CN103131431A

CN103131431A - Display material, liquid crystal alignment agent and liquid crystal display element

Info

Publication number: CN103131431A
Application number: CN2012105133250A
Authority: CN
Inventors: 清水成夫; 平野哲; 川又俊友; 山边敦美; 石川晓
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2011-12-05
Filing date: 2012-12-04
Publication date: 2013-06-05
Anticipated expiration: 2032-12-04
Also published as: TWI510464B; KR101881803B1; JP2013117681A; CN103131431B; KR20130062871A; TW201323389A; TW201602072A

Abstract

The invention provides a display material, a liquid crystal alignment agent, a liquid crystal display device and a manufacturing method thereof. The object of the present invention is to provide the liquid crystal alignment agent capable of acquiring excellent vertical orientation and possessing high UV resistance. The liquid crystal alignment agent includes at least polysiloxane and a solvent, and is characterized in that: the solvent includes a compound as shown in the following formula (S1): R10O-((CR112)m1-O)m2-H (S1), wherein R10 is phenyl or benzyl, the phenyl or the benzyl can also be substituted by halogen atoms, cyano groups, and C1-C4 alkyl, R11 is a hydrogen atom or a C1-C8 alkyl, m1 is an integer of 2-8, m2 is an integer of 1-4, a plurality of R11 may be identical or different from each other, and in case of a plurality of m1 s, the plurality of m1 may be identical or different from each other.

Description

MATERIALS FOR DISPLAY, crystal aligning agent and liquid crystal display device

Technical field

The present invention relates to a kind of MATERIALS FOR DISPLAY, particularly a kind of crystal aligning agent.More specifically, relate to a kind of crystal aligning agent that obtains the vertical orientation excellence and have the liquid crystal orienting film of ultraviolet resistance highly.

Background technology

As liquid crystal display device, except using with twisted nematic (Twisted Nematic, TN) type, STN Super TN (Super Twisted Nematic, STN) beyond the liquid crystal display device for the horizontal direction matching pattern of the nematic liquid crystal with positive dielectric anisotropy of representative such as type, also known vertical orientation (Vertical Alignment, VA) the type liquid crystal display device that vertical (homeotropic) alignment mode that uses the nematic liquid crystal with negative dielectric anisotropic is arranged.

This kind liquid crystal display device comprises and has the liquid crystal orienting film that makes the function of liquid crystal alignment on certain orientation.As the material that consists of this liquid crystal orienting film, known have polyamic acid, polyimide, polymeric amide, polyester, an organopolysiloxane etc., particularly comprise the thermotolerance, physical strength of the liquid crystal orienting film of polyamic acid or polyimide, with the affinity excellence of liquid crystal molecule etc., therefore just preferably used since before by (patent documentation 1～patent documentation 3).

And, disclosed the crystal aligning agent that contains organopolysiloxane in patent documentation 4, described organopolysiloxane is that the mixture that makes 3 officials can reach the water-disintegrable silane compound of 4 officials' energy reacts and the organopolysiloxane of gained under the existence of oxalic acid and alcohol, and vertical orientation and excellent heat resistance by the formed liquid crystal orienting film of this crystal aligning agent have been described.

The development of well-known liquid crystal display device is remarkable in recent years, the high-quality demonstration that becomes and to carry out the demonstration of fine and carry out animation responsiveness excellence at a high speed, except TV, also be widely applicable in vehicle-mounted type display unit, game machine, portable animation player etc.And, can carry out the demonstration of high brightness along with becoming, the situation of liquid crystal display device as above outdoor application by day increases, so liquid crystal display device and the liquid crystal orienting film that comprises thereof become and be exposed to for a long time under the strong ultraviolet ray that reckons without in use aspect before.Therefore, in known before LCD alignment mould material, do not have the ultraviolet resistance that can adapt to present use aspect, the ultraviolet resistance of expectation liquid crystal orienting film improves.

Wherein, the liquid crystal display device of polymer-stabilized alignment (Polymer Sustained Alignment, PSA) pattern has been proposed in recent years.The PSA pattern is following technology: comprising with the substrate of pattern-like conducting film and with the gap of a pair of substrate of the substrate of the figuratum conducting film of tool not or comprise 2 pieces of gaps with a pair of substrate of the substrate of pattern-like conducting film and seize the liquid-crystal composition that contains polymerizable compound on both sides by the arms, execute irradiation ultraviolet radiation under alive state and make the polymerizable compound polymerization between to conducting film, show therefrom the tilt angle characteristic, thereby control the alignment direction of liquid crystal.If utilize this technology, can be the high speed that specific formation realizes expansion and the liquid crystal molecule response at visual angle by making conducting film, and in multi-zone vertical alignment nematic (Multi-domain Vertical Alignment, MVA) profile plate inevitably the problem of transmissivity and contrast gradient deficiency also can be resolved.Yet, in the PSA pattern, must irradiation for example 10 for the polymerization of described polymerizable compound, 000J/m ²Above a large amount of ultraviolet ray.Therefore, there is as can be known following situation: produce deteriorated abnormal of liquid crystal orienting film in the uviolizing step.

