl three isopropoxy silane, to styryl three n-butoxy silane, to styryl three isobutoxy silane, to styryl three tert-butoxy silane, (methyl) acryloyloxymethyl Trimethoxy silane, (methyl) acryloyloxymethyl triethoxyl silane, (methyl) acryloyloxymethyl three positive propoxy silane, (methyl) acryloyloxymethyl three isopropoxy silane, (methyl) acryloyloxymethyl three n-butoxy silane, (methyl) acryloyloxymethyl propyl group three sec-butoxy silane, 2-(methyl) acryloyl-oxyethyl Trimethoxy silane, 2-(methyl) acryloyl-oxyethyl triethoxyl silane, 2-(methyl) acryloyl-oxyethyl three positive propoxy silane, 2-(methyl) acryloyl-oxyethyl three isopropoxy silane, 2-(methyl) acryloyl-oxyethyl three n-butoxy silane, 2-(methyl) acryloyl-oxyethyl propyl group three sec-butoxy silane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, 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,
4-(methyl) acryloxy butyl trimethoxy silane, 4-(methyl) acryloxy butyl triethoxyl silane, 4-(methyl) acryloxy butyl three positive propoxy silane, 4-(methyl) acryloxy butyl three isopropoxy silane, 4-(methyl) acryloxy butyl three n-butoxy silane, 4-(methyl) acryloxy butyl propyl group three sec-butoxy silane, 5-(methyl) acryloxy amyltrimethoxysilane, 5-(methyl) acryloxy amyl triethoxysilane, 5-(methyl) acryloxy amyl group three positive propoxy silane, 5-(methyl) acryloxy amyl group three isopropoxy silane, 5-(methyl) acryloxy amyl group three n-butoxy silane, 5-(methyl) acryloxy amyl group propyl group three sec-butoxy silane, 6-(methyl) acryloxy hexyl Trimethoxy silane, 6-(methyl) acryloxy hexyl triethoxyl silane, 6-(methyl) acryloxy hexyl three positive propoxy silane, 6-(methyl) acryloxy hexyl three isopropoxy silane, 6-(methyl) acryloxy hexyl three n-butoxy silane, 6-(methyl) acryloxy hexyl propyl group three sec-butoxy silane, acryloyloxymethyl Trimethoxy silanes etc., preferably select more than one to use from these materials.Be more preferably be selected from vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, to styryl Trimethoxy silane, more than one materials to styryl triethoxyl silane, (methyl) acryloyloxymethyl Trimethoxy silane, 2-(methyl) acryloyl-oxyethyl Trimethoxy silane and 3-(methyl) acryloxypropyl Trimethoxy silane.
Above-mentioned silane compound (a2-1) is the silane compound with epoxy group(ing) and alkoxyl group, is preferably following formula (a2-1)
(R 5) h(R 6) iSi(OR 7) 4-h-i(a2-1)
(in formula (a2-1), R 5for having 1 valency group of epoxy group(ing),
R 6for the alkyl of carbonatoms 1 ~ 3,
R 7for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, h is the integer of 1 ~ 3, and i is the integer, wherein of 0 ~ 2, h+i≤3) compound that represents.
As the R in formula (a2-1) 5, such as 3-glycidoxypropyl group, 2-(3,4-epoxycyclohexyl) ethyl etc. can be enumerated.As R 6, preferable methyl.About R 7, and about the R in above-mentioned formula (a1) 1above-mentioned situation identical.Preferably h is 1, i is respectively 0 or 1.
As the object lesson of silane compound (a2-1), such as 3-glycidoxypropyltrime,hoxysilane can be enumerated, 3-glycidoxypropyl group triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl group dimethyl methoxy silane, 3-glycidoxypropyl group dimethylethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl triethoxysilane etc., can more than one be selected to use from these materials.
Above-mentioned silane compound (a2-2) is the silane compound (a2) beyond silane compound (a2-1), is do not have the alkyl of carbonatoms 8 ~ 30 and fluoridize the silane compound of any group in alkyl.As this silane compound (a2-2), such as following formula (a2-2) can be enumerated
(R 8) jSi(OR 9) 4-j(a2-2)
(in formula (a2-2), R 8for the alkyl or phenyl of carbonatoms 1 ~ 7, R 9for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, j is the integer of 0 ~ 3) compound that represents.R in above-mentioned formula (a2-2) 9with about the R in above-mentioned formula (a1) 1above-mentioned situation identical.
As the object lesson of silane compound (a2-2), j be 0 compound can enumerate such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four secondary npropoxysilane, four n-butoxy silane, four sec-butoxy silane etc.;
J be 1 compound can enumerate such as methyltrimethoxy silane, Union carbide A-162, methyl three positive propoxy silane, methyl three isopropoxy silane, methyl three n-butoxy silane, methyl three sec-butoxy silane, methyl three n-pentyloxy silane, methyl three sec-butoxy silane, methyl triple phenoxyl silane, methyl three pairs of methylenedioxy phenoxy base silanes, 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 n-pentyloxy silane, ethyl three sec-butoxy silane, ethyl triple phenoxyl silane, ethyl three pairs of methylenedioxy phenoxy base silanes, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, n-propyl three positive propoxy silane, n-propyl three isopropoxy silane, n-propyl three n-butoxy silane, n-propyl three sec-butoxy silane, n-propyl three n-pentyloxy silane, n-propyl three sec-butoxy silane, n-propyl triple phenoxyl silane, n-propyl three pairs of methylenedioxy phenoxy base silanes, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, n-butyltrimethoxysilane, ne-butyltriethoxysilaneand, normal-butyl three positive propoxy silane, normal-butyl three isopropoxy silane, normal-butyl three n-butoxy silane, normal-butyl three sec-butoxy silane, normal-butyl three n-pentyloxy silane, normal-butyl three sec-butoxy silane, normal-butyl triple phenoxyl silane, normal-butyl three pairs of methylenedioxy phenoxy base silanes, n-pentyl Trimethoxy silane, n-pentyl triethoxyl silane, n-pentyl three positive propoxy silane, n-pentyl three isopropoxy silane, n-pentyl three n-butoxy silane, n-pentyl three sec-butoxy silane, n-pentyl three n-pentyloxy silane, n-pentyl three sec-butoxy silane, n-pentyl triple phenoxyl silane, n-pentyl three pairs of methylenedioxy phenoxy base silanes, hexyl Trimethoxy silane, hexyl triethoxyl silane, heptyl Trimethoxy silane, heptyl triethoxyl silane etc.,
J be 2 compound can enumerate such as dimethyldimethoxysil,ne, diethyldimethoxysilane, diη-propyl dimethoxysilane, diisopropyl dimethoxy silane, dimethyldiethoxysilane, diethyldiethoxysilane, diη-propyl diethoxy silane, diisopropyldiethoxysilane, dimethyl-diisopropoxy silane, diethyl-diisopropoxy silane, diη-propyl-diisopropoxy silane, di-isopropyl-diisopropoxy silane, dimethyl-two sec-butoxy silane, diethyl-two sec-butoxy silane, diη-propyl-two sec-butoxy silane, di-isopropyl-two sec-butoxy silane etc.,
J be 3 compound can enumerate such as trimethylmethoxysilane, triethyl methoxy silane, three n-propyl methoxy silane, triisopropyl methoxy silane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane, three n-propyl Ethoxysilanes, triisopropyl Ethoxysilane, trimethyl-n-propoxy silane, triethyl-positive propoxy silane, three n-propyls-positive propoxy silane, triisopropyl-positive propoxy silane, trimethylammonium-isopropoxy silane, triethyl-isopropoxy silane, three n-propyls-isopropoxy silane, triisopropyl-isopropoxy silane, trimethylammonium-sec-butoxy silane, triethyl-sec-butoxy silane, three n-propyls-sec-butoxy silane, triisopropyl-sec-butoxy silane etc., more than one uses in these materials can be selected.
As the R in formula (a2-2) 8, the alkyl or phenyl of preferred carbonatoms 1 ~ 3.As silane compound (a2-2), more preferably j in above-mentioned formula (a2-2) is used to be the compound of 0 or 1, more preferably more than one materials selected the group formed from ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, tetramethoxy-silicane and tetraethoxysilane are used to use, particularly preferably use j in above-mentioned formula (a2-2) to be the compound of 0, wherein preferably from tetramethoxy-silicane and tetraethoxysilane, select more than one to use.
When manufacturing by manufacturing process 1 organopolysiloxane (A) that contain in liquid crystal aligning agent of the present invention, as the silane compound that its raw material uses, relative to whole silane compound preferably containing silane compound as above (a1) more than 1mol%, more preferably containing 1 ~ 60mol%, further preferably containing 2 ~ 50mol%, particularly preferably containing 2 ~ 30mol%.In manufacturing process 1, preferably except above-mentioned silane compound, also use silane compound (a2-2).For its usage ratio, be preferably below 60mol% relative to whole silane compound, be more preferably 0 ~ 40mol%, be particularly preferably 0 ~ 20mol%.
When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 2, as the silane compound that its raw material uses, relative to whole silane compound preferably containing silane compound as above (a1) more than 1mol%, more preferably containing 1 ~ 60mol%, further preferably containing 2 ~ 50mol%, particularly preferably containing 2 ~ 30mol%.When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 2, except above-mentioned silane compound (a1), use silane compound (a2-1).For the usage ratio of this silane compound (a2-1), be preferably more than 10mol% relative to whole silane compound, be more preferably 20 ~ 90mol%, be particularly preferably 30 ~ 60mol%.
When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 3, precursor organopolysiloxane (A iI) a part of carbon-to-carbon double bond of having consumes by reacting with nucleophilic compound (1), the usage ratio of the silane compound therefore used as raw material should consider that this consumption part sets.From this side considerations, for in manufacturing process 3 as raw material use silane compound, preferably contain more than 10mol% silane compound (a1) as above, more preferably containing 10 ~ 80mol%, particularly preferably containing 20 ~ 70mol% relative to whole silane compound.
When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 4, for the silane compound used as its raw material, preferably contain more than 20mol% silane compound (a2-1) as above, more preferably containing 40mol% relative to whole silane compound.
When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 5, precursor organopolysiloxane (A i) epoxy group(ing) that has is provided to the reaction carried out with carboxylic acid (1-1) and reaction two aspect of carrying out with carboxylic acid (1-2).Therefore, should consider that this consumption part sets as the usage ratio of the silane compound of raw material use in manufacturing process 5.From this side considerations, in manufacturing process 5 as the silane compound that raw material uses, preferably contain more than 20mol% silane compound (a2-1) as above, more preferably containing 40mol% relative to whole silane compound.
When carrying out the manufacture of organopolysiloxane (A) by manufacturing process 6, for the silane compound used as its raw material, preferably contain more than 20mol% silane compound (a2-1) as above, more preferably containing 40mol% relative to whole silane compound.
In manufacturing process 2 ~ 6, preferably do not use silane compound (a2-2).
[polycondensation of silane compound]
Organopolysiloxane (A) in above-mentioned manufacturing process 1, the precursor organopolysiloxane (A in manufacturing process 2 i), the precursor organopolysiloxane (A in manufacturing process 3 iI) or manufacturing process 4 ~ 6 in precursor organopolysiloxane (A iII) polycondensation can be carried out manufacture by making silane compound as above (or its mixture).The polycondensation of silane compound can by making silane compound as above, and the method (condensation methods 1) of such as carrying out reacting under the existence of dicarboxylic acid and alcohol, the method (condensation methods 2) etc. of hydrolytic condensation manufacture respectively.
Below, successively condensation methods 1 and condensation methods 2 are described.
[condensation methods 1]
Condensation methods 1 makes silane compound as above under the existence of dicarboxylic acid and alcohol, carry out the method for reacting.
As dicarboxylic acid used herein, can be oxalic acid, compound, benzene dicarboxylic acid etc. that the alkylidene group of propanedioic acid, carbonatoms 2 ~ 4 is formed in conjunction with two carboxyls.Specifically, such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid etc. can be enumerated, preferably from these materials, select more than one and use.Particularly preferably oxalic acid.
For the usage ratio of dicarboxylic acid, be preferably the total 1mol of the alkoxyl group had relative to the silane compound used as raw material, carboxyl amount reaches the amount of 0.2 ~ 2.0mol, is more preferably the amount that carboxyl amount reaches 0.5 ~ 1.5mol.
As above-mentioned alcohol, preferably primary alconol can be used.As its object lesson, such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, tertiary amyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol-3, n-Octanol, 2-Ethylhexyl Alcohol, nonanol-, 2 can be enumerated, 6-dimethyl enanthol-4, nonylcarbinol, phenol, hexalin, methyl-cyclohexanol, 3,3,5-cyclonol, benzyl alcohol, Pyranton etc., preferably select more than one and use from these materials.As alcohol used herein, be preferably the aliphatic primary alcohol of carbonatoms 1 ~ 4, more preferably from methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, sec-butyl alcohol and the trimethyl carbinol, select more than one materials use, from methyl alcohol and ethanol, particularly preferably select more than one materials to use.
For the usage ratio of alcohol in condensation methods 1, the ratio preferably making silane compound and dicarboxylic acid account for reaction soln total amount reaches the ratio of 3 ~ 80 % by weight, is more preferably the ratio reaching 25 ~ 70 % by weight.
Temperature of reaction is preferably 1 ~ 100 DEG C, is more preferably 15 ~ 80 DEG C.Reaction times is preferably 0.5 ~ 24 hour, is more preferably 1 ~ 8 hour.
In condensation methods 1, preferably do not use other solvent beyond alcohol as above.
For condensation methods 1 as above, can infer that the intermediate that generated by the reaction of silane compound and dicarboxylic acid and alcohol are had an effect, thus generate the organopolysiloxane of the condenses as silane compound (a1), or generate the organopolysiloxane of the cocondensation compound as silane compound (a1) and silane compound (a2).
[condensation methods 2]
Condensation methods 2 is that silane compound as above is hydrolyzed the method for condensation.
This hydrolysis-condensation reaction can, by making silane compound and water under the existence of preferred catalyst, preferably carry out reacting implementing in suitable organic solvent.
For the ratio of water used herein, as the amount of the total 1mol of the alkoxyl group had relative to the silane compound used as raw material, be preferably 0.5 ~ 2.5mol.
As above-mentioned catalyzer, acid, alkali, metallic compound etc. can be enumerated.As the object lesson of this catalyzer, such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, toxilic acid etc. can be enumerated as acid.
As alkali, the arbitrary substance in mineral alkali and organic bases can be used, such as ammoniacal liquor, sodium hydroxide, potassium hydroxide, potassium methylate, sodium ethylate, potassium ethylate etc. can be enumerated as mineral alkali; As organic bases, the trimethylamine of such as triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine and so on can be enumerated; Tetramethylammonium hydroxide etc.
As metallic compound, such as titanium compound, zirconium compounds etc. can be enumerated.
For the usage ratio of catalyzer, be preferably below 10 weight parts relative to total 100 weight part of the silane compound used as raw material, be more preferably 0.001 ~ 10 weight part, more preferably 0.001 ~ 1 weight part.
As above-mentioned organic solvent, such as alcohol, ketone, acid amides, ester and other aprotic compound can be enumerated.As above-mentioned alcohol, the alcohol with a hydroxyl, the alcohol with multiple hydroxyl can be used and have multiple hydroxyl alcohol part ester in arbitrary substance.As above-mentioned ketone, can preferably use single ketones and beta-diketon.
As the object lesson of this organic solvent, the alcohol with a hydroxyl can enumerate such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, tertiary amyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, enanthol-3, n-Octanol, 2-Ethylhexyl Alcohol, nonanol-, 2,6-dimethyl enanthol-4, nonylcarbinol, phenol, hexalin, methyl-cyclohexanol, 3,3,5-cyclonol, benzyl alcohol, Pyranton etc.;
The alcohol with multiple hydroxyl can enumerate such as ethylene glycol, 1,2-PD, 1,3 butylene glycol, pentanediol-2,4,2 hexylene glycol-2,4, hexylene glycol-2,5, heptanediol-2,4,2-Rutgers 612-1,3, Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol etc.;
The part ester with the alcohol of multiple hydroxyl can enumerate such as ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list propyl ether, ethylene glycol monobutyl ether, ethylene glycol mono hexyl ether, ethylene glycol list phenyl ether, ethylene glycol list-2-ethyl-butyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol monopropyl ether, glycol monobutyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether etc.,
Single ketones can enumerate such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-normal-butyl ketone, metacetone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-normal-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2,4-diacetylmethanes, acetonyl-acetone, methyl phenyl ketone, fenchone etc.;
Above-mentioned beta-diketon can enumerate such as methyl ethyl diketone, 2,4-hexanediones, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 3,5-acetyl caproyls, 2,4-the ninth of the ten Heavenly Stems diketone, 3,5-diketone in the ninth of the ten Heavenly Stems, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl--3,5-heptadione, 1,1,1,5,5,5-hexafluoro-2,4-heptadione etc.;
Acid amides can enumerate such as methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetylmorpholine, N-Acetylpiperidin, N-acetyl-pyrrolidine etc.;
Ester can enumerate such as diethyl carbonate, ethylene carbonate, Texacar PC, diethyl carbonate, ritalin, vinyl acetic monomer, gamma-butyrolactone, γ-valerolactone, n-propyl acetate, Iso Butyl Acetate, n-butyl acetate, isobutyl acetate, 2-butyl acetate, n-Amyl acetate, the secondary pentyl ester of acetic acid, acetic acid 3-methoxybutyl, acetic acid methyl pentyl ester, acetic acid 2-ethyl butyl ester, acetic acid 2-ethylhexyl, Benzyl Acetate, cyclohexyl acetate, methyl cyclohexanol acetate, acetic acid ester in the positive ninth of the ten Heavenly Stems, methyl acetoacetate, methyl aceto acetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid TC, acetic acid Diethylene Glycol list-n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid propylene glycol monoethyl, acetic acid propylene glycol monopropyl ether, acetic acid glycol monobutyl ether, acetic acid DPGME, acetic acid dihydroxypropane single-ethyl ether, two ethylene glycol acetates, acetic acid methoxyl group triglycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, oxalic acid diethyl ester, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, diethyl malonate, dimethyl phthalate, phthalic acid diethyl etc.,
Other non-protonic solvent can enumerate such as acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ', N '-tetraethyl-sulphonamide, hexamethyl phosphoric triamide, N-methylmorpholine ketone, N-methylpyrrole, N-N-ethyl pyrrole N-, N-methyl-Δ 3-pyrroline, N-methyl piperidine, N-ethylpiperidine, N, N-lupetazin, N-Methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, METHYLPYRROLIDONE, 1, 3-dimethyl-2-imidazolidone, 1, 3-dimethyl tetrahydro-2 (1H)-pyrimidone etc., more than one can selecting in these materials use.