At this on the one hand, the technology (patent documentation 5) about the more novel display format that replaces above-mentioned PSA pattern has been proposed recently.This techniques attempt is shone the not ultraviolet ray of polarisation to the Kapton that comprises the laurate structure with light functionality, utilizes the molecule rotation that the photoisomerization of described laurate structure produces and gives desired tilt angle expression power.Yet, in order to give desired tilt angle expression power, need the ultraviolet ray of irradiation a great deal of, the one-period time (takt time) when making liquid crystal display device is elongated, perhaps because strong ultraviolet ray produces following disadvantage: diminish the electrical specification of formed liquid crystal orienting film, particularly voltage retention etc.

As mentioned above, along with the exploitation of the variation of the use aspect of liquid crystal display device, new display format, to the raising ultraviolet resistance of LCD alignment mould material want changes persuing large, pump up urgent countermeasure.

On the other hand, the manufacturing step of liquid crystal display device has also reached larger progress in recent years.The technology such as the large substrate conveyance technology that particularly adopts along with the maximization of substrate or liquid crystal drop add mode (One DropFill mode, in the art referred to as " ODF mode ") receive publicity.Wherein, the ODF mode is the liquid crystal in the number place's dropping necessary amount that is formed with the regulation on the substrate of liquid crystal orienting film, press on whole that is disseminated to substrate with another baseplate-laminating and with liquid crystal in a vacuum, then the sealing agent in order to encapsulated liquid crystals is carried out ultraviolet ray (Ultra Violet, UV) sclerosis, in the method for whole middle filling liquid crystal of panel, it is Comparatively speaking can significantly shorten the technology in the treatment time of liquid crystal filling step with the vacuum injection mode of carrying out before therefrom.Yet if adopted the ODF mode in the manufacturing of the VA type liquid crystal display device of known liquid crystal orienting film before comprising, exist to produce following abnormal phenomenon: it is uneven to produce the demonstration that is called as " ODF is uneven ".Think that this phenomenon results from the vertical orientation restraint of liquid crystal orienting film not enough.

Therefore, the crystal aligning agent of the liquid crystal orienting film that does not produce above-mentioned ODF inequality and the liquid crystal display device of display quality excellence are made in requirement with can not undermining the desired various requirement performance of crystal aligning agent.

The prior art document

Patent documentation

Patent documentation 1 Japanese patent laid-open 4-153622 communique

The patent documentation 2 clear 56-91277 communiques of Japanese Patent Laid-Open

Patent documentation 3 Japanese patent laid-open 11-258605 communiques

Patent documentation 4 Japanese patent laid-open 9-281502 communiques

No. 2009/0325453 specification sheets of patent documentation 5 U.S. Patent Application Publications

Patent documentation 6 Japanese patent laid-open 6-222366 communiques

Patent documentation 7 Japanese patent laid-open 6-281937 communiques

Patent documentation 8 Japanese patent laid-open 5-107544 communiques

Patent documentation 9 Japanese Patent Laid-Open 2010-97188 communiques

Non-patent literature

The people such as non-patent literature 1T.J.Scheffer, applicating physical magazine (J.Appl.Phys.) the 48th volume, the 1783rd page (1977)

The people such as non-patent literature 2F.Nakano, Japanese applicating physical magazine (JPN.J.Appl.Phys.) the 19th volume, the 2013rd page (1980)

Summary of the invention

The present invention forms in view of the above fact, and its purpose is to provide:

A kind of vertical orientation particularly of obtaining is excellent and have a kind of MATERIALS FOR DISPLAY, crystal aligning agent and liquid crystal display device and a manufacture method thereof of liquid crystal orienting film of the ultraviolet resistance of height.

According to the present invention, above-mentioned problem of the present invention can be reached by following MATERIALS FOR DISPLAY, crystal aligning agent and liquid crystal display device and manufacture method thereof.The present invention proposes a kind of MATERIALS FOR DISPLAY, and it is the MATERIALS FOR DISPLAY that contains at least polysiloxane and solvent, it is characterized in that:

Above-mentioned solvent contains the represented compound of following formula (S1),

R ¹⁰O-((CR ¹¹ ₂) _m1-O) _m2-H (S1)

In formula (S1), R ¹⁰Be phenyl or benzyl, wherein, these phenyl or benzyl can be also 1～4 alkyl replacement through halogen atom, cyano group, carbon number,

R ¹¹That hydrogen atom or carbon number are 1～8 alkyl,

M1 is 2～8 integer,

M2 is 1～4 integer,

Wherein, a plurality of R ¹¹Can be identical also can be mutually different,

In the situation that there are a plurality of m1, a plurality of m1 can be identical also can be mutually different.

The present invention proposes a kind of crystal aligning agent, and it is the crystal aligning agent that contains at least polysiloxane and solvent, it is characterized in that:

Described solvent contains the represented compound of following formula (S1),

R ¹⁰O-((CR ¹¹ ₂) _m1-O) _m2-H (S1)

(in formula (S1), R ¹⁰Be phenyl or benzyl, wherein, these phenyl or benzyl can be also 1～4 alkyl replacement through halogen atom, cyano group, carbon number,

R ¹¹That hydrogen atom or carbon number are 1～8 alkyl,

M1 is 2～8 integer,

M2 is 1～4 integer,

Wherein, a plurality of R ¹¹Can be identical also can be mutually different,

In the situation that there are a plurality of m1, a plurality of m1 can be identical also can be mutually different).

The present invention proposes a kind of formation method of liquid crystal orienting film, it is characterized in that through following steps:

Coating above-mentioned crystal aligning agent and forming is filmed on substrate, secondly above-mentioned filming is heated.

The present invention proposes a kind of manufacture method of liquid crystal display device, it is characterized in that through following steps:

Be coated with respectively above-mentioned crystal aligning agent and form on the above-mentioned conducting film of a pair of substrate that comprises conducting film and film;

Make to be formed with above-mentioned above-mentioned a pair of substrate Jie who films every layer of liquid crystal molecule, and with above-mentioned mode subtend configuration of filming relative, thereby liquid crystal cells formed; And

Execute under alive state between the above-mentioned conducting film that above-mentioned a pair of substrate has, above-mentioned liquid crystal cells is carried out rayed.

The effect of invention

Crystal aligning agent of the present invention can obtain the liquid crystal orienting film that vertical orientation is excellent and have the ultraviolet resistance of height.

Therefore, crystal aligning agent of the present invention is except applicable in the liquid crystal display device of VA type known since before, also can not make liquid crystal orienting film realize desired display quality in manufacturing step even need in its manufacturing step to be applicable in the liquid crystal display device of display format of the PSA pattern of strong uviolizing or renewal deterioratedly.

The ultraviolet resistance that is had height by the formed liquid crystal orienting film of crystal aligning agent of the present invention, even the liquid crystal display device that therefore comprises this liquid crystal orienting film under strong uviolizing condition, the outdoor long-time use on for example daytime, its display quality is also not deteriorated.

And, according to particularly preferred aspect of the present invention, if use crystal aligning agent of the present invention in the manufacturing of VA type liquid crystal display device, even in the situation that adopt liquid crystal drop add mode (ODF mode) in the liquid crystal filling step, also has excellent vertical orientation restraint, can positively form the liquid crystal orienting film that the ODF inequality do not occur, therefore consider extremely beneficial from the viewpoint of product yield.

Material of the present invention also can be used as MATERIALS FOR DISPLAY and in order to form such as used for liquid crystal display element protective membrane, insulating film or distance piece or organic EL with protective membrane, insulating film or barrier material etc. except crystal aligning agent.

Embodiment

As mentioned above, crystal aligning agent of the present invention contains organopolysiloxane and solvent at least.

＜organopolysiloxane 〉

There is no particular restriction for organopolysiloxane contained in crystal aligning agent of the present invention, but have the situation that preferably comprises the particular functional base according to the purposes of crystal aligning agent of the present invention.

In the situation that use crystal aligning agent of the present invention in the manufacturing of VA type liquid crystal display device, in this crystal aligning agent, contained organopolysiloxane preferably comprises the base (hereinafter referred to as " LCD alignment base ") with the function that makes liquid crystal alignment.