As the usage ratio of organic solvent, the ratio preferably making the total weight of the composition in reaction soln beyond organic solvent account for reaction soln total amount reaches the ratio of 1 ~ 90 % by weight, more preferably reaches the ratio of 10 ~ 70 % by weight.
In condensation methods 2, for the water that adds when manufacturing organopolysiloxane, can be dissolved in as the silane compound of raw material or by silane compound in the solution that organic solvent formed and add intermittently or continuously.
Catalyzer can add in the silane compound as raw material or by solution formed in organic solvent for silane compound dissolving in advance, or also can be dissolved or dispersed in added water.
Temperature of reaction is preferably 1 ~ 100 DEG C, is more preferably 15 ~ 80 DEG C.Reaction times is preferably 0.5 ~ 24 hour, is more preferably 1 ~ 8 hour.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 1, organopolysiloxane (A) can be obtained in a manner described.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 2, by making the precursor organopolysiloxane (A obtained in a manner described i) react with the carboxylic acid containing carboxylic acid (1-1) again, organopolysiloxane (A) can be obtained.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 3, by making the precursor organopolysiloxane (A obtained in a manner described i) react with nucleophilic compound (1) again, organopolysiloxane (A) can be obtained.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 4, by making the precursor organopolysiloxane (A obtained in a manner described iII) react with the carboxylic acid containing carboxylic acid (1-2) again, organopolysiloxane (A) can be obtained.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 5, by making the precursor organopolysiloxane (A obtained in a manner described iII) react again with containing carboxylic acid (1-1) and carboxylic acid (1-2) both carboxylic acids, organopolysiloxane (A) can be obtained.
As the manufacture method of organopolysiloxane (A), when adopting manufacturing process 6, by making the precursor organopolysiloxane (A obtained in a manner described iII) react with the carboxylic acid containing carboxylic acid (1-2) again, first obtain precursor organopolysiloxane (A iV) after, then react with nucleophilic compound (1), organopolysiloxane (A) can be obtained.
Further, as precursor organopolysiloxane (A iI), except the product manufactured by aforesaid method, also can use the commercially available prod such as such as AC-SQ TA-100 (East Asia synthesis (strain) system).
[carboxylic acid]
The carboxylic acid (1-1) used in above-mentioned manufacturing process 2 and 5 is the compound with liquid crystal aligning group and carboxyl.About the liquid crystal aligning group that carboxylic acid (1-1) has, situation when carrying out above-mentioned explanation with the liquid crystal aligning group that can have arbitrarily for organopolysiloxane (A) is identical.
As the carboxylic acid (1-1) used in manufacturing process 3, preferably there is the carboxylic acid of the group that above-mentioned formula (D ') represents, more preferably following formula (b2-1)
D’-COOH (b2-1)
The compound that (in formula (b2-1), the group that D ' represents for above-mentioned formula (D ')) represents.As this carboxylic acid (1-1), such as longer chain fatty acid can be enumerated, there is the benzoic acid derivative of chain alkyl, there is the benzoic acid derivative of long-chain alkoxy base, there is the benzoic acid derivative of steroid skeleton, there is other carboxylic acid of steroid skeleton, there is the benzoic acid derivative of polynuclear plane, there is other carboxylic acid of polynuclear plane, there is the carboxylic acid etc. of fluoroalkyl.As their object lesson,
As longer chain fatty acid, such as caproic acid, n-caprylic acid, n-capric acid, dodecanoic acid, Palmiticacid, stearic acid etc. can be enumerated;
As the benzoic acid derivative with chain alkyl, such as 4-positive hexyl phenenyl formic acid, 4-n-octyl formic acid, the positive decyl phenylformic acid of 4-, 4-n-dodecane yl benzoic acid, 4-n-hexadecane yl benzoic acid, 4-stearyl phenylformic acid etc. can be enumerated;
As the benzoic acid derivative with long-chain alkoxy base, the positive hexyloxybenzoate of such as 4-, 4-n-octyloxy phenylformic acid, 4-n-decyloxy phenylformic acid, 4-n-dodecane aminobenzoic acid, 4-n-hexadecane aminobenzoic acid, the stearic aminobenzoic acid of 4-etc. can be enumerated;
As the benzoic acid derivative with steroid skeleton, such as cholestane aminobenzoic acid, cholestene aminobenzoic acid, lanostane aminobenzoic acid, cholestane oxygen carbonyl benzoic acid, cholestene oxygen carbonyl benzoic acid, lanostane oxygen carbonyl benzoic acid, succsinic acid-5 ξ-cholestane-3-ester, succsinic acid-5 ξ-cholestene-3-ester, succsinic acid-5 ξ-lanostane-3-ester etc. can be enumerated;
As other the carboxylic acid with steroid skeleton, the compound etc. that such as following formula (1) or (2) represent respectively can be enumerated;
As the benzoic acid derivative with polynuclear plane, such as 4-(4-amyl group-cyclohexyl) phenylformic acid can be enumerated, 4-(4-hexyl-cyclohexyl) phenylformic acid, 4-(4-heptyl-cyclohexyl) phenylformic acid, 4 '-amyl group-dicyclohexyl-4-carboxylic acid, 4 '-hexyl-dicyclohexyl-4-carboxylic acid, 4 '-heptyl-dicyclohexyl-4-carboxylic acid, 4 '-amyl group-biphenyl-4-carboxylic acid, 4 '-hexyl-biphenyl-4-carboxylic acid, 4 '-heptyl-biphenyl-4-carboxylic acid, 4-(4 '-amyl group-dicyclohexyl-4-base) phenylformic acid, 4-(4 '-hexyl-dicyclohexyl-4-base) phenylformic acid, 4-(4 '-heptyl-dicyclohexyl-4-base) phenylformic acid etc.,
As other carboxylic acid with polynuclear plane, such as 6-(4 '-cyanobiphenyl-4-oxygen base) caproic acid, 3-carboxyl can be enumerated and bend;
As the carboxylic acid with fluoroalkyl, such as following formula (b2-1-1) and (b2-1-2) can be enumerated
CF 3-(CF 2) k-(CH 2) n-COOH (b2-1-1)
The compound etc. that (in formula (b2-1-1) and (b2-1-2), k is the integer of 0 ~ 2 separately, and n is the integer of 3 ~ 18 separately) represents respectively, can select more than one to use from these materials.
As the carboxylic acid (1-1) used in manufacturing process 2 and 5, be preferably selected from the benzoic acid derivative with polynuclear plane, the benzoic acid derivative with steroid skeleton and there is more than one the material of other carboxylic acid of steroid skeleton.
The carboxylic acid (1-2) used in above-mentioned manufacturing process 4 ~ 6 is the compound with group containing polymerizability carbon-to-carbon double bond and carboxyl, preferably there is the carboxylic acid of the group that above-mentioned formula (A) represents, the Direct Bonding carboxylic acid of carboxyl (that is, following formula (b2-2) on the group represented particularly preferably in above-mentioned formula (A)
A-COOH (b2-2)
The compound that (in formula (b2-2), A is the group that above-mentioned formula (A) represents) represents).
As the object lesson of this carboxylic acid (1-2); such as (methyl) vinylformic acid, β-crotonic acid, α-ethylacrylate, α-n-propyl vinylformic acid, α-n-butyl, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, 6-{ [6-(acryloxy) caproyl] oxygen base can be enumerated } caproic acid, linolic acid, linolenic acid, TRANSCINNAMIC ACID etc., can more than one be selected to use from these materials.
In above-mentioned manufacturing process 2, only can use carboxylic acid as above (1-1);
In manufacturing process 4 and 6, only can use carboxylic acid as above (1-2);
In manufacturing process 5, only can use carboxylic acid as above (1-1) and carboxylic acid (1-2), or except these carboxylic acids, can be used together the carboxylic acid (hereinafter referred to as " carboxylic acid (2) ") beyond carboxylic acid (1-1) and carboxylic acid (1-2).This carboxylic acid (2) is the carboxylic acid without any group in polymerizability carbon-to-carbon double bond and liquid crystal aligning group; such as formic acid, acetic acid, propionic acid, anthraquinone-2-carboxylic acid, 2-(4-diethylamino-2-hvdroxv-benzovl)-phenylformic acid etc. can be enumerated, can more than one be selected to use from these materials.
As the usage ratio of carboxylic acid (1-1) in manufacturing process 2, relative to precursor organopolysiloxane (A i) the epoxy group(ing) 1mol that has, be preferably 0.1 ~ 0.9mol, be more preferably 0.2 ~ 0.8mol, more preferably 0.25 ~ 0.75mol.Herein, when carboxylic acid (1-1) and carboxylic acid (2) being used, preferably make the total usage ratio of carboxylic acid (1-1) and (2) relative to precursor organopolysiloxane (A simultaneously i) the epoxy group(ing) 1mol that has is preferably 0.1 ~ 0.9mol, be more preferably 0.1 ~ 0.6mol, and the usage ratio making carboxylic acid (1-1) add up to relative to carboxylic acid (1-1) and (2) is preferably more than 60mol%, be more preferably more than 70mol% and less than 100mol%.
As the usage ratio of carboxylic acid (1-2) in manufacturing process 4, relative to precursor organopolysiloxane (A iII) the epoxy group(ing) 1mol that has, be preferably 0.1 ~ 0.9mol, be more preferably 0.2 ~ 0.6mol.Herein, when carboxylic acid (1-2) and carboxylic acid (2) being used, preferably make the total usage ratio of carboxylic acid (1-2) and (2) relative to precursor organopolysiloxane (A simultaneously iII) the epoxy group(ing) 1mol that has is preferably 0.1 ~ 0.9mol, be more preferably 0.1 ~ 0.6mol, and the usage ratio making carboxylic acid (1-2) add up to relative to carboxylic acid (1-2) and (2) is preferably more than 50mol%, is more preferably 60 ~ 95mol%.
In manufacturing process 5, the usage ratio of carboxylic acid is as follows.
The total usage ratio of carboxylic acid: relative to precursor organopolysiloxane (A iII) the epoxy group(ing) 1mol that has, be preferably 0.1 ~ 0.9mol, be more preferably 0.2 ~ 0.7mol, more preferably 0.3 ~ 0.5mol.
Carboxylic acid (1-1): relative to whole carboxylic acid, is preferably below 50mol%, is more preferably 1 ~ 30mol%, more preferably 5 ~ 10mol%.
Carboxylic acid (1-2): relative to whole carboxylic acid, is preferably more than 50mol%, is more preferably more than 70mol%, more preferably more than 90mol%.
Carboxylic acid (2): relative to whole carboxylic acid, is preferably below 50mol%, is more preferably below 30mol%, more preferably below 10mol%.
In manufacturing process 4 and 5, most preferably do not use carboxylic acid (2).
In manufacturing process 6, owing to needing that a part for used carboxylic acid (1-2) is used for follow-up reaction that is that carry out and nucleophilic compound (1), therefore need the usage ratio setting carboxylic acid (1-2) from this side considerations.From this side considerations, as the usage ratio of carboxylic acid (1-2) in manufacturing process 6, preferably relative to precursor organopolysiloxane (A iII) the epoxy group(ing) 1mol that has is 0.1 ~ 0.9mol, is more preferably 0.2 ~ 0.6mol.Herein, when carboxylic acid (1-2) and carboxylic acid (2) being used, preferably make the total usage ratio of carboxylic acid (1-2) and (2) relative to precursor organopolysiloxane (A simultaneously iII) the epoxy group(ing) 1mol that has is preferably 0.1 ~ 0.9mol, be more preferably 0.1 ~ 0.6mol, and the usage ratio making carboxylic acid (1-1) add up to relative to carboxylic acid (1-2) and (2) is preferably more than 50mol%, is more preferably 60 ~ 95mol%.
[precursor organopolysiloxane (A i) or (A iII) and the reaction of carboxylic acid]
Precursor organopolysiloxane (A i) or (A iII) reaction of (they being collectively referred to as " precursor organopolysiloxane " below) and carboxylic acid preferably carries out under suitable catalyzer and suitable organic solvent exist.
As the catalyzer used in the reaction of precursor organopolysiloxane and carboxylic acid, except suitable use such as organic bases, the so-called curing catalyst of the reaction promoting epoxy compounds and acid anhydrides can also be used as the catalyzer in this reaction.As above-mentioned organic bases, such as uncle or secondary organic amine, trimethylamine, organic quaternary amine etc. can be enumerated;
As above-mentioned curing catalyst, can enumerate such as tertiary amine (wherein as organic bases trimethylamine except), imdazole derivatives, organo phosphorous compounds, quaternary alkylphosphonium salt, Diazabicycloalkene, organometallic compound, quaternary ammonium halides, metal halogen compound, On The Latent Accelerator etc.As above-mentioned On The Latent Accelerator etc., the hot cationic polymerization type On The Latent Accelerator etc. of such as high-melting-point decentralized On The Latent Accelerator (such as amine add-on type promotor etc.), microcapsule-type On The Latent Accelerator, amine salt type latent curing agent promotor, thermal dissociation type can be enumerated.
As the object lesson of described catalyzer, above-mentioned uncle or secondary organic amine can enumerate such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles etc.;
Above-mentioned trimethylamine can enumerate such as triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene etc.;
Above-mentioned season, organic amine salt can enumerate such as Tetramethylammonium hydroxide etc.;
Above-mentioned tertiary amine (wherein as organic bases trimethylamine except) such as benzyl dimethyl amine, 2,4,6-tri-(dimethylaminomethyl) phenol, cyclohexyldimethyl amine, trolamine etc. can be enumerated;
Above-mentioned imdazole derivatives can enumerate such as 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 dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis-(methylol) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4,5-bis-((2 '-cyanoethoxy) methyl) imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trimellitate, 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine, 2,4-diamino-6-(2 '-n-undecane base imidazolyl) ethyl-s-triazine, 2,4-diamino-6-(2 '-ethyl-4 '-methylimidazolyl-(1 ')) ethyl-s-triazine, the isocyanuric acid adduct of glyoxal ethyline, the isocyanuric acid adduct of 2-phenylimidazole, the isocyanuric acid adduct etc. of 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine,
Above-mentioned organo phosphorous compounds can enumerate such as diphenylphosphine, triphenylphosphine, triphenyl phosphite etc.;
Above-mentioned quaternary alkylphosphonium salt can enumerate such as benzyltriphenyl phosphonium phosphonium chloride, four normal-butyl phosphonium bromides, first base three phenyl phosphonium bromide, second base three phenyl phosphonium bromide, normal-butyl three phenyl phosphonium bromide, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, the acid of ethyl triphenyl vinegar Phosphonium, four positive fourth base Phosphonium o, o-diethyl dithiophosphate, four positive fourth base Phosphonium benzotriazole salt, four positive fourth base Phosphonium a tetrafluoro borates, four positive fourth base Phosphonium tetraphenyl borate salts, tetraphenylphosphoniphenolate tetraphenyl borate salts etc.;
Above-mentioned Diazabicycloalkene can enumerate such as 1,8-diazabicyclo [5.4.0] hendecene-7, its organic acid salt etc.;
Above-mentioned organometallic compound can enumerate such as zinc octoate, stannous octoate, aluminium acetylacetonate complex etc.;
Above-mentioned quaternary ammonium halides can enumerate such as tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride etc.;
Above-mentioned metal halogen compound can enumerate the boron compound of such as boron trifluoride, boric acid triphenyl and so on; Zinc chloride, tin chloride etc.;
Above-mentioned high-melting-point decentralized On The Latent Accelerator can enumerate the affixture etc. of such as Dyhard RU 100 or amine and epoxy resin;
Above-mentioned microcapsule-type On The Latent Accelerator can enumerate the On The Latent Accelerator etc. such as formed with the surface of the curing catalysts such as the above-mentioned imdazole derivatives of polymer overmold, organo phosphorous compounds, quaternary alkylphosphonium salt;
The hot cationic polymerization type On The Latent Accelerator of above-mentioned thermal dissociation type can enumerate such as lewis acid, Bu Langsi Taide hydrochlorate etc., can more than one be selected to use from these materials.
In these materials, preferably use organic quaternary ammonium salt or quaternary ammonium halides.
For the usage ratio of catalyzer, be preferably 0.01 ~ 100 weight part relative to precursor organopolysiloxane 100 weight part, be more preferably 0.1 ~ 20 weight part.
As the organic solvent used in the reaction of precursor organopolysiloxane and carboxylic acid, such as ketone, ether, ester, acid amides, alcohol etc. can be enumerated.As the object lesson of described organic solvent, above-mentioned ketone can enumerate such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.;
Above-mentioned ether can enumerate such as ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, tetrahydrofuran (THF), dioxane etc.;
Above-mentioned ester can enumerate such as vinyl acetic monomer, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetic ester, ethyl lactate etc.;
Above-mentioned acid amides can enumerate such as methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetylmorpholine, N-Acetylpiperidin, N-acetyl-pyrrolidine etc.;
Above-mentioned acid amides can enumerate such as methane amide, N-METHYLFORMAMIDE, N, dinethylformamide, N-ethyl-formamide, N, N-diethylformamide, ethanamide, N-methylacetamide, N, N-N,N-DIMETHYLACETAMIDE, N-ethyl acetamide, N, N-diethyl acetamide, N-methyl propanamide, N-Methyl pyrrolidone, N-formyl morpholine, N-formyl piperidine, N-carbonyl pyrrolidine, N-acetylmorpholine, N-Acetylpiperidin, N-acetyl-pyrrolidine etc.;
Above-mentioned alcohol can enumerate such as 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list-n-propyl ether, ethylene glycol list-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol list-n-propyl ether etc., can more than one be selected to use from these materials.
For the usage ratio of organic solvent, the ratio preferably making the total weight of the composition in reaction soln beyond organic solvent account for reaction soln total amount reaches the ratio of 0.1 ~ 50 % by weight, more preferably makes it reach the ratio of 5 ~ 50 % by weight.