Use crystal aligning agent of the present invention, the base that in this crystal aligning agent, contained organopolysiloxane preferably has above-mentioned LCD alignment base and comprises the two keys of polymerizability in the manufacturing of the liquid crystal display device of (these patterns also broadly be contained in the VA type in) in the situation that the new display format of putting down in writing in PSA pattern or patent documentation 5.

And, have carboxyl by making organopolysiloxane, and the coating of the crystal aligning agent that contains this organopolysiloxane is further improved, thus preferred the use.

In addition, by making organopolysiloxane have epoxy group(ing), and make by the physical strength of the formed liquid crystal orienting film of crystal aligning agent that contains this organopolysiloxane excellent, the liquid crystal display device of all excellent performances such as can making thermotolerance, photostabilization that become, thereby preferred the use.

Above-mentioned LCD alignment base is such as enumerating the represented base of following formula (D ') etc.

(in formula (D '), R ^IBe that carbon number is that 1～40 alkyl, carbon number are 1～40 fluoroalkyl, cyano group or fluorine atom, or the carbon number with steroid skeleton is 17～51 alkyl;

Z ^IBe singly-bound, ^*-O-, ^*-COO-or ^*(wherein, the key with " * " is R to-OCO- ^ISide),

R ^IIBe cyclohexylidene or phenylene, wherein this cyclohexylidene or phenylene can be also 1～3 alkyl replacement through cyano group, fluorine atom, trifluoromethyl or carbon number,

N1 is 1 or 2,

Wherein, be 2 o'clock at n1,2 R ^IICan be mutually identical also can be different, n2 is 0 or 1;

Z ^IIBe singly-bound, ^*-O-, ^*-COO-or ^*(wherein, the key with " * " is R to-OCO- ^ISide),

N3 is 0～2 integer,

N4 is 0 or 1)

R in above-mentioned formula (D ') ^ICarbon number be that 1～40 alkyl is preferably straight chained alkyl, particularly, such as enumerating methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-octyl, positive decyl, dodecyl, n-hexadecyl, stearyl etc.;

Carbon number is that 1～40 fluoroalkyl is preferably the straight chain fluoroalkyl, particularly, for example can enumerate 3-trifluoromethyl propyl group, 4-trifluoromethyl butyl, 6-trifluoromethyl hexyl, 10-trifluoromethyl decyl, 3-pentafluoroethyl group propyl group, 4-pentafluoroethyl group butyl, 8-pentafluoroethyl group octyl group, 3,3,4,4,5,5,5-, seven fluorine amyl groups, 3,3,4,4,5,5,6,6,7,7,8,8,8-, ten trifluoro octyl groups, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-, 17 fluorine decyls etc.;

Above-mentioned carbon number with steroid skeleton is that 17～51 alkyl is such as enumerating 3-cholestane base, 3-cholesteryl, 3-lanostane base, 3-cholane base, 3-pregnane base, 3-androstane alkyl, the female alkyl of 3-etc.

At R ^IFor the both sides of alkyl and n2 and n4 are 0 o'clock, R ^IAlkyl to be preferably carbon number be 4～40 straight chained alkyl.

R in above-mentioned formula (D ') ^IICyclohexylidene and phenylene be preferably respectively Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylene.As in above-mentioned formula (D ')-(R ^II) _n1-represented divalent base is in the situation that n1 is 1, such as enumerating Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene etc. as preferred base;

In the situation that n1 is 2, for example can enumerate 4,4 '-biphenylene, 4,4 '-Ya bi(cyclohexan)yl, following formula respectively the base etc. of expression as preferred base.

(in above-mentioned formula, the key of having " * " is R ^ISide)

N3 in above-mentioned formula (D ') is preferably 2.

Preferably in above-mentioned formula (D '), n2 be 1 or n2 be 0, and R ^IThat carbon number with steroid skeleton is 17～51 alkyl.

By making organopolysiloxane comprise the represented base of the above-mentioned formula of this kind (D '), can make by the good LCD alignment ability of the formed film performance of the crystal aligning agent that contains it, thus preferred the use.

In the situation that use crystal aligning agent of the present invention in the manufacturing of VA type liquid crystal display device, for 1 mole of the contained Siliciumatom of organopolysiloxane, the ratio that exists of the LCD alignment base in this crystal aligning agent in contained organopolysiloxane is preferably ratio below 0.7 mole, more preferably the ratio below 0.5 mole, be particularly preferably the ratio of 0.1 mole～0.5 mole.

The above-mentioned base of the two keys of polymerizability that comprises is such as enumerating the represented base of following formula (A) etc.