The reaction of precursor organopolysiloxane and carboxylic acid, preferably at 0 ~ 200 DEG C, is more preferably preferably carried out 0.1 ~ 50 hour, is more preferably carried out 0.5 ~ 20 hour at the temperature of 50 ~ 150 DEG C.
In manufacturing process 2,4 and 5, organopolysiloxane (A) can be obtained as above.
In manufacturing process 6, precursor organopolysiloxane (A can be obtained as above iV), then by reacting with nucleophilic compound (1), organopolysiloxane (A) can be obtained.
[nucleophilic compound]
The nucleophilic compound (1) used in manufacturing process 3 and manufacturing process 6 is the nucleophilic compound of at least one material be selected from amine and mercaptan, and wherein this nucleophilic compound has liquid crystal aligning group.This nucleophilic compound (1) preferably has the nucleophilic compound of the group that above-mentioned formula (D ') represents.
Time amine (hereinafter referred to as " compound (c1) ") that nucleophilic compound (1) is the group that has above-mentioned formula (D ') and represent, as the R in above-mentioned formula (D ') i, be preferably the alkyl of carbonatoms 4 ~ 20 or the fluoroalkyl of carbonatoms 4 ~ 20.
As compound (c1), preferably use primary amine or secondary amine.As the compound (c1) belonging to primary amine, such as octylame, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, heptadecyl-amine, n-Laurylamine, tridecylamine, four decyl amine, pentadecyl amine, cetylamine, heptadecylamine (HDA), octadecylamine, nonadecane amine, 4-(4-pentylcyclohexyl)-aniline, 4-octyloxy aniline etc. can be enumerated;
As the compound (c1) belonging to secondary amine, such as dibutylamine, diamylamine, dihexylamine, two heptyl amices, Di-Octyl amine, nonyl amine, didecylamine, two undecyl amine, two lauryl amine, two three decyl amine, two four decyl amine, two pentadecyl amine, double hexadecyl amine, two heptadecyl amine, dioctadecylamine, two nonadecyl amine etc. can be enumerated, can preferably from these materials, select more than one to use.
As the R in compound (c1) Chinese style (D ') i, be preferably the alkyl of carbonatoms 4 ~ 12 or the fluoroalkyl of carbonatoms 4 ~ 12.
In above-claimed cpd (c1), from the viewpoint of gelation not easily occurring when reacting with the organopolysiloxane with (methyl) acryl and synthesizing easy, preferably use the compound (c1) belonging to secondary amine.
As the usage ratio of compound (c1), compound (c1) is relative to precursor organopolysiloxane (A iI) or (A iV) the mole number ratio of polymerizability carbon-to-carbon double bond that has is preferably more than 1mol% and less than 100mol%, is more preferably 3 ~ 50mol%, more preferably 5 ~ 30mol%.
As the amine of the nucleophilic compound belonged in the present invention, compound as above (c1) and other amine beyond it can be used simultaneously.As other amine this, such as methylamine, dimethylamine, diethylamine, dipropyl amine, aniline etc. can be enumerated, at least one in these materials can be selected, preferably use according to the scope adding up to below 40mol% relative to amine.Wherein in the present invention, as amine, preferably only use compound as above (c1).
Time mercaptan (hereinafter referred to as " compound (c2) ") that nucleophilic compound (1) is the group that has above-mentioned formula (D ') and represent, as the R in above-mentioned formula (D ') ibe preferably the alkyl of carbonatoms 4 ~ 20 or the fluoroalkyl of carbonatoms 4 ~ 20, or the substituted-phenyl of the fluothane group for the alkyl with carbonatoms 2 ~ 12 or carbonatoms 2 ~ 12, or the group of polynuclear plane with the band alkyl of carbonatoms 2 ~ 12 or the fluoroalkyl of carbonatoms 2 ~ 12.As this polynuclear plane, such as dicyclohexyl structure, biphenyl structural, phenylcyclohexane based structures etc. can be enumerated.
As compound (c2), such as butanethiol can be enumerated, amyl mercaptan, hexyl mercaptans, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decylthiol, undecyl mercaptan, lauryl mercaptan, three decylthiol, four decylthiol, pentadecyl mercaptan, hexadecyl mercaptan, heptadecane thiol, Stearyl mercaptan, nonadecyl mercaptan, 4-butyl phenyl mercaptan, 4-amyl group phenyl mercaptan, 4-hexyl phenyl mercaptan, 4-heptyl phenyl mercaptan, 4-octyl phenyl mercaptan, 4-nonyl phenyl mercaptan, 4-decyl phenyl mercaptan, 4-undecyl phenyl mercaptan, 4-dodecylphenyl mercaptan, 4-tri-decyl phenyl mercaptan, 4-tetra-decyl phenyl mercaptan, 4-pentadecylphenyl mercaptan, 4-hexadecyl phenyl mercaptan, 4-heptadecyl phenyl mercaptan, 4-octadecylphenyl mercaptan, 4-nonadecyl phenyl mercaptan, 4-butoxy phenyl mercaptan, 4-pentyloxy phenyl mercaptan, 4-Hexyloxy-phenyl mercaptan, 4-heptyloxybenzene base mercaptan, 4-octyloxyphenyl mercaptan, 4-oxygen in ninth of the ten Heavenly Stems base phenyl mercaptan, 4-oxygen in last of the ten Heavenly stems base phenyl mercaptan, 4-dodecyloxy phenyl mercaptan, 4-undecane oxygen base phenyl mercaptan, 4-dodecyloxy phenyl mercaptan, 4-(4 '-butylcyclohexyl) phenyl mercaptan, 4-(4 '-pentylcyclohexyl) phenyl mercaptan, 4-(4 '-hexyl cyclohexyl) phenyl mercaptan, 4-(4 '-heptyl cyclohexyl) phenyl mercaptan, 4-(4 '-octyl group cyclohexyl) phenyl mercaptan etc., can preferably select more than one to use from these materials.
As the usage ratio of compound (c2), compound (c2) is relative to precursor organopolysiloxane (A iI) or (A iV) the mole number ratio of polymerizability carbon-to-carbon double bond that has is preferably more than 1mol% and less than 100mol%, is more preferably 3 ~ 50mol%, more preferably 5 ~ 30mol%.
As the mercaptan belonging to nucleophilic compound in the present invention, compound as above (c2) and other mercaptan beyond it can be used simultaneously.As other mercaptan, such as methyl mercaptan, ethanethio, propyl group mercaptan, phenyl mercaptan etc. can be enumerated, at least one in these materials can be selected, preferably use according to the scope adding up to below 40mol% relative to mercaptan.Wherein in the present invention, as mercaptan, preferably only use compound as above (c2).
[precursor organopolysiloxane (A i) or (A iII) and the reaction of nucleophilic compound]
About precursor organopolysiloxane (A i) or (A iII) reaction of (they are referred to below " precursor organopolysiloxane ") and nucleophilic compound, be divided into the situation of nucleophilic compound for the amine containing compound (c1) and the mercaptan situation containing compound (c2), be described successively.
{ nucleophilic compound is the situation of the amine containing compound (c1) }
Nucleophilic compound, can by making both preferably in presence of organic solvent, carry out reacting implementing under the existence of optional catalyst with the reaction of precursor organopolysiloxane for during containing the amine of compound (c1).
As organic solvent operable in the reaction of precursor organopolysiloxane and amine, preferably can use polar compound, such as nitrile, sulfoxide, ether, ester, alcohol etc. can be enumerated.As their object lesson, above-mentioned nitrile can enumerate such as acetonitrile etc.; Above-mentioned sulfoxide can enumerate such as dimethyl sulfoxide (DMSO) etc.; Above-mentioned ether can enumerate such as Anaesthetie Ether, dipropyl ether etc.; Above-mentioned ester can enumerate such as vinyl acetic monomer, N-BUTYL ACETATE etc.; Above-mentioned alcohol can enumerate such as trifluoroethanol, hexafluoro ethanol etc.In these materials, when using nitrile or sulfoxide, be preferred from the viewpoint of reaction stability.For solvent, from the viewpoint of speed of response, preferably according to make solid concentration (the total weight of the composition in reaction soln beyond solvent accounts for the ratio of total solution weight) be more than 40 % by weight ratio use, more preferably use according to the ratio being 50 ~ 90 % by weight.
As the catalyzer that can optionally use in precursor organopolysiloxane and amine and reaction, such as aluminum chloride, formic acid etc. can be enumerated.
Temperature of reaction is preferably 10 ~ 100 DEG C, is more preferably 60 ~ 100 DEG C.Reaction times is preferably 0.5 ~ 8 hour, is more preferably 1 ~ 6 hour.
{ nucleophilic compound is the situation of the mercaptan containing compound (c2) }
On the other hand, nucleophilic compound is (during the mercaptan of c2, preferably can carry out reacting implementing under the existence of organic solvent and catalyzer by making both with the reaction of precursor organopolysiloxane containing compound.
As organic solvent operable in precursor organopolysiloxane and thiol reactant, can preferably use such as polar compound, such as nitrile, sulfoxide, ether, ester etc. can be enumerated.As their object lesson, above-mentioned nitrile can enumerate such as acetonitrile etc.; Above-mentioned sulfoxide can enumerate such as dimethyl sulfoxide (DMSO) etc.; Above-mentioned ether can enumerate such as Anaesthetie Ether, dipropyl ether etc.; Above-mentioned ester can enumerate such as vinyl acetic monomer, N-BUTYL ACETATE etc.For solvent, preferably according to make solid concentration (the total weight of the composition in reaction soln beyond solvent accounts for the ratio of total solution weight) be more than 40 % by weight ratio use, more preferably use according to the ratio being 50 ~ 90 % by weight.
As the catalyzer preferably used in precursor organopolysiloxane and mercaptan and reaction, such as organic bases etc. can be enumerated, in more detail, can tertiary amine be enumerated, be specially Trimethylamine 99, diethylmethyl amine, ethyldimethyl amine, triethylamine, tripropylamine etc.The usage ratio of catalyzer is preferably below 50 weight parts relative to mercaptan 100 weight part, is more preferably 10 ~ 30 weight parts.
Temperature of reaction is preferably 10 ~ 100 DEG C, is more preferably 40 ~ 80 DEG C.Reaction times is preferably 0.5 ~ 8 hour, is more preferably 1 ~ 6 hour.
The organopolysiloxane (A) in the present invention can be manufactured preferably by any one method in above-mentioned manufacturing process 1 ~ 6.
Other composition of < >
Liquid crystal aligning agent of the present invention preferably containing the as above organopolysiloxane (A) manufactured as required composition, only otherwise reduce effect of the present invention, also can contain other composition if desired.As other composition described, compound (hereinafter referred to as " epoxy compounds "), functional silanes compound, tensio-active agent, the latent curing agent etc. in the polymkeric substance (hereinafter referred to as " other polymkeric substance ") beyond organopolysiloxane (A), polymerizable unsaturated compound, Photoepolymerizationinitiater initiater, free radical scavenger, molecule with at least one epoxy group(ing) can be enumerated, can more than one be selected to use from these materials.
[other polymkeric substance]
Other polymkeric substance above-mentioned can be use to improve the solution properties of liquid crystal aligning agent, the electrical specification of the liquid crystal orientation film of formation and the liquid crystal aligning that obtain further.Other polymkeric substance described is the polymkeric substance beyond organopolysiloxane as above (A), the organopolysiloxane (hereinafter referred to as " other organopolysiloxane ") beyond such as organopolysiloxane (A), polyamic acid, polyimide, poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc. can be enumerated, can more than one be selected to use from these materials.
When using other polymkeric substance in the present invention, preferably from other organopolysiloxane, polyamic acid and polyimide, more than one are selected to use.
-other have organopolysiloxane-
Other organopolysiloxane above-mentioned is the organopolysiloxane of the group do not had containing polymerizability carbon-to-carbon double bond, optionally can also have at least one group being selected from liquid crystal aligning group and epoxy group(ing).
When formation has the organopolysiloxane of liquid crystal aligning group, ratio is there is as the liquid crystal aligning group in this organopolysiloxane, be preferably the ratio of more than 0.2mol relative to having the 1mol Siliciumatom contained in the organopolysiloxane of liquid crystal aligning group, be more preferably the ratio of 0.3 ~ 0.8mol, be particularly preferably the ratio of 0.4 ~ 0.7mol.
About other organopolysiloxane, be preferably 500 ~ 1,000,000 by the polystyrene conversion weight-average molecular weight of gel permeation chromatography, be more preferably 1,000 ~ 100,000, more preferably 1,000 ~ 50,000.
As other organopolysiloxane this, above-mentioned silane compound (a1) and carboxylic acid (1-2) is prohibitted the use as raw material, except allowing the compound using above-mentioned formula (1) to represent as except raw silicon hydride compounds, can manufacture according to the manufacturing process of above-mentioned organopolysiloxane (A).
Other organopolysiloxane can preferably by making silane compound (a2-2), or the method (manufacturing process 7) that silane compound (a2-2) and the mixture of silane compound (hereinafter referred to as " silane compound (a3) ") with liquid crystal aligning group and alkoxyl group carry out polycondensation manufactures, in addition, also can pass through in the above-mentioned methods, by silane compound (a2-1) as starting compound at least partially, first the organopolysiloxane with epoxy group(ing) is manufactured, then itself and the above-mentioned carboxylic acid containing carboxylic acid (1-1) is made (wherein, this carboxylic acid is not containing carboxylic acid (1-2)) method (manufacturing process 8) of carrying out reacting manufactures.
As above-mentioned silane compound (a3), such as following formula (a3-1) can be enumerated
(R 2) f(R 3) gSi(OR 4) 4-f-g(a3-1)
(in formula (a3-1), R 2for the alkyl of carbonatoms 8 ~ 30, the fluoroalkyl of carbonatoms 8 ~ 30 or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton, R 3for the alkyl of carbonatoms 1 ~ 3, R 4for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, f is the integer of 1 ~ 3, and g is the integer of 0 ~ 2, wherein, f+g≤3) compound, the following formula (a3-2) that represent
(in formula (a3-2), about R i, R iI, Z i, Z iI, n1, n3 and n4, identical with the implication in above-mentioned formula (D ') respectively, n2 is 1, R 10alkyl for carbonatoms 1 ~ 3) compound that represents.
As the compound that above-mentioned formula (a3-1) represents, such as n-octyl Trimethoxy silane can be enumerated, n-octytriethoxysilane, n-octyl three positive propoxy silane, n-octyl three isopropoxy silane, n-octyl three n-butoxy silane, n-octyl three sec-butoxy silane, n-octyl three n-pentyloxy silane, n-octyl three sec-butoxy silane, n-octyl triple phenoxyl silane, n-octyl three pairs of methylenedioxy phenoxy base silanes, positive decyl Trimethoxy silane, positive decyl triethoxyl silane, positive decyl three positive propoxy silane, positive decyl three isopropoxy silane, positive decyl three n-butoxy silane, positive decyl three sec-butoxy silane, positive decyl three n-pentyloxy silane, positive decyl three sec-butoxy silane, positive decyl triple phenoxyl silane, positive decyl three pairs of methylenedioxy phenoxy base silanes, dodecyl Trimethoxy silane, dodecyl triethoxyl silane, dodecyl three positive propoxy silane, dodecyl three isopropoxy silane, dodecyl three n-butoxy silane, dodecyl three sec-butoxy silane, dodecyl three n-pentyloxy silane, dodecyl three sec-butoxy silane, dodecyl triple phenoxyl silane, dodecyl three pairs of methylenedioxy phenoxy base silanes, Octadecane base Trimethoxy silane, Octadecane ethyl triethoxy silicane alkane, Octadecane base three positive propoxy silane, Octadecane base three isopropoxy silane, Octadecane base three n-butoxy silane, Octadecane base three sec-butoxy silane, Octadecane base three n-pentyloxy silane, Octadecane base three sec-butoxy silane, Octadecane base triple phenoxyl silane, Octadecane base three pairs of methylenedioxy phenoxy base silanes,
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-(perfluor-n-octyl) ethyl trimethoxy silane, 2-(perfluor-n-octyl) ethyl triethoxysilane, 2-(perfluor-n-octyl) ethyl three positive propoxy silane, 2-(perfluor-n-octyl) ethyl three isopropoxy silane, 2-(perfluor-n-octyl) ethyl three n-butoxy silane, 2-(perfluor-n-octyl) ethyl three sec-butoxy silane, 3-cholestane base Trimethoxy silane, 3-cholestane ethyl triethoxy silicane alkane, 3-cholestane base three positive propoxy silane, 3-cholestane base three isopropoxy silane, 3-cholestane base three n-butoxy silane, 3-cholestane base three sec-butoxy silane, 3-cholesteryl Trimethoxy silane, 3-cholesteryl triethoxyl silane, 3-cholesteryl three positive propoxy silane, 3-cholesteryl three isopropoxy silane, 3-cholesteryl three n-butoxy silane, 3-cholesteryl three sec-butoxy silane etc.,
As the compound that above-mentioned formula (a3-2) represents, such as 4-pentyloxy phenyltrimethoxysila,e, 4-pentyloxy phenyl triethoxysilane, 4-Hexyloxy-phenyl Trimethoxy silane, 4-Hexyloxy-phenyl triethoxyl silane, 4-octyloxyphenyl Trimethoxy silane, 4-octyloxyphenyl triethoxyl silane, 4-dodecyloxy phenyltrimethoxysila,e, 4-dodecyloxy phenyl triethoxysilane etc. can be enumerated.
For the usage ratio of silane compound (a3) in above-mentioned manufacturing process 7, be preferably below 70mol% relative to the total amount of raw silicon hydride compounds, be more preferably 5 ~ 70mol%, be particularly preferably 5 ~ 50mol%.For the polycondensation in manufacturing process 7, except using silane compound as above as except raw material, implement by the operation identical with polycondensation when manufacturing organopolysiloxane (A).
The usage ratio of the silane compound (a2-1) used when synthesis has the organopolysiloxane of epoxy group(ing) in above-mentioned manufacturing process 8, more than 20mol% is preferably relative to the total amount of raw silicon hydride compounds, be more preferably 30 ~ 70mol%, more preferably 40 ~ 60mol%.For the polycondensation in manufacturing process 8, except using silane compound as above as except raw material, implement by the operation identical with polycondensation when manufacturing organopolysiloxane (A).