(in formula (A), R is hydrogen atom or methyl,

X ^IAnd X ^IIRespectively that Isosorbide-5-Nitrae-phenylene, methylene radical or carbon number are 2～8 alkylidene group,

Z be Sauerstoffatom ,-COO- ^*Or-OCO- ^*(wherein, the key with " * " is X ^IISide),

A, b, c and d are respectively 0 or 1,

Wherein, c be 0 and d be 1 o'clock, X ^IIIsosorbide-5-Nitrae-phenylene,

Be 0 o'clock at b, d is 0)

as the concrete example of the represented base of above-mentioned formula (A), for example can enumerate vinyl, allyl group, to styryl, (methyl) acryloyl-oxy ylmethyl, 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) acryloyl-oxy ylmethyl) 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) acryloxy methoxymethyl, 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, the acryloyl-oxy ylmethyl, 6-{[6-(acryloxy) caproyl] the oxygen base } hexyl etc.Can enumerate vinyl, allyl group in these bases, to styryl, (methyl) acryloyl-oxy ylmethyl, 2-((methyl) acryloxy) ethyl, 3-((methyl) acryloxy) propyl group and 6-{[6-(acryloxy) caproyl] the oxygen base hexyl is as preferred base.

Basic Z in above-mentioned formula (A) is preferably Sauerstoffatom.

in the situation that use crystal aligning agent of the present invention in the manufacturing of the liquid crystal display device of the new display format of putting down in writing in PSA pattern or patent documentation 5, for 1 mole of Siliciumatom contained in organopolysiloxane, the ratio that in this crystal aligning agent, contained organopolysiloxane is preferably with 0.01 mole～0.80 mole contains the base that comprises the two keys of polymerizability, be preferably the represented base of above-mentioned formula (A), more preferably be selected from the base more than a kind in above-mentioned illustrated concrete base, more preferably contain described base with the ratio of 0.02 mole～0.70 mole, further more preferably contain described base with the ratio of 0.2 mole～0.60 mole.

In the situation that in crystal aligning agent of the present invention, contained organopolysiloxane contains carboxyl, for 1 mole of Siliciumatom contained in organopolysiloxane, the ratio that exists of carboxyl is preferably ratio below 0.8 mole, the ratio of more preferably 0.01 mole～0.6 mole is particularly preferably the ratio of 0.1 mole～0.4 mole.

Above-mentioned epoxy group(ing) is the concept that comprises the both sides of Oxyranyle (1,2-epoxy group(ing)) and propylene oxide base (1,3-epoxy group(ing)).Optimization ethylene oxide base wherein.As this Oxyranyle, can be consist of in the carbon atom of oxyethane basic ring only wherein a side have key, with the situation of the Siliciumatom bond of organopolysiloxane, can be also perhaps the situation of cyclic rings oxirane group structure (both sides that consist of in the carbon atom of oxyethane basic ring become the carbon atom that consists of alicyclic ring) by this bond (be situated between according to circumstances every in conjunction with base).

In the situation that in crystal aligning agent of the present invention, contained organopolysiloxane contains epoxy group(ing), for 1 mole of Siliciumatom contained in organopolysiloxane, the ratio that exists of epoxy group(ing) is preferably ratio below 0.95 mole, the ratio of more preferably 0.10 mole～0.90 mole.

In the situation that organopolysiloxane comprises the multiple functional group in above-mentioned, the whole of each functional group can be contained in the organopolysiloxane of single kind, also the organopolysiloxane with the part in desired functional group can be mixed into mixture and use with the organopolysiloxane with residue functional group.Certainly, also organopolysiloxane more than 3 kinds can be mixed and use, also the organopolysiloxane more than 2 kinds with identical functional group can be mixed and use.From be no matter which kind of aspect all can viewpoint, if whole as the organopolysiloxane of single thing or mixture, as long as have above-mentioned each functional group with above-mentioned scope, can effectively show the desired effect of the application.Therefore, in the situation that organopolysiloxane is made mixture and use, above-mentioned each functional group's preferable range is interpreted as respectively the mole number take the gross weight of polyorganosiloxane mixtures as benchmark.

For organopolysiloxane contained in crystal aligning agent of the present invention, utilize the polystyrene conversion weight average molecular weight that gel permeation chromatography is measured to be preferably 500～1,000,000, more preferably 1,000～100,000, further more preferably 1,000～50,000.In the situation that organopolysiloxane is the mixture of organopolysiloxane more than 2 kinds, possess above-mentioned molecular weight as all of mixture and get final product, but preferably each of each organopolysiloxane possesses above-mentioned molecular weight.

[manufacturing process of organopolysiloxane]

Organopolysiloxane as above no matter by which kind of method obtain all can, for example can utilize method as described below and synthesize.

In crystal aligning agent of the present invention, contained preferred organopolysiloxane for example can utilize any means of following 3 kinds of methods and synthesize.

(1) utilize through the method for following steps and can synthesize the organopolysiloxane that comprises the LCD alignment base: the step (manufacturing process 1) that makes the mixture of the silane compound (hereinafter referred to as " silane compound (a1) ") that comprises LCD alignment base and alkoxyl group or silane compound (a1) and other silane compounds carry out polycondensation.

(2) utilize through the method for following steps and can synthesize the organopolysiloxane that comprises the LCD alignment base: make to have the base that contains the two keys of polymerizability and the silane compound (hereinafter referred to as " silane compound (a2) ") of alkoxyl group, or the mixture of silane compound (a2) and other silane compounds step of carrying out polycondensation, at first synthetic organopolysiloxane (hereinafter referred to as " forerunner's organopolysiloxane (A1) ") with the two keys of polymerizability, the step (manufacturing process 2) that next reacts this forerunner's organopolysiloxane (A1) and the compound (hereinafter referred to as " the nucleophilicity compound that contains the LCD alignment base ") that comprises LCD alignment base and nucleophilicity base.

In this manufacturing process 2, by together also using the compound (hereinafter referred to as " the nucleophilicity compound that contains carboxyl ") with carboxyl and nucleophilicity base with the nucleophilicity compound that contains the LCD alignment base, can synthesize the organopolysiloxane that has simultaneously LCD alignment base and carboxyl.

In addition, in manufacturing process 2, amount by making the two keys of polymerizability that total usage quantity that the nucleophilicity compound that contains the LCD alignment base and (in the situation that use) are contained the nucleophilicity compound of carboxyl has than forerunner organopolysiloxane (A1) still less can be synthesized the organopolysiloxane of have the LCD alignment base (and carboxyl) and polymerizability two keys.

(3) utilize the method for process following steps can synthesize the organopolysiloxane that comprises the LCD alignment base: to make the silane compound (hereinafter referred to as " silane compound (a3) ") with epoxy group(ing) and alkoxyl group, or the mixture of silane compound (a3) and other silane compounds step of carrying out polycondensation, at first synthetic organopolysiloxane (hereinafter referred to as " forerunner's organopolysiloxane (A2) ") with epoxy group(ing), the step (manufacturing process 3) that next reacts this forerunner's organopolysiloxane (A2) and the compound (hereinafter referred to as " carboxylic acid that contains the LCD alignment base ") with LCD alignment base and carboxyl.

When forerunner's organopolysiloxane (A2) of synthetic this manufacturing process 3, (a3) together uses other silane compounds with silane compound, and use silane compound (a2) at least a portion of these other silane compounds, can synthesize thus the organopolysiloxane that has simultaneously LCD alignment base and the two keys of polymerizability.

In addition, in manufacturing process 3, the amount of the epoxy group(ing) that the usage quantity by making the carboxylic acid that contains the LCD alignment base has than forerunner organopolysiloxane (A2) still less can be synthesized the organopolysiloxane of have the LCD alignment base (and the two keys of polymerizability) and epoxy group(ing).

In above-mentioned, so-called " other silane compounds " means the silane compound beyond necessary silane compound in this manufacturing process.Therefore, for example in manufacturing process (1), necessary silane compound is only silane compound (1), therefore this moment " other silane compounds " comprises silane compound (a2) and silane compound (a3), further also comprises silane compound (a1)～silane compound (a3) silane compound (hereinafter referred to as " silane compound (a4) ") in addition.Similarly, " other silane compounds " in manufacturing process 2 comprises silane compound (a1), silane compound (a3) and silane compound (a4);

" other silane compounds " in manufacturing process 3 comprises silane compound (a1), silane compound (a2) and silane compound (a4).In addition, in above-mentioned manufacturing process 2, in the situation that also use the nucleophilicity compound that contains carboxyl as the nucleophilicity compound, the silane compound that uses in preferred polycondensation does not contain silane compound (a3).

If gather above manufacture method, table 1 described as follows is arranged like that.

Table 1

＜silane compound 〉

Contain the LCD alignment base: the silane compound (silane compound (a1)) with LCD alignment base and alkoxyl group

Contain C=C: the silane compound (silane compound (a2)) with the two keys of polymerizability and alkoxyl group

Contain epoxy group(ing): the silane compound (silane compound (a3)) with epoxy group(ing) and alkoxyl group

Other: the alkoxysilane compound containing trialkylsilyl group in molecular structure (a4) beyond above-mentioned

＜footnote 〉

¹⁾In the situation that and preferably do not use with the nucleophilicity compound that contains carboxyl.