In manufacturing process 8, by make the organopolysiloxane with epoxy group(ing) that obtains in a manner described then with the carboxylic acid containing carboxylic acid (1-1) (wherein, this carboxylic acid is not containing carboxylic acid (1-2)) react, the organopolysiloxane with liquid crystal aligning group can be formed.Herein, as carboxylic acid, only can use carboxylic acid (1-1), or also can be used together carboxylic acid (1-1) and above-mentioned and carboxylic acid (2).
As the usage ratio of carboxylic acid (1-1), relative to the epoxy group(ing) 1mol that the organopolysiloxane with epoxy group(ing) has, be preferably 0.1 ~ 0.9mol, be more preferably 0.2 ~ 0.8mol, more preferably 0.25 ~ 0.75mol.When carboxylic acid (1-1) and carboxylic acid (2) are used simultaneously, the epoxy group(ing) 1mol preferably making the total usage ratio of carboxylic acid (1-1) and (2) have relative to the organopolysiloxane with epoxy group(ing) is preferably 0.1 ~ 0.9mol, be more preferably 0.1 ~ 0.6mol, and make carboxylic acid (1-1) be preferably more than 60mol% relative to the usage ratio of the total of carboxylic acid (1-1) and (2), be more preferably more than 70mol%.
The reaction of the organopolysiloxane and carboxylic acid in manufacturing process 8 with epoxy group(ing) can be implemented according to the reacting phase mode together with precursor organopolysiloxane in manufacturing process 2 and 4 ~ 6 and carboxylic acid.
When liquid crystal aligning agent of the present invention contains other organopolysiloxane, it is preferably below 80 weight parts containing proportional relative to organopolysiloxane (A) 100 weight part, is more preferably below 50 weight parts.
-polyamic acid and polyimide-
Above-mentioned polyamic acid can pass through, such as, use the tetracarboxylic dianhydride recorded in patent documentation 9 (Japanese Unexamined Patent Publication 2010-97188 publication) and diamines, make them be undertaken reacting manufacturing by known method.
Polyimide can carry out imidization to manufacture by known method dehydration closed-loop by making above-mentioned polyamic acid.
When liquid crystal aligning agent of the present invention contains more than one polymkeric substance being selected from polyamic acid and polyimide, for it containing proportional, relative to organopolysiloxane (A) 100 weight part, the total amount of polyamic acid and polyimide is preferably below 60 weight parts, is more preferably below 30 weight parts.
[polymerizable unsaturated compound]
In the present invention, the optional polymerizable unsaturated compound used preferably comprises in molecule and has at least one following formula (B-I)
-X 1-Y 1-X 2- (B-I)
(in formula (B-I), X 1and X 2be Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene independently of one another, Y 1for the divalent alkyl of singly-bound, carbonatoms 1 ~ 4, Sauerstoffatom, sulphur atom or-COO-, wherein above-mentioned X 1and X 2can be replaced by the alkoxyl group of the alkyl of one or more carbonatoms 1 ~ 4, carbonatoms 1 ~ 4, fluorine atom or cyano group) the divalent group that represents and at least two following formula (B-II)
(in formula (B-II), R is hydrogen atom or methyl, Y 2and Y 3independently of one another for Sauerstoffatom or sulphur atom) unsaturated compound of the compound (hereinafter referred to as " compound (B-1) ") of 1 valency group that represents.As this unsaturated compound, only can use compound (B-1), also can be used together compound (B-1) and other unsaturated compound.
In compound (B-1), the quantity of the 1 valency group that above-mentioned formula (B-II) represents is preferably two.
As the divalent alkyl of the carbonatoms 1 ~ 4 in above-mentioned formula (B-I), such as methylene radical, dimethylated methylene base etc. can be enumerated.As the divalent group that above-mentioned formula (B-I) represents, such as following formula (B-I-1) ~ (B-I-6) can be enumerated
The group etc. represented respectively.Phenyl ring in above-mentioned formula (B-I-1) ~ (B-I-6) and cyclohexane ring can be replaced by the alkoxyl group of the alkyl of carbonatoms 1 ~ 4, carbonatoms 1 ~ 4, fluorine atom or cyano group respectively.
As the Y in above-mentioned formula (B-II) 2, be preferably Sauerstoffatom.
As the compound used in the present invention (B-1), can enumerate
(the divalent group that above-mentioned formula (B-I) represents is the group that above-mentioned formula (B-I-1) represents, the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of biphenyl structural 2and Y 3be Sauerstoffatom separately),
(the divalent group that above-mentioned formula (B-I) represents is the group that above-mentioned formula (B-I-2) represents, the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of phenyl-cyclohexa based structures 2and Y 3be Sauerstoffatom separately),
(the divalent group that above-mentioned formula (B-I) represents is the group that above-mentioned formula (B-I-3) represents, the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of 2,2-diphenylprop alkyl structure 2and Y 3be Sauerstoffatom separately),
(the divalent group that above-mentioned formula (B-I) represents is the group that above-mentioned formula (B-I-4) represents, the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of diphenylmethyl alkyl structure 2and Y 3be Sauerstoffatom separately),
(the divalent group that above-mentioned formula (B-I) represents is the group that above-mentioned formula (B-I-5) represents, the Y in above-mentioned formula (B-II) to have dithio (methyl) acrylate of diphenylsulfide structure 2for Sauerstoffatom, Y 3for sulphur atom) and other compound (B-1).
As the object lesson of these materials, two (methyl) acrylate with biphenyl structural can enumerate such as 4 '-acryloxy-biphenyl-4-base-acrylate,
4 '-methacryloxy-biphenyl-4-base-methacrylic ester,
2-[4 '-(2-Aciyloyloxy-ethoxy)-biphenyl-4-oxygen base]-ethyl propylene acid esters,
2-[4 '-(2-methacryloxy-oxyethyl group)-biphenyl-4-oxygen base]-ethylmethyl acrylate,
Two hydroxyl-oxethyl biphenyl diacrylate, two hydroxyl-oxethyl biphenyl dimethacrylate,
2-(2-{4 '-[2-(2-Aciyloyloxy-ethoxy)-oxyethyl group]-biphenyl-4-oxygen base }-oxyethyl group)-ethyl propylene acid esters,
2-(2-{4 '-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-biphenyl-4-oxygen base }-oxyethyl group)-ethylmethyl acrylate,
The diacrylate of the ethylene oxide adduct of biphenyl,
The dimethacrylate of the ethylene oxide adduct of biphenyl,
The diacrylate of the propylene oxide adduct of biphenyl,
The dimethacrylate of the propylene oxide adduct of biphenyl,
2-(4 '-acryloxy-biphenyl-4-oxygen base)-ethyl propylene acid esters,
2-(4 '-methacryloxy-biphenyl-4-oxygen base)-ethylmethyl acrylate etc.;
Two (methyl) acrylate with phenyl-cyclohexa based structures can enumerate such as 4-(4-acryloxy-phenyl)-cyclohexylacrylic ester,
4-(4-methacryloxy-phenyl)-cyclohexyl methacrylate,
2-{4-[4-(2-Aciyloyloxy-ethoxy)-phenyl]-cyclohexyloxy }-ethyl propylene acid esters,
2-{4-[4-(2-methacryloxy-oxyethyl group)-phenyl]-cyclohexyloxy }-ethylmethyl acrylate,
2-[2-(4-{4-[2-(2-Aciyloyloxy-ethoxy)-oxyethyl group]-phenyl }-cyclohexyloxy)-oxyethyl group]-ethyl propylene acid esters,
2-[2-(4-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-phenyl }-cyclohexyloxy)-oxyethyl group]-ethylmethyl acrylate etc.;
Two (methyl) acrylate with 2,2-diphenylprop alkyl structure can enumerate such as 4-[1-(4-acryloxy-phenyl)-1-methyl-ethyl]-phenyl acrylate,
4-[1-(4-methacryloxy-phenyl)-1-methyl-ethyl]-phenyl methacrylate,
2-(4-{1-[4-(2-Aciyloyloxy-ethoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethyl propylene acid esters,
2-(4-{1-[4-(2-methacryloxy-oxyethyl group)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethylmethyl acrylate, two hydroxyl-oxethyl-bisphenol a diacrylate,
Two hydroxyl-oxethyl-bisphenol a dimethacrylate,
2-{2-[4-(1-{4-[2-(2-Aciyloyloxy-ethoxy)-oxyethyl group]-phenyl }-1-methyl-ethyl)-phenoxy group]-oxyethyl group }-ethyl propylene acid esters,
2-{2-[4-(1-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-phenyl }-1-methyl-ethyl)-phenoxy group]-oxyethyl group }-ethylmethyl acrylate,
The diacrylate of the ethylene oxide adduct of dihydroxyphenyl propane,
The dimethacrylate of the ethylene oxide adduct of dihydroxyphenyl propane,
The diacrylate of the propylene oxide adduct of dihydroxyphenyl propane,
The dimethacrylate of the propylene oxide adduct of dihydroxyphenyl propane,
2-(4-{1-[4-(2-acryloxy-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl acrylate,
2-(4-{1-[4-(2-methacryloxy-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl methacrylic ester,
2-{2-[4-(1-{4-[2-(2-acryloxy-propoxy-)-propoxy-]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-ethoxy }-1-methyl-ethyl acrylate,
2-{2-[4-(1-{4-[2-(2-methacryloxy-propoxy-)-propoxy-]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-ethoxy }-1-methyl-ethyl methacrylic ester,
3-{4-[1-(3-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl acrylate,
3-{4-[1-(3-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl methacrylic ester,
3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl acrylate,
3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl methacrylate,
3-(5-{1-[6-(3-acryloxy-2-hydroxy-propoxy)-biphenyl-3-base]-1-methyl-ethyl }-biphenyl-2-oxygen base)-2-hydroxyl-propyl acrylate,
3-(5-{1-[6-(3-methacryloxy-2-hydroxy-propoxy)-biphenyl-3-base]-1-methyl-ethyl }-biphenyl-2-oxygen base)-2-hydroxyl-propyl methacrylic ester,
3-{4-[1-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-3-methylphenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxv }-2-hydroxyl-propyl acrylate,
3-{4-[1-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-3-methylphenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxv }-2-hydroxyl-propyl methacrylic ester,
3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl acrylate,
3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl methacrylic ester,
3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl acrylate,
3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl methacrylic ester,
3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl acrylate,
3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxy-propoxy]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl methacrylic ester,
1-(2-{4-[1-(4-{2-[2-hydroxyl-3-(1-methylene radical-allyloxy)-propoxy-]-propoxy-}-phenyl)-1-methyl-ethyl]-oxygen base }-1-methyl-ethoxy)-3-(1-methylene radical-allyloxy)-propane-2-alcohol etc.;
Two (methyl) acrylate with diphenylmethyl alkyl structure can enumerate such as 4-(4-acryloxy-benzyl)-phenyl acrylate,
4-(4-methacryloxy-benzyl)-phenyl methacrylate,
2-{4-[4-(2-Aciyloyloxy-ethoxy)-benzyl]-phenyl }-ethyl propylene acid esters,
2-{4-[4-(2-methacryloxy-oxyethyl group)-benzyl]-phenyl }-ethylmethyl acrylate,
The diacrylate of the ethylene oxide adduct of Bisphenol F,
The dimethacrylate of the ethylene oxide adduct of Bisphenol F,
The diacrylate of the propylene oxide adduct of Bisphenol F,
The dimethacrylate of the propylene oxide adduct of Bisphenol F,
2-[2-(4-{4-[2-(2-Aciyloyloxy-ethoxy)-oxyethyl group]-benzyl }-phenoxy group)-oxyethyl group]-ethyl propylene acid esters,
2-[2-(4-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-benzyl }-phenoxy group)-oxyethyl group]-ethylmethyl acrylate,
2-{4-[4-(2-acryloxy-propoxy-)-Benzyl-phenoxy }-1-methyl-ethyl acrylate,
2-{4-[4-(2-methacryloxy-propoxy-)-Benzyl-phenoxy }-1-methyl-ethyl methacrylic ester,
2-[2-(4-{4-[2-(2-acryloxy-propoxy-)-propoxy-]-benzyl }-phenoxy group)-1-methyl-ethoxy]-1-methyl-ethyl ethyl propylene acid esters,
2-[2-(4-{4-[2-(2-methacryloxy-propoxy-)-propoxy-]-benzyl }-phenoxy group)-1-methyl-ethoxy]-1-methyl-ethyl ethylmethyl acrylate etc.;
Dithio (methyl) acrylate with diphenylsulfide structure can enumerate such as 4-(4-sulfo-acryloyl sulfenyl-thiophenyl)-phenyl dithio acrylate,
4-(4-sulphomethyl acryloyl sulfenyl-thiophenyl)-phenyl dimethylthiazol acrylate,
Two (4-methacryloyl sulfenyl phenyl) thioether etc.;
Other compound (B-1) can enumerate such as 2,5-two { 4-(3-acryloxy-propoxy-)-phenylformic acid } toluene etc.
For described compound (B-1), except synthesizing by suitably combining vitochemical ordinary method, also can obtain as commercially available prod.As the commercially available prod of compound (B-1), such as two hydroxyl-oxethyl BP diacrylate, two hydroxyl-oxethyl Bis-A diacrylate (Honshu chemical industry (strain) system) can be enumerated;
ア ロ ニ Star Network ス M-208, M-210 (East Asia synthesis (strain) system);
SR-349, SR-601, SR-602 (サ mono-ト マ mono-society system);
KAYARAD R-712, R-551 (Japanese chemical drug (strain) system);
NK エ ス テ Le BPE-100, NK エ ス テ Le BPE-200, NK エ ス テ Le BPE-500, NK エ ス テ Le BPE-1300, NK エ ス テ Le A-BPE-4 (Xin Zhong village chemical industry (strain) system), Actilane420 (Japanese シ イ ベ Le ヘ グ Na one (strain) system);
ラ イ ト エ ス テ Le BP-2EM, ラ イ ト ア Network リ レ mono-ト BP-4EA, ラ イ ト ア Network リ レ mono-ト BP-4PA, エ Port キ シ エ ス テ Le 3000M, エ Port キ シ エ ス テ Le 3000A (common prosperity society chemistry (strain) system);
V#540, V#700 (Osaka Organic Chemical Industry (strain) system);
FA-321M (Hitachi Chemical Industries (Ltd.) system);
MPSMA (Sumitomo refine society's system);
リ Port キ シ VR-77 (Showa polymer (strain) system) etc.
As the compound used in the present invention (B-1), preferably from above-mentioned illustrative compound, at least one is selected to use.
As other unsaturated compound above-mentioned, tilt angle can be made closer to 90 ° to reach, thus the desired result of the more effective the application of realization object and be contained in the liquid crystal aligning agent in the present invention.Other unsaturated compound this preferably has the compound of a carbon-to-carbon double bond, is more preferably and has a carbon-to-carbon double bond and the compound as liquid crystal aligning group illustrated in foregoing.As other the object lesson of unsaturated compound this, such as methacrylic acid-5 ξ-cholestane-3-base, methacrylic acid 4-(4 '-phenyl-dicyclohexyl-4-base) phenyl ester, methacrylic acid 4-octyloxy phenyl ester, methacrylic acid 4-(4-pentylcyclohexyl) phenyl ester etc. can be enumerated.
As the usage ratio of the polymerizable unsaturated compound in liquid crystal aligning agent of the present invention, relative to total 100 weight part of organopolysiloxane (A) and other polymkeric substance, be preferably 1 ~ 100 weight part, be more preferably 5 ~ 50 weight parts.
As polymerizable unsaturated compound, by compound (B-1) with other unsaturated compound with when entering to use, as its usage ratio, be preferably below 50 weight parts relative to the total amount of unsaturated compound, be more preferably below 25 weight parts.For other unsaturated compound, by being that more than 5 weight parts use by it according to the total amount relative to polymerizable unsaturated compound, its expected effect can be realized.
[Photoepolymerizationinitiater initiater]
As above-mentioned Photoepolymerizationinitiater initiater, such as α-diketone, acyloin, acyloin ether, benzophenone cpd, acetophenone compound, naphtoquinone compounds, halogen compounds, acylphosphine oxide, organo-peroxide etc. can be enumerated.As their object lesson, α-diketone can enumerate such as benzyl, biacetyl etc.;
Acyloin can enumerate such as bitter almond oil camphor etc.;
Acyloin ether can enumerate such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether etc.;
Benzophenone cpd can enumerate such as thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone, phenyl-(4-is to Tolylsulfanvl-phenyl)-ketone etc.;
Acetophenone compound can enumerate such as methyl phenyl ketone, to dimethylamino benzoylformaldoxime, 4-(α, α '-dimethoxy acetoxyl group) benzophenone, 2,2 '-dimethoxy-2-phenyl acetophenone, p-methoxy-acetophenone, 2-methyl-2-morpholinyl-1-(4-methylthiophenyi)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone etc.;
Naphtoquinone compounds can enumerate such as anthraquinone, 1,4-naphthoquinone etc.;
Halogen compounds can enumerate such as chloro-acetophenone, trisbromomethyl phenyl sulfone, three (trichloromethyl)-s-triazine etc.;
Acylphosphine oxide can enumerate such as TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide etc.;
Organo-peroxide can enumerate such as di-t-butyl peroxide etc., can more than one be selected to use from these materials.
As the commercially available prod of Photoepolymerizationinitiater initiater, can enumerate such as IRGACURE-124, with-149, with-184, with-369, with-500, with-651, with-819, with-907, with-1000, with-1700, with-1800, with-1850, with-2959, Darocur-1116, with-1173, with-1664, with-2959, with-4043 (more than, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ Inc.);
KAYACURE-BMS, with-DETX, with-MBP, with-DMBI, with-EPA, with-OA (more than, Japanese chemical drug (strain) make);
LUCIRIN TPO (BASF society system);
VICURE-10, together-55 (more than, STAUFFER society system);
TRIGONALP1 (AKZO society system);
SANDORAY 1000 (SANDO Z society system);
DEAP (APJOHN society system);
Q UANTACURE-PDO, together-ITX, together-EPD (more than, W ARDBLEKINSOP society system) etc.
As Photoepolymerizationinitiater initiater, from the viewpoint of thermostability height, preferably use benzophenone cpd.
For the usage ratio of the Photoepolymerizationinitiater initiater in liquid crystal aligning agent of the present invention, the occasion of polymerizable unsaturated compound is there is not in liquid crystal aligning agent, below 30 weight parts are preferably relative to 100 weight part organopolysiloxane (A), be more preferably 0.5 ~ 30 weight part, be particularly preferably 1 ~ 20 weight part.Again, the occasion of polymerizable unsaturated compound is there is in liquid crystal aligning agent, the usage ratio of Photoepolymerizationinitiater initiater is relative to total 100 weight part of organopolysiloxane (A) and polymerizable unsaturated compound, be preferably below 30 weight parts, be more preferably 0.5 ~ 30 weight part, be particularly preferably 1 ~ 20 weight part.
[free radical scavenger]
When above-mentioned free radical scavenger applies liquid crystal aligning agent of the present invention as film on substrate, preferably heat, generation polymerizability carbon-to-carbon double bond can be avoided by this heating and preferably not react, therefore can contain in liquid crystal aligning agent of the present invention.
As the object lesson of this free radical scavenger, such as tetramethylolmethane four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], two [the 3-(3 of thiodiethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N '-hexane-1, two [the 3-(3 of 6-bis-base, 5-di-tert-butyl-hydroxy phenyl propionic acid amide), 3, 3 ', 3 ", 5 ', 5 "-six-tertiary butyl-α, α ', α "-(sym-trimethylbenzene-2, 4, 6-tri-base) three p-cresol, 4, two (octylsulfo the methyl)-ortho-cresol of 6-, 4, two (the dodecylthiomethyl)-ortho-cresol of 6-, two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic ester of ethylenebis (oxygen ethylidene), two [the 3-(3 of hexa-methylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 1, 3, 5-tri-[(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethylbenzene) methyl]-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 2, 6-di-t-butyl-4-(4, two (octylsulfo)-1 of 6-, 3, 5-triazine-2-base amine) phenol etc., can more than one be selected to use from these materials.
As the commercially available prod of these materials, ア デ カ ス タ Block AO-20, ア デ カ ス タ Block AO-30, ア デ カ ス タ Block AO-40, ア デ カ ス タ Block AO-50, ア デ カ ス タ Block AO-60, ア デ カ ス タ Block AO-70, ア デ カ ス タ Block AO-80, ア デ カ ス タ Block AO-330 that (strain) ADEKA manufactures can be enumerated;
SumilizerGM, sumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizer W X-R, sumilizerGA-80 that Sumitomo Chemical (strain) manufactures;
IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295 that チ バ ジ ヤ パ Application (strain) manufactures;
Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 etc. that (strain) API Corporation manufactures.
As the usage ratio of the free radical scavenger in the liquid crystal aligning agent in the present invention, the occasion of polymerizable unsaturated compound is there is not in liquid crystal aligning agent, be preferably below 10 mass parts relative to organopolysiloxane (A) 100 mass parts, be more preferably 0.1 ~ 5 mass parts.Again, the occasion of polymerizable unsaturated compound is there is in liquid crystal aligning agent, the relative organopolysiloxane of usage ratio (A) of free radical scavenger and total 100 weight part of polymerizable unsaturated compound, be preferably below 10 mass parts, be more preferably 0.1 ~ 5 mass parts.
[epoxy compounds]
Above-mentioned epoxy compounds is the compound in molecule with at least one epoxy group(ing), wherein has except the situation of epoxy group(ing) at above-mentioned organopolysiloxane (A) and other organopolysiloxane.
As described epoxy compounds, except such as 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, trihydroxymethylpropanyltri diglycidyl ether, 2, outside 2-dibromoneopentyl glycol diglycidylether etc., can also enumerate and there is N, the compound of N-diglycidyl amino.
As the epoxy compounds in the present invention, preferably there is N, the compound of N-diglycidyl amino, as its object lesson, such as N can be enumerated, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc., can more than one be selected to use from these materials.
As the mixing ratio of these epoxy compoundss, be preferably below 40 weight parts relative to organopolysiloxane (A) 100 weight part, be more preferably below 30 weight parts.
[functional silanes compound]
As above-mentioned functional silanes compound, such as 3-TSL 8330 can be enumerated, 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-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, glycidyl oxy methyl Trimethoxy silane, glycidyl oxy methyl triethoxyl silane, 2-glycidoxyethyl Trimethoxy silane, 2-glycidoxyethyl triethoxyl silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxyl silane etc.
As the mixing ratio of these functional silanes compounds, relative to organopolysiloxane (A) 100 weight part, be preferably below 2 weight parts, be more preferably below 0.2 weight part.
[tensio-active agent]
As above-mentioned tensio-active agent, such as nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc. can be enumerated.
When liquid crystal aligning agent of the present invention contains tensio-active agent, as it containing proportional, relative to whole liquid crystal aligning agent 100 weight part, be preferably below 10 weight parts, be more preferably below 1 weight part.
[latent curing agent]
Above-mentioned latent curing agent is, in the storage of liquid crystal aligning agent, do not have solidified nature, wherein after coating of liquid crystalline alignment agent, obtains the composition of the function having given play to curing performance by heating.By making liquid crystal aligning agent of the present invention contain this latent curing thing, while the liquid crystal orientation film that can form thermotolerance and excellent in light-resistance, also having excellent package stability, is preferred.
As the latent curing agent in the present invention, preferably can use in such as molecule and there is the compound that two or more is selected from least one structure of the tert-butyl ester structure of the acetal ester structure of carboxylic acid, the ketal ester structure of carboxylic acid, the 1-alkyl-cycloalkyl ester structure of carboxylic acid and carboxylic acid.Latent curing agent can be the compound of the same structure had in these structures of two or more, also can be the not homostructural compound had in these structures of two or more.
As the group of the acetal ester structure of the above-mentioned carboxylic acid of formation, following formula (C-1) and (C-2) can be enumerated
(in formula (C-1), R αand R βbe separately the aralkyl of the alkyl of carbonatoms 1 ~ 20, the ester ring type group of carbonatoms 3 ~ 10, the aryl of carbonatoms 6 ~ 10 or carbonatoms 7 ~ 10, in formula (C-2), m1 is the integer of 2 ~ 10) group that represents respectively.Herein, as the R in above-mentioned formula (C-1) αalkyl, preferable methyl; As ester ring type group, preferred cyclohexyl; As aryl, preferred phenyl; As aralkyl, preferred benzyl, as the alkyl of R β, the alkyl of preferred carbonatoms 1 ~ 6; As ester ring type group, the ester ring type group of preferred carbonatoms 6 ~ 10; As aryl, preferred phenyl; As aralkyl, preferred benzyl or 2-phenylethyl, as the m1 in formula (C-2), be preferably 3 or 4.
As the group that above-mentioned formula (C-1) represents, such as 1-methoxyl group ethoxycarbonyl can be enumerated, 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxycarbonyl, 1-isopropoxy ethoxycarbonyl, 1-n-butoxy ethoxycarbonyl, 1-isobutoxy ethoxycarbonyl, 1-sec-butoxy ethoxycarbonyl, 1-tert.-butoxy ethoxycarbonyl, 1-cyclopentyloxy ethoxycarbonyl, 1-cyclohexyloxy ethoxycarbonyl, 1-norcamphane oxygen base ethoxycarbonyl, 1-borneol oxygen base ethoxycarbonyl, 1-phenoxy group ethoxycarbonyl, 1-(1-naphthyloxy) ethoxycarbonyl, 1-benzyloxy ethoxycarbonyl, 1-benzene ethoxy ethoxy carbonyl, (cyclohexyl) (methoxyl group) methoxycarbonyl, (cyclohexyl) (oxyethyl group) methoxycarbonyl, (cyclohexyl) (positive propoxy) methoxycarbonyl, (cyclohexyl) (isopropoxy) methoxycarbonyl, (cyclohexyl) (cyclohexyloxy) methoxycarbonyl, (cyclohexyl) (phenoxy group) methoxycarbonyl, (cyclohexyl) (benzyloxy) methoxycarbonyl, (phenyl) (methoxyl group) methoxycarbonyl, (phenyl) (oxyethyl group) methoxycarbonyl, (phenyl) (positive propoxy) methoxycarbonyl, (phenyl) (isopropoxy) methoxycarbonyl, (phenyl) (cyclohexyloxy) methoxycarbonyl, (phenyl) (phenoxy group) methoxycarbonyl, (phenyl) (benzyloxy) methoxycarbonyl, (benzyl) (methoxyl group) methoxycarbonyl, (benzyl) (oxyethyl group) methoxycarbonyl, (benzyl) (positive propoxy) methoxycarbonyl, (benzyl) (isopropoxy) methoxycarbonyl, (benzyl) (cyclohexyloxy) methoxycarbonyl, (benzyl) (phenoxy group) methoxycarbonyl, (benzyl) (benzyloxy) methoxycarbonyl etc.,
As the group that above-mentioned formula (C-2) represents, such as 2-tetrahydrofuran oxygen carbonyl, 2-tetrahydropyran oxygen carbonyl etc. can be enumerated.In these groups, preferred 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxycarbonyl, 1-cyclohexyloxy ethoxycarbonyl, 2-tetrahydropyran oxygen carbonyl, 2-tetrahydropyran oxygen carbonyl etc.
As the group of the ketal ester structure of the above-mentioned carboxylic acid of formation, such as following formula (C-3) ~ (C-5) can be enumerated
(in formula (C-3), R γfor the alkyl of carbonatoms 1 ~ 12, R δand R εbe respectively the aralkyl of the alkyl of carbonatoms 1 ~ 12, the ester ring type base of carbonatoms 3 ~ 20, the aryl of carbonatoms 6 ~ 20 or carbonatoms 7 ~ 20, in formula (C-4), R Φfor the alkyl of carbonatoms 1 ~ 12, m2 is the integer of 2 ~ 8, in formula (C-5), and R ηfor the alkyl of carbonatoms 1 ~ 12, m3 is the integer of 2 ~ 8) group that represents respectively.Herein, as the R in above-mentioned formula (C-3) γalkyl, preferable methyl, as R δalkyl, preferable methyl; As ester ring type group, preferred cyclohexyl; As aryl, preferred phenyl; As aralkyl, preferred benzyl.As R εalkyl, the alkyl of preferred carbonatoms 1 ~ 6; As ester ring type group, the ester ring type group of preferred carbonatoms 6 ~ 10; As aryl, preferred phenyl; As aralkyl, preferred benzyl or 2-phenylethyl.As the R in formula (C-4) Φalkyl, preferable methyl; As m2, be preferably 3 or 4, as the R in formula (C-5) ηalkyl, preferable methyl; As m3, be preferably 3 or 4.
As the group that above-mentioned formula (C-3) represents, such as 1-methyl isophthalic acid-methoxyl group ethoxycarbonyl can be enumerated, 1-methyl isophthalic acid-ethoxy ethoxy carbonyl, 1-methyl isophthalic acid-positive propoxy ethoxycarbonyl, 1-methyl isophthalic acid-isopropoxy ethoxycarbonyl, 1-methyl isophthalic acid-n-butoxy ethoxycarbonyl, 1-methyl isophthalic acid-isobutoxy ethoxycarbonyl, 1-methyl isophthalic acid-sec-butoxy ethoxycarbonyl, 1-methyl isophthalic acid-tert.-butoxy ethoxycarbonyl, 1-methyl isophthalic acid-cyclopentyloxy ethoxycarbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxycarbonyl, 1-methyl isophthalic acid-norcamphane oxygen base ethoxycarbonyl, 1-methyl isophthalic acid-borneol oxygen base ethoxycarbonyl, 1-methyl isophthalic acid-phenoxy group ethoxycarbonyl, 1-methyl isophthalic acid-(1-naphthyloxy) ethoxycarbonyl, 1-methyl isophthalic acid-benzyloxy ethoxycarbonyl, 1-methyl isophthalic acid-benzene ethoxy ethoxy carbonyl, 1-cyclohexyl-1-methoxyl group ethoxycarbonyl, 1-cyclohexyl-1-ethoxy ethoxy carbonyl, 1-cyclohexyl-1-positive propoxy ethoxycarbonyl, 1-cyclohexyl-1-isopropoxy ethoxycarbonyl, 1-cyclohexyl-1-cyclohexyloxy ethoxycarbonyl, 1-cyclohexyl-1-phenoxy group ethoxycarbonyl, 1-cyclohexyl-1-benzyloxy ethoxycarbonyl, 1-phenyl-1-methoxyl group ethoxycarbonyl, 1-phenyl-1-ethoxy ethoxy carbonyl, 1-phenyl-1-positive propoxy ethoxycarbonyl, 1-phenyl-1-isopropoxy ethoxycarbonyl, 1-phenyl-1-cyclohexyloxy ethoxycarbonyl, 1-phenyl-1-phenoxy group ethoxycarbonyl, 1-phenyl-1-benzyloxy ethoxycarbonyl, 1-benzyl-1-methoxyl group ethoxycarbonyl, 1-benzyl-1-ethoxy ethoxy carbonyl, 1-benzyl-1-positive propoxy ethoxycarbonyl, 1-benzyl-1-isopropoxy ethoxycarbonyl, 1-benzyl-1-cyclohexyloxy ethoxycarbonyl, 1-benzyl-1-phenoxy group ethoxycarbonyl, 1-benzyl-1-benzyloxy ethoxycarbonyl etc.,
As the group that above-mentioned formula (C-4) represents, such as 2-(2-methyltetrahydrofuran base) oxygen carbonyl, 2-(2-methyl THP trtrahydropyranyl) oxygen carbonyl etc. can be enumerated;
As the group that above-mentioned formula (C-5) represents, such as 1-methoxy basic ring penta oxygen carbonyl, 1-methoxycyclohexyl oxygen carbonyl etc. can be enumerated.In these groups, preferred 1-methyl isophthalic acid-methoxyl group ethoxycarbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxycarbonyl etc.
As the group of the 1-alkyl-cycloalkyl ester structure of the above-mentioned carboxylic acid of formation, such as following formula (C-6) can be enumerated
(in formula (C-6), R κfor the alkyl of carbonatoms 1 ~ 12, m4 is the integer of 1 ~ 8) group that represents.Herein, as the R in above-mentioned formula (C-6) κalkyl, the alkyl of preferred carbonatoms 1 ~ 10.
As the group that above-mentioned formula (C-6) represents, such as 1-methyl ring third oxygen carbonyl can be enumerated, 1-methyl ring butoxy carbonyl, 1-methyl ring penta oxygen carbonyl, 1-methyl cyclohexane oxygen carbonyl, 1-methyl ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-methyl ring, 1-methyl ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-methyl ring oxygen in last of the ten Heavenly stems carbonyl, 1-ethyl ring third oxygen carbonyl, 1-ethyl ring butoxy carbonyl, 1-ethyl ring penta oxygen carbonyl, 1-cyclohexyl oxygen carbonyl, 1-ethyl ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-ethyl ring, 1-ethyl ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-ethyl ring oxygen in last of the ten Heavenly stems carbonyl, 1-(different) propyl group ring third oxygen carbonyl, 1-(different) propyl group ring butoxy carbonyl, 1-(different) propyl group ring penta oxygen carbonyl, 1-(different) cyclohexyl oxygen carbonyl, 1-(different) propyl group ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) propyl group ring, 1-(different) propyl group ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) propyl group ring oxygen in last of the ten Heavenly stems carbonyl, 1-(different) butyl ring third oxygen carbonyl, 1-(different) butyl ring butoxy carbonyl, 1-(different) butyl ring penta oxygen carbonyl, 1-(different) butylcyclohexyl oxygen carbonyl, 1-(different) butyl ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) butyl ring, 1-(different) butyl ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) butyl ring oxygen in last of the ten Heavenly stems carbonyl, 1-(different) amyl group ring third oxygen carbonyl, 1-(different) amyl group ring butoxy carbonyl, 1-(different) amyl group ring penta oxygen carbonyl, 1-(different) amyl group hexamethylene oxygen carbonyl, 1-(different) amyl group ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) amyl group ring, 1-(different) amyl group ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) amyl group ring oxygen in last of the ten Heavenly stems carbonyl,
1-(different) hexyl ring third oxygen carbonyl, 1-(different) hexyl ring butoxy carbonyl, 1-(different) hexyl ring penta oxygen carbonyl, 1-(different) hexyl hexamethylene oxygen carbonyl, 1-(different) hexyl ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) hexyl ring, 1-(different) hexyl ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) hexyl ring oxygen in last of the ten Heavenly stems carbonyl, 1-(different) heptyl ring third oxygen carbonyl, 1-(different) heptyl ring butoxy carbonyl, 1-(different) heptyl ring penta oxygen carbonyl, 1-(different) heptyl hexamethylene oxygen carbonyl, 1-(different) heptyl ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) heptyl ring, 1-(different) heptyl ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) heptyl ring oxygen in last of the ten Heavenly stems carbonyl, 1-(different) octyl group ring third oxygen carbonyl, 1-(different) octyl group ring butoxy carbonyl, 1-(different) octyl group ring penta oxygen carbonyl, 1-(different) octyl group hexamethylene oxygen carbonyl, 1-(different) octyl group ring oxygen in heptan carbonyl, the pungent oxygen carbonyl of 1-(different) octyl group ring, 1-(different) octyl group ring oxygen in ninth of the ten Heavenly Stems carbonyl, 1-(different) octyl group ring oxygen in last of the ten Heavenly stems carbonyl etc.
The so-called group forming the tert-butyl ester structure of above-mentioned carboxylic acid refers to tertbutyloxycarbonyl.
As the latent curing agent in the present invention, preferred following formula (C)
B1 mR (C)
(in formula (C), B1 is the group or tertbutyloxycarbonyl that in above-mentioned formula (C-1) ~ (C-5), arbitrary formula represents, m is 2 and R is singly-bound, or m is the integer of 2 ~ 10 and the m valency alkyl of the group that R is the hydrogen removing m valency from the heterogeneous ring compound of carbonatoms 3 ~ 10 to be obtained or carbonatoms 1 ~ 18) compound that represents.As m, be preferably 2 or 3.
As the object lesson of R in above-mentioned formula (C), when m is 2, the alkylidene group, 1 of singly-bound, methylene radical, carbonatoms 2 ~ 12 can be enumerated, 2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene, 2,6-naphthylidenes, 5-sodium sulfonic group-1,3-phenylene, 5-4-butyl-phosphonium sulfonic group-1,3-phenylene etc.;
When m is 3, following formula can be enumerated
The group, benzene-1,3,5-tri-base etc. that represent.As above-mentioned alkylidene group, preferred straight chain type.