²⁾The kind that depends on the silane compound that uses in polycondensation.

³⁾The amount that depends on the compound that uses in the reaction in the 2nd stage.

These methods at random can be made up and synthetic organopolysiloxane with desired base, utilize these methods and synthetic organopolysiloxane one kind or two or more by suitable selection, can be used as the organopolysiloxane that contains in crystal aligning agent of the present invention and use.

Below, the synthetic method of above-mentioned organopolysiloxane is described in detail.

Above-mentioned silane compound (a1) is the silane compound with LCD alignment base and alkoxyl group.

The LCD alignment base that silane compound (a1) has with as LCD alignment base that organopolysiloxane preferably had and above-mentioned illustrated identical.

This kind silane compound (a1) for example can be enumerated the represented compound of following formula (a1).

(in formula (a1), R ^I, R ^II, Z ^I, Z ^II, n1, n2, n3 and n4 respectively with above-mentioned formula (D ') in synonym, R ¹Be that carbon number is that 1～12 alkyl or carbon number are 6～12 aryl, e is 1～3 integer.)

R in above-mentioned formula (a1) ¹Carbon number be 1～12 alkyl to be preferably carbon number be 1～4 alkyl, as its concrete example, such as enumerating methyl, ethyl, n-propyl, normal-butyl, sec-butyl, the tertiary butyl etc., be preferably methyl, ethyl or n-propyl, be particularly preferably ethyl.Carbon number is that 6～12 aryl is such as enumerating phenyl, p-methylphenyl etc.

E in above-mentioned formula (a1) is preferably 1 or 2, is particularly preferably 1.

as the concrete example of this kind silane compound (a1), for example can enumerate the n-octyl Trimethoxy silane, positive decyl Trimethoxy silane, the dodecyl Trimethoxy silane, Octadecane base Trimethoxy silane, 3-cholestane base Trimethoxy silane, 3-cholesteryl Trimethoxy silane, 4-pentyloxy phenyl Trimethoxy silane, 4-hexyloxy phenyltrimethoxysila,e, 4-octyloxyphenyl Trimethoxy silane, 4-dodecyloxy phenyltrimethoxysila,e, 4-(4-propyl group cyclohexyl) phenyltrimethoxysila,e, 4-(4-butyl cyclohexyl) phenyltrimethoxysila,e, 4-(4-amyl group cyclohexyl) phenyltrimethoxysila,e, 4-(4-hexyl cyclohexyl) phenyltrimethoxysila,e, 4-(4-heptyl cyclohexyl) phenyltrimethoxysila,e, 4-(4-octyl group cyclohexyl) phenyltrimethoxysila,e, 4-(4-decyl cyclohexyl) phenyltrimethoxysila,e, 4-(4-propyl group bi(cyclohexan)yl) Trimethoxy silane, 4-(4-butyl bi(cyclohexan)yl) Trimethoxy silane, 4-(4-amyl group bi(cyclohexan)yl) Trimethoxy silane, 4-(4-hexyl bi(cyclohexan)yl) Trimethoxy silane, 4-(4-heptyl bi(cyclohexan)yl) Trimethoxy silane, 4-(4-octyl group bi(cyclohexan)yl) Trimethoxy silane, 4-(4-decyl bi(cyclohexan)yl) Trimethoxy silane etc., preferred use be selected from these compounds more than a kind.

Above-mentioned silane compound (a2) is the silane compound with the two keys of polymerizability and alkoxyl group.

The two keys of the polymerizability that silane compound (a2) has with as polymerizability pair keys that organopolysiloxane preferably had and above-mentioned illustrated identical.

This kind silane compound (a2) is such as enumerating the represented compound of following formula (a2) etc.