As the usage ratio of latent curing agent in liquid crystal aligning agent of the present invention, be preferably below 40 weight parts relative to organopolysiloxane (A) 100 weight part, be more preferably 5 ~ 20 weight parts.
When organopolysiloxane (A) has epoxy group(ing), latent curing agent can play its desired result to greatest extent.In this case, as the preferred usage ratio of latent curing agent, relative to the epoxy group(ing) 1mol that organopolysiloxane (A) has, the total mole number of at least one structure in the group of the tert-butyl ester Structure composing of the acetal ester structure of what preferred latent curing agent had be selected from carboxylic acid, the ketal ester structure of carboxylic acid, the 1-alkyl-cycloalkyl ester structure of carboxylic acid and carboxylic acid reaches the ratio of 0.1 ~ 10mol, more preferably reach the ratio of 0.4 ~ 4mol, preferably reach the ratio of 1.5 ~ 2mol further.Therefore, when the compound using above-mentioned formula (C) to represent is as latent curing agent, as the usage ratio of the compound that this above-mentioned formula (C) represents, the epoxy group(ing) 1mol preferably had relative to organopolysiloxane (A) is 0.1/mmol ~ 10/mmol, be more preferably 0.4/mmol ~ 4/mmol, more preferably 1.5/mmol ~ 2/mmol.
Wherein in above content, m is identical with the implication that above-mentioned formula (C) is.
< liquid crystal aligning agent >
Liquid crystal aligning agent of the present invention as organopolysiloxane (A) and optional other composition used preferably comprised by dissolving in organic solvent the liquid composition that formed form.
As the organic solvent that can be used to liquid crystal aligning agent of the present invention, such as METHYLPYRROLIDONE can be enumerated, gamma-butyrolactone, butyrolactam, DMF, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, N-BUTYL ACETATE, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list-n-propyl ether, ethylene glycol list-isopropyl ether, ethylene glycol list-n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol list propyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetic ester, TC acetic ester, Diethylene Glycol list propyl ether acetic ester, diethylene glycol monobutyl ether acetic ester, diisobutyl ketone, isopentyl propionic ester, isopentyl isobutyrate, diisoamyl ether, ethylene carbonate, Texacar PC, methyl alcohol, ethanol, propyl alcohol, butanols, Pyranton, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), monoethylene glycol, Diethylene Glycol, MPG, single hexylene glycol, propylene glycol monomethyl ether, glycol monobutyl ether, propylene glycol list phenyl ether, ritalin, vinyl acetic monomer, ethyl lactate, dimethyl sulfoxide (DMSO), tetramethyl-urea, hexamethylphosphorictriamide, meta-cresols etc., preferably select more than one and use from these solvents.
For the solid concentration (the total weight of the composition beyond the solvent of liquid crystal aligning agent accounts for the ratio of the gross weight of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention, suitably select from the viewpoint of viscosity, volatility etc., wherein preferred in the scope of 1 ~ 10 % by weight.Namely, liquid crystal aligning agent of the present invention is coated on substrate surface as described later, the film as liquid crystal orientation film is formed preferably by heating, when wherein solid concentration is less than 1 % by weight, the thickness of this film is too small, can not obtain good liquid crystal orientation film, on the other hand, if solid concentration is more than 10 % by weight, then the thickness of film is excessive, can not obtain good liquid crystal orientation film.
The scope of particularly preferred solid concentration is different according to the method used during coating of liquid crystalline alignment agent on substrate.Such as adopt spinner method time particularly preferably solid concentration in the scope of 1.5 ~ 7.5 % by weight.When adopting print process, particularly preferably solid concentration is in the scope of 6 ~ 15 % by weight, and therefore soltion viscosity is in the scope of 8 ~ 50mPas.When adopting ink jet method, particularly preferably solid concentration is in the scope of 3 ~ 10 % by weight, and therefore soltion viscosity is in the scope of 3 ~ 15mPas.
Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
The manufacture method > of < liquid crystal display device
Liquid crystal display device of the present invention possesses the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention as above.
Liquid crystal display device of the present invention can be manufactured by any one such as following method.
The liquid crystal display device of known action pattern can carry out manufacturing (manufacture method 1 of liquid crystal display device) through the operation (1) to (3) below such as all the time.
(1) use liquid crystal aligning agent of the present invention formed on substrate film operation,
(2) enter as required to coated surface apply polished finish operation and
(3) between a pair substrate, clamp liquid crystal and form the operation of liquid crystal cell.
By configuring Polarizer on two faces of the liquid crystal cell obtained in a manner described, liquid crystal display device can be manufactured.
In addition, the operation (1 ') to (3 ') that the liquid crystal display device of the new display format of substituting PS A pattern can be passed through such as carries out manufacturing (manufacture method 2 of liquid crystal display device).
(1 ') on this conducting film of a pair substrate with conducting film, be coated with liquid crystal aligning agent of the present invention respectively and formed film operation,
(2 ') makes a pair substrate defining above-mentioned film sandwich the layer of liquid crystal molecule according to centre and the relative mode of above-mentioned film is configured in opposite directions, thus form liquid crystal cell operation and
(3 ') carries out the operation of illumination execute alive state between the conducting film had a pair substrate under to above-mentioned liquid crystal cell.
By the liquid crystal cell two sides configuration Polarizer after the illumination obtained in a manner described, liquid crystal display device can be manufactured.
Below above-mentioned each manufacture method is described successively.
[manufacture method 1 of liquid crystal display device]
Operation (1) in the manufacture method 1 of liquid crystal display device is different according to the pattern of expection.Operation (2) and (3) are general under each pattern.
(1) first on substrate, liquid crystal aligning agent of the present invention is coated with, then by forming film to coated face heating on substrate.
(1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, to two plate bases of patterned transparent conducting film be provided with as a pair, in its each transparent conductive film forming surface, liquid crystal aligning agent of the present invention is coated with respectively, then by forming film to each coated face heating preferably by adherography, spin-coating method or ink jet printing method.Herein, as substrate, the such as glass such as float glass, soda glass can be used; The transparency carrier formed by the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).As the nesa coating arranged on a face of substrate, can use by stannic oxide (SnO 2) formed NESA film (PPG register of company of U.S. trade mark), by indium oxide-tin oxide (In 2o 3-SnO 2) ito film etc. that formed, in order to obtain patterned transparent conducting film, the method being formed pattern after such as forming patternless nesa coating by photoetching, the method etc. using the mask with expection pattern when forming nesa coating can be adopted.During coating of liquid crystalline alignment agent, in order to make the connecing property of substrate surface and nesa coating and film better, the pre-treatment of preliminary election coating functional silanes compound, functionality titanium compound etc. also can be applied on the face that should form interior film of substrate surface.
After coating of liquid crystalline alignment agent, in order to prevent the liquid drippage of the alignment agent be coated with, preferably carry out preheating (prebake).Prebake temperature is preferably 30 ~ 200 DEG C, is more preferably 40 ~ 150 DEG C, is particularly preferably 40 ~ 100 DEG C.The prebake time is preferably 0.25 ~ 10 minute, is more preferably 0.5 ~ 5 point.Afterwards, completely except desolventizing, so in order to remove organopolysiloxane (A) manufacture in the remaining dicarboxylic acid of the occasion of employing manufacture method 1, implement to fire (curing afterwards) operation.This is fired (curing afterwards) has temperature to be preferably 80 ~ 300 DEG C, is more preferably 120 ~ 250 DEG C, after the time of curing be preferably 5 ~ 200 points, be more preferably 10 ~ 100 points.The thickness of the film formed in such a way is preferably 0.001 ~ 1 μm, more preferably 0.005 ~ 0.5 μm.
(1-2) on the other hand, when manufacturing IPS type liquid crystal display device, be provided with the nesa coating forming combed pattern substrate conducting film forming surface and do not arrange on a face of substrate in opposite directions of conducting film, being coated with liquid crystal aligning agent of the present invention respectively, then forming film by heating each coated face.
About the heating means after the patterning method of the material of the substrate now used and nesa coating, nesa coating, the pre-treatment of substrate, the coating process of liquid crystal aligning agent and coating, and the preferred thickness of the film formed, identical with above-mentioned (1-1).
(2) when the liquid crystal display device manufactured by method of the present invention is the liquid crystal display device of VA type, the film formed in a manner described directly can be used as liquid crystal orientation film, and after wherein also can carrying out the polished finish of the following stated according to expection, supply uses.
On the other hand, when manufacturing the liquid crystal display device beyond VA type, liquid crystal orientation film can be formed by applying polished finish to the film formed in a manner described.
Polished finish can by for the coated surface formed in a manner described, carries out with being wound with to be rubbed in certain direction by the roller of the fibroplastic cloth such as such as nylon, artificial silk, cotton.Thus, the orientation energy of liquid crystal molecule can be given to film, thus form liquid crystal orientation film.
In addition, also can for the liquid crystal orientation film formed in a manner described, as disclosed in such as patent documentation 6 (Japanese Unexamined Patent Publication 6-222366 publication) and patent documentation 7 (Japanese Unexamined Patent Publication 6-281937 publication), the process of the tilt angle in a part of region changing liquid crystal orientation film is carried out by a part of irradiation ultraviolet radiation to liquid crystal orientation film, after the part implemented resembling disclosed in patent documentation 8 (Unexamined Patent 5-107544 publication) on liquid crystal orientation film surface forms resist film, carry out the polished finish different from previous polished finish direction, then the process of resist film is removed, by making each region of liquid crystal orientation film, there is different liquid crystal aligning energy, the visual field characteristic etc. of the liquid crystal display device obtained can be improved.
(3) preparing the substrate that two panels defines liquid crystal orientation film in a manner described, manufacturing liquid crystal cell by configuring liquid crystal between two plate bases configured in opposite directions.Herein, when carrying out polished finish to film, two plate bases are according to the angle making the friction direction on each film be in regulation, and such as orthogonal or antiparallel mode configures in opposite directions.
In order to manufacture liquid crystal cell, two kinds of such as following methods can be enumerated.
First method is all the time known method.First, sandwich gap (box gap) according to making each liquid crystal orientation film mode in opposite directions in centre thus configure two plate bases opposite to each other, to fit with sealing agent the peripheral part of two plate bases, to inject in the box gap built by substrate surface and sealing agent and after filling liquid crystal, close filling orifice, thus can liquid crystal cell be manufactured.
Second method is the method being called as ODF (One Drop Fill) mode.Predetermined portion on a substrate in two plate bases defining liquid crystal orientation film is coated with such as ultraviolet light curable sealing material, liquid crystal is dripped again on liquid crystal aligning face, then to fit another substrate according to the mode making liquid crystal orientation film relative, then to whole irradiating ultraviolet light of substrate, make sealant cures, thus can liquid crystal cell be manufactured.Also have, when liquid crystal aligning agent of the present invention contains organopolysiloxane (A) manufactured by manufacturing process 2,3,5 or 6, even if adopt ODF mode in the manufacture of VA type liquid crystal display device, also there will not be ODF uneven, therefore this liquid crystal aligning agent is particularly suitable for adopting the manner.
Herein, as sealing agent, the epoxy resin etc. such as containing solidifying agent and the alumina balls as spacer can be used.
As above-mentioned liquid crystal, such as nematic liquid crystal, smectic liquid crystal etc. can be used, preferably nematic liquid crystal wherein.When VA type liquid crystal cell, preferably there is the nematic liquid crystal of negative dielectric anisotropic, such as dicyano benzene series liquid crystal, pyridazine system liquid crystal, Schiff's base system liquid crystal, azoxy system liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal etc. can be used.When TN type liquid crystal cell or STN type liquid crystal cell, preferably there is the nematic liquid crystal of positive dielectric anisotropy, such as biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, cyclohexyl biphenyl hexane system liquid crystal, pyrimidine system liquid crystal, dioxane system liquid crystal, double-octane system liquid crystal, cube methane series liquid crystal etc. can be used.Also the cholesteryl liquid crystals such as such as chlorination cholestane, cholesteryl nonanoate, cholesteryl carbonate can be added further in these liquid crystal; With that chiral agent that trade(brand)name C-15, CB-15 (メ ルク society system) sell; To oxygen base benzal-use Ferroelectric liquid Crystals etc. such as amino-2-methyl butyl laurates in the last of the ten Heavenly stems.
No matter adopt any method, for the liquid crystal cell manufactured in a manner described, preferably reheat the temperature that liquid crystal used takes to wait Fang Xingxiang, be then slowly cooled to room temperature, thus eliminate flow orientation when liquid crystal is filled.
So, by Polarizer of fitting on the outer surface of liquid crystal cell, can liquid crystal display device be obtained.As this Polarizer, can enumerate and carry out stretch orientation by polyvinyl alcohol, while the light polarizing film being called as " H film " absorbing iodine and formed is clamped in the Polarizer obtained in cellulose acetate protective membrane or the Polarizer be made up of H film itself.
[manufacture method 2 of liquid crystal display device]
(1 ') first, on this conducting film of a pair substrate with conducting film, is coated with liquid crystal aligning agent of the present invention respectively, forms film.Can the film after being formed directly be provided in following operation (2 '), wherein also optionally can apply to resemble the polished finish the operation (2) in manufacture method 1.
A pair substrate defining above-mentioned film is sandwiched the layer of liquid crystal molecule according to centre and above-mentioned film mode is in opposite directions configured in opposite directions by (2 '), thus forms liquid crystal cell.
These operations can be carried out according to the mode identical with operation (1) to (3) in manufacture method 1.As liquid crystal molecule used herein, preferably there is the nematic liquid crystal of negative dielectric anisotropic, such as dicyano benzene series liquid crystal, pyridazine system liquid crystal, Schiff's base system liquid crystal, azoxy system liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal etc. can be used.The thickness of the layer of liquid crystal molecule is preferably 1 ~ 5 μm.
(3 ') carries out illumination to above-mentioned liquid crystal cell execute alive state between the conducting film had above-mentioned a pair substrate under.
As the light irradiated, ultraviolet and the visible ray of the light such as containing 150 ~ 800nm wavelength can be used, the ultraviolet of the light wherein preferably containing 300 ~ 400nm wavelength.Make the light source irradiating light, such as Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc. can be used.The ultraviolet in above-mentioned optimal wavelength region can be obtained by the means etc. above-mentioned light source and such as spectral filter, diffraction grating etc. used simultaneously.As the irradiation dose of light, be preferably 1,000J/m 2above and less than 100,000J/m 2, be more preferably 1,000 ~ 50,000J/m 2.When the manufacture of liquid crystal display device manufacturing all the time known PSA pattern, need irradiation 100,000J/m 2the light of degree, wherein in the method for the invention, even if be 50,000J/m in rayed amount 2below, even 10,000J/m 2when following, also can obtain desired liquid crystal display device, except contributing to cutting down except the manufacturing cost of liquid crystal display device, low, the long-term reliability of the electrical specification that strong illumination can also be avoided to cause low.
By Polarizer of fitting on the outer surface being applied with the liquid crystal cell after processing as above, liquid crystal display device can be obtained.As this Polarizer, the Polarizer identical with manufacture method 1 can be used.
Embodiment
Illustrate further the present invention by the following examples, wherein the present invention is not by the restriction of these embodiments.In following content, the weight-average molecular weight of organo-siloxanes polymer is evaluated by the following method.
[weight-average molecular weight]
The weight-average molecular weight of organo-siloxanes polymer is by using with lower device, is obtained under the following conditions by the result of gel permeation chromatography, is to use monodisperse polystyrene as the polystyrene conversion value of reference material.
Determinator: eastern ソ mono-(strain) system, model " 8120-GPC "
Post: eastern ソ mono-(strain) system, " TSKgelGRCXLII "
Solvent: tetrahydrofuran (THF)
Sample solution concentration: 5 % by weight
Sample injection rate: 100 μ L
Column temperature: 40 DEG C
Column pressure: 68kgf/cm 2
Synthesis (1) > of < organopolysiloxane (A)
Synthesis example A-1
In the reaction vessel being equipped with agitator, thermometer, dropping funnel and reflux condensing tube, drop into 13.9g oxalic acid and 19.5g ethanol, stir, the ethanolic soln of preparation oxalic acid.Then under nitrogen atmosphere this solution is heated to 70 DEG C, then drips the mixture be made up of 15.1g tetraethoxysilane and the 1.6g vinyltriethoxysilane as raw silicon hydride compounds wherein.After dropping terminates, keep keeping for 6 hours at the temperature of 70 DEG C, be then cooled to 25 DEG C, then add 40.0g ethylene glycol butyl ether, thus make containing the solution as the organopolysiloxane (A-1) of organopolysiloxane (A).
The weight-average molecular weight Mw of the organopolysiloxane (A-1) contained in this solution is 12,000.
Synthesis example A-2 ~ A-10
In above-mentioned synthesis example A-1, using the kind of silane compound that uses as raw material and consumption, and the oxalic acid used and the amount of ethanol be set as respectively recording in 1 of table 1 such, in addition prepare respectively containing the solution as organopolysiloxane (A-2) ~ (A-10) of organopolysiloxane (A) according to the mode identical with above-mentioned synthesis example A-1.
In synthesis example A-7 and A-8, silane compound (a2-3) respectively uses two kinds.
The weight-average molecular weight Mw of each organopolysiloxane contained in each solution is shown in 1 of table 1 together, and synthesis example A-9 and A-10 is with reference to synthesis example.
Other synthesis (1) > of organopolysiloxane of <
Synthesis example B-1 and B-2
In above-mentioned synthesis example A-1, using the kind of silane compound that uses as raw material and consumption, and the oxalic acid used and the amount of ethanol be set as respectively recording in 1 of table 1 such, in addition prepare respectively containing as the organopolysiloxane (B-1) of other organopolysiloxane and the solution of (B-2) according to the mode identical with above-mentioned synthesis example A-1.
The weight-average molecular weight Mw of each organopolysiloxane contained in each solution is shown in 1 of table 1 together.
Synthesis example D-1
In above-mentioned synthesis example A-1, using the kind of silane compound that uses as raw material and consumption, and the oxalic acid used and the amount of ethanol be set as respectively recording in 1 of table 1 such, in addition prepare containing the solution as the organopolysiloxane (D-1) of other organopolysiloxane according to the mode identical with above-mentioned synthesis example A-1.In this synthesis example, silane compound (a2-3) uses two kinds.
The weight-average molecular weight Mw of the organopolysiloxane contained in above-mentioned solution is shown in 1 of table 1 together.
The synthesis (1) of 1 organopolysiloxane of table 1
Table 11 in the abbreviation of silane compound be respectively following implication.
[silane compound (a1)]
VTES: vinyltriethoxysilane
STMS: styryl Trimethoxy silane
ATES: allyltriethoxysilane
MPTMS:3-methacryloxypropyl trimethoxy silane
APTMS:3-acryloxypropyl Trimethoxy silane
[silane compound (a2-1)]
TEOS: tetraethoxysilane
MTES: Union carbide A-162
PTES: phenyl triethoxysilane
[other silane compound (silane compound (a3-1))]
ODES: octadecyltriethoxy silane
DDES: dodecyl triethoxysilane
In the silane compound hurdle of 1 of table 1, "-" represents in this hurdle and does not use this raw material.
Other synthesis (2) > of organopolysiloxane of <
Synthesis example C-1
In the reaction vessel being equipped with agitator, thermometer, dropping funnel and reflux condensing tube, add the 2-(3 of 99g as silane compound, 4-epoxycyclohexyl) ethyl trimethoxy silane, 500g, at room temperature mix as the triethylamine of catalyzer as the methyl iso-butyl ketone (MIBK) of solvent and 10g.Then, dripped 100g deionized water by dropping funnel through 30 minutes, then under the backflow of 80 DEG C, Keep agitation reacts for 6 hours.After reaction terminates, take out organic layer, the aqueous ammonium nitrate solution washing with 0.2 % by weight, until the water after washing is in neutral, is under reduced pressure heated up in a steamer desolventizing and water, thus is obtained the organopolysiloxane with epoxy group(ing) as viscosity transparent liquid.
For this, there is the organopolysiloxane of epoxy group(ing), carry out 1when H-NMR analyzes, near chemical shift (δ)=3.2ppm, obtain the peak based on epoxy group(ing) identical with theoretical strength, the side reaction that epoxy group(ing) does not occur in reacting can be confirmed.
Then in the there-necked flask of 200mL, add obtained above there is epoxy group(ing) organopolysiloxane, 30g as the methyl iso-butyl ketone (MIBK) of solvent, 30g as the 4-octyloxy phenylformic acid (epoxy group(ing) being equivalent to have relative to the above-mentioned organopolysiloxane with epoxy group(ing) is 30mol%) of carboxylic acid and the 0.10g UCAT 18X (trade(brand)name as catalyzer, the curing catalyst of the epoxy compounds that サ Application ア プ ロ (strain) manufactures), stir at 100 DEG C and react for 48 hours.After reaction terminates, in reaction mixture, add vinyl acetic monomer, 3 washings are carried out to the organic layer obtained, after using dried over mgso, heats up in a steamer desolventizing, thus obtain the organopolysiloxane (C-1) of the organopolysiloxane as other.For this organopolysiloxane (C-1), be 7,200 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
Synthesis (2) > of < organopolysiloxane (A)
Synthesis example A-11 ~ A-16
In above-mentioned synthesis example C-1, using the kind of silane compound that uses as raw material and consumption, and the kind of carboxylic acid used and consumption be set as respectively recording in 2 of table 1 such, in addition obtain organopolysiloxane (A-11) ~ (A-16) as organopolysiloxane (A) respectively according to the mode identical with above-mentioned synthesis example C-1.For these organopolysiloxane, be shown in together in 2 of table 1 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
In synthesis example A-14 ~ A-16, carboxylic acid uses two kinds respectively.
The synthesis (2) of 2 organopolysiloxane of table 1
Table 12 in silane compound and the abbreviation of carboxylic acid be respectively following implication.
[silane compound (a1)]
MPTMS:3-methacryloxypropyl trimethoxy silane
[silane compound (a2-1)]
ECETS:2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane
[carboxylic acid (1-1)]
OCTBA:4-n-octyloxy phenylformic acid
PCHBA:4-(4-n-pentyl-cyclohexyl) phenylformic acid
SACE: succsinic acid-5 ξ-cholestane-3-base
[carboxylic acid (2)]
AQCA: anthraquinone-2-carboxylic acid
DAHBBA:2-(4-diethylamino-2-hvdroxv-benzovl)-phenylformic acid
Table 12 silane compound hurdle and carboxylic acid hurdle in, "-" represents in this hurdle and does not use this raw material.
Synthesis (3) > of < organopolysiloxane (A)
Synthesis example A-17
In the reaction vessel being equipped with agitator, thermometer, dropping funnel and reflux condensing tube, add the 124.2g 3-methacryloxypropyl trimethoxy silane (MPTMS) as silane compound and 123.2g 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS), 500g as the methyl iso-butyl ketone (MIBK) of solvent and 10.0g triethylamine, at room temperature mix.Then pass through dropping funnel and dripped deionized water 100g through 30 minutes, then mixing under reflux, reacting 6 hours at 80 DEG C.After reaction terminates, take out organic layer, the aqueous ammonium nitrate solution washing with 0.2 % by weight, until the water after washing is in neutral, is under reduced pressure heated up in a steamer desolventizing and water, thus is obtained the organopolysiloxane with epoxy group(ing) as viscosity transparent liquid.
For this, there is the organopolysiloxane of epoxy group(ing), carry out 1when H-NMR analyzes, near chemical shift (δ)=3.2ppm, obtain the peak based on epoxy group(ing) identical with theoretical strength, the side reaction that epoxy group(ing) does not occur in reacting can be confirmed.
Then in the there-necked flask of 200mL, add obtained above there is epoxy group(ing) organopolysiloxane, 30g as the methyl iso-butyl ketone (MIBK) of solvent, 42.1g as the 4-n-pentyl-4 of carboxylic acid '-carboxyl dicyclohexyl (PBCHCA) (epoxy group(ing) being equivalent to have relative to the above-mentioned organopolysiloxane with epoxy group(ing) is 60mol%) and 0.10g be as the UCAT 18X (trade(brand)name of catalyzer, the curing catalyst of the epoxy compounds that サ Application ア プ ロ (strain) manufactures), stir at 100 DEG C and react for 48 hours.After reaction terminates, in reaction mixture, add vinyl acetic monomer, 3 washings are carried out to the organic layer obtained, after using dried over mgso, heats up in a steamer desolventizing, thus obtain the organopolysiloxane (A-17) as organopolysiloxane (A).For this organopolysiloxane (A-17), be 4,500 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
Synthesis example A-18 ~ A-23
In above-mentioned synthesis example A-17, using the kind of silane compound that uses as raw material and consumption, and the kind of carboxylic acid used and consumption be set as respectively recording in 3 of table 1 such, in addition obtain organopolysiloxane (A-18) ~ (A-23) as organopolysiloxane (A) respectively according to the mode identical with above-mentioned synthesis example A-17.For these organopolysiloxane, be shown in together in 3 of table 1 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
In synthesis example A-22 ~ A-23, carboxylic acid uses two kinds respectively.
The synthesis (3) of 3 organopolysiloxane of table 1
Table 13 in silane compound and the abbreviation of carboxylic acid be respectively following implication.
[silane compound (a1)]
MPTMS:3-methacryloxypropyl trimethoxy silane
APTMS:3-acryloxypropyl Trimethoxy silane
[silane compound (a2-1)]
ECETS:2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane
[silane compound (a2-2)]
TEOS: tetraethoxysilane
[carboxylic acid (1-1)]
PBCHA:4-n-pentyl-4 '-carboxyl dicyclohexyl
OCTBA:4-n-octyloxy phenylformic acid
PCHBA:4-(4-n-pentyl-cyclohexyl) phenylformic acid
SACE: succsinic acid-5 ξ-cholestane-3-base
CNPPA:2E-3 (4-(((3-cyano-phenyl) carbonyl) oxygen) phenyl) the third-2-olefin(e) acid
[carboxylic acid (1-2)]
ACDHA:6-{ [6-(acryloxy) caproyl] oxygen } caproic acid
Synthesis (4) > of < organopolysiloxane (A)
Synthesis example A-24
In the reaction vessel being equipped with agitator, thermometer, dropping funnel and reflux condensing tube, add 67g as the 3-acryloxypropyl Trimethoxy silane (APTMS) of silane compound, 125g as the methyl iso-butyl ketone (MIBK) of solvent and 2.5g triethylamine, at room temperature mix.Then pass through dropping funnel and dripped deionized water 25g through 30 minutes, then mixing under reflux, reacting 6 hours at 80 DEG C.After reaction terminates, take out organic layer, the aqueous ammonium nitrate solution washing with 0.2 % by weight, until the water after washing is in neutral, is under reduced pressure heated up in a steamer desolventizing and water, thus is obtained the organopolysiloxane with carbon-to-carbon double bond as viscosity transparent liquid.
Then in the there-necked flask of 200mL, add obtained above there is carbon-to-carbon double bond organopolysiloxane, 40mL as the acetonitrile of solvent, 34.7g as the 3-sulfydryl cholestane (CHOSH) of the mercaptan of nucleophilic compound and the 6.68g triethylamine as catalyzer, be warmed up to 50 DEG C to stir 90 minutes, implement reaction.After reaction terminates, after adding methyl iso-butyl ketone (MIBK) 1,000g, under reduced pressure heat up in a steamer desolventizing and catalyzer, thus obtain the organopolysiloxane (A-24) as organopolysiloxane (A).For this organopolysiloxane (A-24), be 4,100 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
Synthesis example A-25
In above-mentioned synthesis example A-24, as silane compound, the 3-acryloxypropyl Trimethoxy silane (APTMS) of 67g used in combination and 14.9g tetraethoxysilane (TEOS), in addition obtain the organopolysiloxane (A-25) as organopolysiloxane (A) according to the mode identical with above-mentioned synthesis example A-24.For this organopolysiloxane, be 4,800 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
Other synthesis (4) > of organopolysiloxane of <
Synthesis example E-1 and E-2
In above-mentioned synthesis example A-24, using the kind of silane compound that uses as raw material and consumption, and the kind of mercaptan used and consumption be set as respectively recording in 4 of table 1 such, in addition obtain organopolysiloxane (E-1) and (E-2) of the organopolysiloxane as other respectively according to the mode identical with above-mentioned synthesis example A-24.For these organopolysiloxane, be shown in together in 4 of table 1 by the polystyrene conversion weight-average molecular weight Mw of gel permeation chromatography.
The synthesis (4) of 4 organopolysiloxane of table 1
Table 14 in silane compound and the abbreviation of mercaptan be respectively following implication.
[silane compound (a1)]
APTMS:3-acryloxypropyl Trimethoxy silane
[silane compound (a2-3)]
TEOS: tetraethoxysilane
[mercaptan]
CHOSH:3-sulfydryl cholestane
TGA: thioglycolic acid
MPA:3-thiohydracrylic acid
Embodiment 1
The preparation > of < liquid crystal aligning agent
In containing the solution as the organopolysiloxane (A-1) obtained by above-mentioned synthesis example A-1 of organopolysiloxane (A), add ethylene glycol butyl ether, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
The manufacture of <VA type liquid crystal display device and evaluation >
[manufacture of VA type liquid crystal display device]
Spinner is used to be coated on by the liquid crystal aligning agent of above-mentioned preparation on the transparent electrical pole-face with the glass substrate of the transparency electrode formed by ito film, at 80 DEG C, prebake is after 1 minute, in the baking oven carrying out nitrogen replacement at 200 DEG C after cure 1 hour, thus formed thickness film (liquid crystal orientation film).Repeat this operation, make a pair (two panels) substrate with liquid crystal orientation film.
On the periphery with the face of liquid crystal orientation film of a slice in aforesaid substrate, the epoxy resin solid of the alumina balls of diameter 5.5 μm is added by silk screen printing coating, then make the liquid crystal aligning face of a pair substrate relatively carry out stacking and pressing, at 150 DEG C, heating makes solid thermofixation in 21 hours.Then to the gap of substrate, negative type liquid crystal (メ ルク society system is filled from liquid crystal injecting port, MLC-6608), then liquid crystal injecting port is closed with epoxy solid, in order to eliminate flow orientation during Liquid crystal pour, again it is heated 10 minutes at 150 DEG C, then slowly cool to room temperature.
On two faces again outside substrate, according to making the mutually orthogonal mode of its polarization direction fit Polarizer, thus manufacture VA type liquid crystal display device.
[evaluation of VA type liquid crystal display device]
For the VA type liquid crystal display device of above-mentioned manufacture, evaluate in the following manner.Evaluation result is shown in Table 2.
(1) evaluation of liquid crystal aligning
On the liquid crystal display device of above-mentioned manufacture during the voltage of ONOFF (apply remove) 5V, in visual light and shade change, whether there is abnormal territory.
Now, during voltage OFF, do not observe light leak, and when applying voltage, drive area is white display, is considered as liquid crystal aligning when light leak does not appear in region in addition for " good ", be considered as liquid crystal aligning when observing light leak for " bad ".
(2) evaluation of ultraviolet resistance
On the liquid crystal display device of above-mentioned manufacture, according at 70 DEG C with the application time of 60 microseconds, 16.67 milliseconds span apply 1V voltage after, measure from releasing voltage apply (the initial voltage conservation rate VHR of the voltage retention after 16.67 milliseconds bI)." VHR-1 " that determinator uses (strain) Dongyang テ Network ニ カ to manufacture.
Liquid crystal display device after measuring for above-mentioned initial voltage conservation rate, utilizes 800W/m 2the metal halide light irradiation 10,000J/m of illumination 2uV-light, then leave standstill in room temperature and naturally cool to room temperature.Then, again measure voltage retention by mode same as described above and (irradiate rear voltage retention VHR aI).
By following mathematical expression (1)
Calculate the velocity of variation of voltage retention now, when this value is more than 95%, ultraviolet resistance is evaluated as " excellent ", be more than 90% and less than 95% time ultraviolet resistance be evaluated as " good ", during less than 90%, ultraviolet resistance is evaluated as " bad ".
Embodiment 2 ~ 8,11 and 12 and comparative example 1 and 2
What the kind of organopolysiloxane (A) used and consumption are set as respectively recording in table 2 is such, in addition prepares liquid crystal aligning agent according to the mode identical with above-described embodiment 1, manufactures liquid crystal display device and evaluate.Further, "-" in table represents in this hurdle and does not use this composition.
Evaluation result is shown in Table 2.
Further, embodiment 11 and 12 is reference example.
Embodiment 9
Containing in the solution as the organopolysiloxane (A-1) obtained by above-mentioned synthesis example A-1 of organopolysiloxane (A), the organopolysiloxane (C-1) that by above-mentioned synthesis example C-1 obtained of 5 weight parts as other organopolysiloxane is added relative to organopolysiloxane (A-1) 100 weight part in above-mentioned solution, add ethylene glycol butyl ether again, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 10
What the organopolysiloxane (A) used and the kind of other organopolysiloxane and consumption are set as respectively recording in table 2 is such, in addition prepares liquid crystal aligning agent according to the mode identical with above-described embodiment 9, manufactures liquid crystal display device and evaluate.Evaluation result is shown in Table 2.
Embodiment 13
Containing in the solution as the organopolysiloxane (D-1) obtained by above-mentioned synthesis example D-1 of other organopolysiloxane, the organopolysiloxane (A-11) that by above-mentioned synthesis example A-11 obtained of 10 weight parts as organopolysiloxane (A) is added relative to organopolysiloxane (D-1) 90 weight part in above-mentioned solution, add ethylene glycol butyl ether again, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 14 ~ 18
What the consumption of other organopolysiloxane used and the kind of organopolysiloxane (A) and consumption are set as respectively recording in table 2 is such, in addition prepares liquid crystal aligning agent according to the mode identical with above-described embodiment 13, manufactures liquid crystal display device and evaluate.Evaluation result is shown in Table 2.
Embodiment 19
Containing in the solution as the organopolysiloxane (A-6) obtained by above-mentioned synthesis example A-6 of organopolysiloxane (A), the compound that 8 weight parts represent as other additive and as the aftermentioned formula (B-1-1) of polymerizable unsaturated compound is added relative to organopolysiloxane (A-6) 100 weight part in above-mentioned solution, add ethylene glycol butyl ether again, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 20 ~ 23
What the kind of other additive used and consumption are set as respectively recording in table 2 is such, in addition prepares liquid crystal aligning agent according to the mode identical with above-described embodiment 19, manufactures liquid crystal display device and evaluate.Use 2 kinds of other additives respectively in these embodiments.
Evaluation result is shown in Table 2.
Embodiment 24
The organopolysiloxane (A-17) obtained by above-mentioned synthesis example A-17 as organopolysiloxane (A) is dissolved in ethylene glycol butyl ether, forms the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 25 ~ 32
The kind of the organopolysiloxane of use and consumption are set as respectively in table 2 record such, in addition prepare liquid crystal aligning agent according to the mode identical with above-described embodiment 24, manufacture liquid crystal display device with it according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 33 and 34
Containing as in the solution (being equivalent to the amount of organopolysiloxane (A-12) 90 weight part) of the organopolysiloxane (A-12) obtained by above-mentioned synthesis example A-12 of organopolysiloxane (A), add 10 weight parts as the organopolysiloxane (F-1) (embodiment 33) obtained by above-mentioned synthesis example F-1 of other organopolysiloxane or organopolysiloxane (F-2) (embodiment 34), add ethylene glycol butyl ether again, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Embodiment 35
Containing as in the solution (being equivalent to the amount of organopolysiloxane (A-12) 100 weight part) of the organopolysiloxane (A-12) obtained by above-mentioned synthesis example A-12 of organopolysiloxane (A), add 10 weight parts, three (1-butoxyethyl group) benzene-1 belonging to latent curing agent as other additive, 3,5-tricarboxylic acid, add ethylene glycol butyl ether again, form the solution that solid concentration is 5 % by weight.Use this solution of metre filter in 1 μm, aperture, thus preparation liquid crystal aligning agent.
Use this liquid crystal aligning agent, manufacture liquid crystal display device according to the mode identical with above-described embodiment 1 and evaluate.Evaluation result is shown in Table 2.
Table 2 liquid crystal aligning agent and evaluation result (1)
(the 2nd table is continued)
Table 2 liquid crystal aligning agent and evaluation result (1) (Continued)
(the 2nd has shown)
Each composition referred to as following implication in table 2.
[other additive]
Species α: polymerizable unsaturated compound
A-BP-2EO: the compound that following formula (M-1-1) represents
M-211B: in following formula (M-1-2), n is the mixture of the compound of 2 ~ 4
MACE: methacrylic acid-5 ξ-cholestane-3-base
PBCHPM: methacrylic acid 4-(4 '-n-pentyl-dicyclohexyl-4-base) phenyl ester
Species β: Photoepolymerizationinitiater initiater
K-BMS:KAYACURE BMS (Ciba Speciality Chemicals Inc.)
Species γ: free radical scavenger
GA-80:Sumilizer GA-80 (Sumitomo Chemical (strain) system)
Species δ: latent curing agent
TBEBC: three (1-butoxyethyl group) benzene-1,3,5-tricarboxylic acid
Embodiment 36
The manufacture > of < liquid crystal cell
Use the liquid crystal aligning agent prepared by above-described embodiment 2, change pattern (3 kinds) and the ultraviolet irradiation amount (3 levels) of transparency electrode, manufacture and amount to 9 liquid crystal display device, evaluate in the following manner.
[there is the manufacture of the liquid crystal cell of pattern-free transparency electrode]
Use liquid crystal orientation film printing press (Japan's description printing (strain) system), the liquid crystal aligning agent prepared by above-described embodiment 2 is coated on the transparent electrical pole-face of the glass substrate with the transparency electrode formed by ito film, after on the hot-plate of 80 DEG C, heating (prebake) removes desolventizing in 1 minute, the hot-plate of 150 DEG C heats (curing afterwards) 10 minutes, forms average film thickness film.
For this film, utilize and there is the polishing machine of the roller being wound with artificial silk cloth, carry out polished finish by the condition of roller revolution 400rpm, platform movement speed 3cm/ second, fine hair press-in length 0.1mm.Then in ultrapure water, carry out the ultrasonic cleaning of 1 minute, then in the clean baking oven of 100 DEG C dry 10 minutes, thus obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (two panels) has liquid crystal orientation film.
Further, above-mentioned polished finish is to control the toppling over of liquid crystal, carrying out orientation segmentation by easy method and the weak polished finish carried out.
Then, for a slice in above-mentioned a pair substrate, in the outer rim in face with liquid crystal orientation film, coating adds the epoxy resin solid of the alumina balls of diameter 5.5 μm, then according to making the overlapping and pressing by a pair substrate of mode that liquid crystal aligning face is relative, solid is solidified.Then, fill nematic liquid crystal (メ ルク society system, MLC-6608) between from liquid crystal injecting port to a pair substrate, then close liquid crystal injecting port with acrylic photo-curing solid, thus manufacture liquid crystal cell.
Repeat aforesaid operations, manufacture the liquid crystal cell that 3 have pattern-free transparency electrode.One of them is directly used in tilt angle evaluation described later.For all the other two liquid crystal cells, under executing alive state respectively by following method between conducting film, carry out the evaluation for tilt angle and voltage retention after illumination.
For two in liquid crystal cell obtained above, between electrode, apply the 10V voltage of alternating current of frequency 60Hz respectively, under the state driving liquid crystal, use the UV irradiation equipment of metal halide lamp as light source, according to 10,000J/m 2or 100,000J/m 2irradiation dose irradiation ultraviolet radiation.Further, this irradiation dose is the value that use measures with the quantorecorder that wavelength 365nm is assay standard.
[evaluation of tilt angle]
For each liquid crystal cell of above-mentioned manufacture, respectively according to non-patent literature 1 (T.J.Schefferet.al., J.Appl.Phys.vol.48, p1783 (1977)) and non-patent literature 2 (F.Nakano et.al., JPN.J.Appl.Phys.vol.19, p2013 (1980)) the middle method recorded, the liquid crystal molecule measured by using the crystallization rotational method of He-Ne laser, to the value at the inclination angle of real estate, it can be used as tilt angle.
Do not carry out the liquid crystal cell of illumination, irradiation dose is 10,000J/m 2liquid crystal cell and irradiation dose be 100,000J/m 2the respective tilt angle of liquid crystal cell be shown in Table 3.
[there is the manufacture of the liquid crystal cell (1) of patterned transparent electrode]
The liquid crystal aligning agent prepared by above-described embodiment 2 is patterned as slit-shaped as shown in Figure 1, on each electrode surface of glass substrate A and B respectively with the ITO electrode being divided into multiple region, liquid crystal orientation film printing press (Japan's description printing (strain) system) is used to be coated with, after on the hot-plate of 80 DEG C, heating (prebake) removes desolventizing in 1 minute, the hot-plate of 150 DEG C heats (curing afterwards) 10 minutes, and forming average film thickness is film.For this film, in ultrapure water, carry out the ultrasonic cleaning of 1 minute, then in the clean baking oven of 100 DEG C dry 10 minutes, thus obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (two panels) has liquid crystal orientation film.
Then, for a slice in above-mentioned a pair substrate, in the outer rim in face with liquid crystal orientation film, coating adds the epoxy resin solid of the alumina balls of diameter 5.5 μm, then according to making the overlapping and pressing by a pair substrate of mode that liquid crystal aligning face is relative, caking agent is solidified.Then, fill nematic liquid crystal (メ ルク society system, MLC-6608) between from liquid crystal injecting port to a pair substrate, then close liquid crystal injecting port with acrylic photo-curing caking agent, thus manufacture liquid crystal cell.
Repeat aforesaid operations, manufacture the liquid crystal cell that 3 have patterned transparent electrode.One of them is directly used in response speed evaluation described later.For all the other two liquid crystal cells, by the method identical with the above-mentioned manufacture with the liquid crystal cell of pattern-free transparency electrode, execute alive state between conducting film under, according to 10,000J/m 2or 100,000J/m 2irradiation dose carry out for response speed after rayed evaluation.
Further, electrode pattern used herein is the pattern identical with the electrode pattern kind in PSA pattern.
[evaluation of response speed]
Clamp each liquid crystal cell of above-mentioned manufacture with the two panels Polarizer being configured to orthogonal polarization state, then first irradiate visible lamp, by the briliancy of light multitester measuring through the light of liquid crystal cell, using this value as relative permeability 0% not executing in alive situation.Transmitance during 5 60V voltage of alternating current in second is applied, using this value as relative permeability 100% between the electrode being then determined at liquid crystal cell by mode similar to the above.
When applying 60V voltage of alternating current to each liquid crystal cell now, measuring relative permeability moves to 90% time from 10%, is that response speed is evaluated by this timing definition.
Do not carry out the liquid crystal cell of illumination, irradiation dose is 10,000J/m 2liquid crystal cell and irradiation dose be 100,000J/m 2the respective response speed of liquid crystal cell be shown in Table 3.
[there is the manufacture of the liquid crystal cell (2) of patterned transparent electrode]
Use the liquid crystal aligning agent prepared by above-described embodiment 2, and use glass substrate A and B being patterned as the ITO electrode of herring-bone form had respectively as shown in Figure 2, in addition, do not carry out the liquid crystal cell of illumination according to the mode manufacture identical with the manufacture of the liquid crystal cell (1) with above-mentioned patterned transparent electrode, irradiation dose is 10,000J/m 2liquid crystal cell and irradiation dose be 100,000J/m 2liquid crystal cell, be used for the evaluation of response speed according to mode same as described above respectively.Evaluation result is shown in Table 3.
Embodiment 37 ~ 67 and comparative example 3 ~ 5
As liquid crystal aligning agent, the liquid crystal aligning agent prepared in the embodiment listed in use table 3 respectively or comparative example, in addition, manufactures the liquid crystal display device amounting to 9, and evaluates by the mode identical with above-described embodiment 23.
Evaluation result is shown in Table 3.
Table 3 evaluation result (2)
(the 3rd table is continued)
Table 3 evaluation result (2) (Continued)
(the 3rd has shown)
For following embodiment 68 ~ 85 and comparative example 6 and 7, carry out for confirming that liquid crystal aligning agent of the present invention has the experiment of fabulous vertical orientated restraint force.As the too harsh test of vertical orientated property, use the TN type liquid crystal of inherently horizontal alignment tendency, evaluate the vertical orientated property of the liquid crystal orientation film formed.
Embodiment 68
As liquid crystal aligning agent, use the liquid crystal aligning agent prepared by above-described embodiment 13, as liquid crystal, use the TN type liquid crystal " ZLI-5081 " that メ ルク society manufactures, in addition, manufacture VA type liquid crystal display device by the mode identical with [manufacture of VA type liquid crystal display device] of above-described embodiment 1, carry out the evaluation identical with " evaluation of (1) liquid crystal aligning ".
Consequently on above-mentioned liquid crystal display device during the voltage of ONOFF (apply remove) 5V, light leak is not observed during voltage OFF, and when applying voltage, drive area is white display, and do not have the light leak that other region produces, liquid crystal aligning is " good ".
Embodiment 69 ~ 85 and comparative example 6 and 7
As liquid crystal aligning agent, the liquid crystal aligning agent prepared in the embodiment listed in use table 4 respectively or reference example, in addition, manufactures VA type liquid crystal display device by the mode identical with above-described embodiment 68, evaluates liquid crystal orientation.
Evaluation result is shown in Table 4.
The evaluation of the vertical orientated restraint force of table 4
Preparation liquid crystal gathers embodiment number to agent and comparative example number Vertical orientated property
Embodiment 68 Embodiment 13 Good
Embodiment 69 Embodiment 14 Good
Embodiment 70 Embodiment 15 Good
Embodiment 71 Embodiment 16 Good
Embodiment 72 Embodiment 17 Good
Embodiment 73 Embodiment 18 Good
Embodiment 74 Embodiment 24 Good
Embodiment 75 Embodiment 25 Good
Embodiment 76 Embodiment 26 Good
Embodiment 77 Embodiment 27 Good
Embodiment 78 Embodiment 28 Good
Embodiment 79 Embodiment 29 Good
Embodiment 80 Embodiment 30 Good
Embodiment 81 Embodiment 31 Good
Embodiment 82 Embodiment 32 Good
Embodiment 83 Embodiment 33 Good
Embodiment 84 Embodiment 34 Good
Embodiment 85 Embodiment 35 Good
Comparative example 6 Embodiment 11 (reference example) Bad
Comparative example 7 Embodiment 12 (reference example) Bad
From above-mentioned table 4, as the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention, even if use TN type liquid crystal as liquid crystal, also show excellent vertical orientated restraint force.Empirically show, as the liquid crystal orientation film demonstrating this result, even if adopt liquid crystal drop add mode (ODF mode) in liquid crystal filling work procedure, also ODF inequality can not occur.

Claims (9)

1. the manufacture method of liquid crystal display device, it is characterized in that through:
On this conducting film of a pair substrate with conducting film, coating of liquid crystalline alignment agent respectively, thus form film,
Make a pair substrate defining above-mentioned film sandwich the layer of liquid crystal molecule according to centre and the relative mode of above-mentioned film is configured in opposite directions, thus form liquid crystal cell,
Execute alive state between the conducting film had above-mentioned a pair substrate under, above-mentioned liquid crystal cell is carried out to the operation of illumination,
Wherein, the feature of described liquid crystal aligning agent is, containing organopolysiloxane, this organopolysiloxane possesses group that following formula (A) represents and the weight-average molecular weight of this organopolysiloxane is 500 ~ 1000000, wherein, undertaken except the polysiloxane that polycondensation obtains by the organoalkoxysilane comprising compound that following formula (1) represents and the compound that following formula (2) represents
R ASi(OR B) 3(1)
R CSi(OR D) 3(2)
In formula (1), R athe alkyl of the carbonatoms 8 ~ 30 that can be replaced by fluorine atoms, R bit is the alkyl of carbonatoms 1 ~ 5;
In formula (2), R cby the alkyl that acryl or methacryloyl replace, R dthe alkyl of carbonatoms 1 ~ 5,
In formula (A), R is hydrogen atom or methyl, X iand X iIbe respectively the alkylidene group of Isosorbide-5-Nitrae-phenylene, methylene radical or carbonatoms 2 ~ 8, Z is Sauerstoffatom ,-COO- *or-OCO- *, wherein, the connecting key of band " * " is at X iIside, a, b, c and d are respectively 0 or 1, wherein, c be 0 and d is 1 time, X iIfor Isosorbide-5-Nitrae-phenylene, when b is 0, d is 0,
And the group that this formula (A) represents is 0.01 ~ 0.60mol relative to the ratio of the 1mol Siliciumatom contained in organopolysiloxane.
2. the manufacture method of liquid crystal display device according to claim 1, the operation that the silane compound that above-mentioned organopolysiloxane is through the compound represented containing following formula (a1) carries out polycondensation obtains,
In formula (a1), R, X i, X iI, Z, a, b, c and d be identical with the implication in above-mentioned formula (A) respectively, R 1for the alkyl of carbonatoms 1 ~ 12, e is the integer of 1 ~ 3.
3. the manufacture method of liquid crystal display device according to claim 2, above-mentioned silane compound comprises compound that above-mentioned formula (a1) represents and the compound that following formula (a2-2) represents,
(R 5) h(R 6) iSi(OR 7) 4-h-i(a2-2)
In formula (a2-2), R 5for there is 1 valency group of epoxy group(ing), R 6for the alkyl of carbonatoms 1 ~ 3, R 7for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, h is the integer of 1 ~ 3, and i is the integer, wherein of 0 ~ 2, h+i≤3,
And above-mentioned organopolysiloxane is through above-mentioned silane compound and carries out polycondensation, and then obtains with the operation of carboxylic acid reaction, wherein this carboxylic acid comprises the carboxylic acid with the group that following formula (D ') represents,
Formula (D ') in, R ifor the fluoroalkyl of the alkyl of carbonatoms 1 ~ 40, carbonatoms 1 ~ 40, cyano group or fluorine atom or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton;
Z ifor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
R iIfor cyclohexylidene or phenylene, wherein, this cyclohexylidene or phenylene can be replaced by the alkyl of cyano group, fluorine atom, trifluoromethyl or carbonatoms 1 ~ 3,
N1 is 1 or 2, wherein, when n1 is 2, and two R iIcan be the same or different, n2 is 0 or 1;
Z iIfor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
N3 is the integer of 0 ~ 2, and n4 is 0 or 1.
4. the manufacture method of liquid crystal display device according to claim 2, above-mentioned organopolysiloxane is through above-mentioned silane compound and carries out polycondensation, and then obtain with the operation that at least one nucleophilic compound be selected from group that amine and mercaptan forms reacts, wherein, this nucleophilic compound comprises the nucleophilic compound with the group that following formula (D ') represents
Formula (D ') in, R ifor the fluoroalkyl of the alkyl of carbonatoms 1 ~ 40, carbonatoms 1 ~ 40, cyano group or fluorine atom or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton;
Z ifor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
R iIfor cyclohexylidene or phenylene, wherein, this cyclohexylidene or phenylene can be replaced by the alkyl of cyano group, fluorine atom, trifluoromethyl or carbonatoms 1 ~ 3,
N1 is 1 or 2, wherein, when n1 is 2, and two R iIcan be the same or different, n2 is 0 or 1;
Z iIfor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
N3 is the integer of 0 ~ 2, and n4 is 0 or 1.
5. the manufacture method of liquid crystal display device according to claim 1, the silane that above-mentioned organopolysiloxane is through the compound represented containing following formula (a2-2) carries out polycondensation, then obtain with the operation of carboxylic acid reaction, wherein, this carboxylic acid comprises the carboxylic acid with the group that above-mentioned formula (A) represents
(R 5) h(R 6) iSi(OR 7) 4-h-i(a2-2)
In formula (a2-2), R 5for there is 1 valency group of epoxy group(ing), R 6for the alkyl of carbonatoms 1 ~ 3, R 7for the alkyl of carbonatoms 1 ~ 12 or the aryl of carbonatoms 6 ~ 12, h is the integer of 1 ~ 3, and i is the integer, wherein of 0 ~ 2, h+i≤3.
6. the manufacture method of liquid crystal display device according to claim 5, above-mentioned carboxylic acid comprises the carboxylic acid with the group that following formula (D ') represents,
Formula (D ') in, R ifor the fluoroalkyl of the alkyl of carbonatoms 1 ~ 40, carbonatoms 1 ~ 40, cyano group or fluorine atom or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton;
Z ifor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
R iIfor cyclohexylidene or phenylene, wherein, this cyclohexylidene or phenylene can be replaced by the alkyl of cyano group, fluorine atom, trifluoromethyl or carbonatoms 1 ~ 3,
N1 is 1 or 2, wherein, when n1 is 2, and two R iIcan be the same or different, n2 is 0 or 1;
Z iIfor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
N3 is the integer of 0 ~ 2, and n4 is 0 or 1.
7. the manufacture method of liquid crystal display device according to claim 5, above-mentioned organopolysiloxane is through above-mentioned silane compound and carries out polycondensation, then with above-mentioned carboxylic acid reaction, and then obtain with the operation that at least one nucleophilic compound being selected from amine and mercaptan reacts, wherein, this nucleophilic compound comprises the nucleophilic compound with the group that following formula (D ') represents
Formula (D ') in, R ifor the fluoroalkyl of the alkyl of carbonatoms 1 ~ 40, carbonatoms 1 ~ 40, cyano group or fluorine atom or the alkyl of carbonatoms 17 ~ 51 with steroid skeleton;
Z ifor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
R iIfor cyclohexylidene or phenylene, wherein, this cyclohexylidene or phenylene can be replaced by the alkyl of cyano group, fluorine atom, trifluoromethyl or carbonatoms 1 ~ 3,
N1 is 1 or 2, wherein, when n1 is 2, and two R iIcan be the same or different, n2 is 0 or 1;
Z iIfor singly-bound, *-O-, *-COO-or *-OCO-, wherein, the connecting key of band " * " is at R iside,
N3 is the integer of 0 ~ 2, and n4 is 0 or 1.
8. the manufacture method of the liquid crystal display device according to any one of claim 1 ~ 7, wherein said liquid crystal aligning agent is vertical orientating type.
9. liquid crystal display device, is characterized in that, is that the manufacture method of the liquid crystal display device according to any one of claim 1 ~ 7 is obtained.
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