(in formula (a2), R, X ^I, X ^II, Z, a, b, c and d respectively with above-mentioned formula (A) in synonym, R ¹Be that carbon number is that 1～12 alkyl or carbon number are 6～12 aryl, e is 1～3 integer)

About the R in above-mentioned formula (a2) ¹Carbon number be 1～12 alkyl and e, and about the R in above-mentioned formula (a1) ¹And the explanation of e is identical.

as the concrete example of this kind silane compound (a2), for example can enumerate vinyltrimethoxy silane, 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 the styryl Trimethoxy silane, to the 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) acryloxy methyltrimethoxy silane, (methyl) acryloxy Union carbide A-162, (methyl) acryloyl-oxy ylmethyl three positive propoxy silane, (methyl) acryloyl-oxy ylmethyl three-isopropoxy silane, (methyl) acryloyl-oxy ylmethyl three n-butoxy silane, (methyl) acryloxy methyl-propyl three sec-butoxy silane, 2-(methyl) acryloxy ethyl trimethoxy silane, 2-(methyl) acryloxy ethyl triethoxysilane, 2-(methyl) acryloxy ethyl three positive propoxy silane, 2-(methyl) acryloxy ethyl three isopropoxy silane, 2-(methyl) acryloxy ethyl three n-butoxy silane, 2-(methyl) acryloxy ethyl propyl three sec-butoxy silane,

3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group three positive propoxy silane, 3-(methyl) acryloxy propyl group three isopropoxy silane, 3-(methyl) acryloxy propyl group three n-butoxy silane, 3-(methyl) acryloxy propyl group 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, acryloxy methyltrimethoxy silane etc., preferred use be selected from these compounds more than a kind.More than a kind of group that more preferably select free vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, consists of to the styryl Trimethoxy silane, to styryl triethoxyl silane, (methyl) acryloxy methyltrimethoxy silane, 2-(methyl) acryloxy ethyl trimethoxy silane and 3-(methyl) acryloxy propyl trimethoxy silicane.

Above-mentioned silane compound (a3) is the silane compound with epoxy group(ing) and alkoxyl group.

The epoxy group(ing) that silane compound (a2) has with as epoxy group(ing) that organopolysiloxane preferably had and above-mentioned illustrated identical.

This kind silane compound (a3) for example is preferably the represented compound of following formula (a3).

(R ⁵) _h(R ⁶) _iSi(OR ⁷) _4-h-i (a3)

(in formula (a3), R ⁵1 valency base with epoxy group(ing),

R ⁶That carbon number is 1～3 alkyl,

R ⁷Be that carbon number is that 1～12 alkyl or carbon number are 6～12 aryl, h is 1～3 integer, and i is 0～2 integer, wherein, and h+i≤3)

R in formula (a3) ⁵For example can enumerate 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl) ethyl etc.R ⁶Be preferably methyl.About R ⁷, and about the R in above-mentioned formula (a1) ¹And above-mentioned identical.H is preferably 1, i and is preferably 0 or 1.

concrete example as silane compound (a3), for example can enumerate 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane, 3-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, 3-glycidyl ether oxygen base propyl-dimethyl methoxy silane, 3-glycidyl ether oxygen base propyl-dimethyl Ethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc., can use be selected from these compounds more than a kind.

Silane compound (a4) is silane compound (a1)～silane compound (a3) silane compound in addition, and is the silane compound arbitrarily with LCD alignment base, the two keys of polymerizability and epoxy group(ing).This silane compound (a4) for example can be enumerated the represented compound of following formula (a4).

(R ⁸) _jSi(OR ⁹) _4-j (a4)

(in formula (a4), R ⁸That carbon number is 1～7 alkyl or phenyl,

R ⁹Be that carbon number is that 1～12 alkyl or carbon number are 6～12 aryl, j is 0～3 integer.)

About the R in above-mentioned formula (a4) ⁹, and about the R in above-mentioned formula (a2) ¹And above-mentioned identical.

As the concrete example of silane compound (a4), j is that 0 compound is such as enumerating tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four secondary propoxy-silane, four n-butoxy silane, four sec-butoxy silane etc.;

j is that 1 compound for example can be enumerated 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, three pairs of methylenedioxy phenoxy base silanes of methyl, 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, three pairs of methylenedioxy phenoxy base silanes of ethyl, the n-propyl Trimethoxy silane, the 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, three pairs of methylenedioxy phenoxy base silanes of n-propyl, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl three positive propoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, phenyl three sec-butoxy silane, the normal-butyl Trimethoxy silane, 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, three pairs of methylenedioxy phenoxy base silanes of normal-butyl, the n-pentyl Trimethoxy silane, the 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, three pairs of methylenedioxy phenoxy base silanes of n-pentyl, the hexyl Trimethoxy silane, the hexyl triethoxyl silane, the heptyl Trimethoxy silane, the heptyl triethoxyl silane, 3-urea groups propyl-triethoxysilicane etc.,

j is that 2 compound for example can be enumerated dimethyldimethoxysil,ne, diethyl dimethoxy silane, diη-propyl dimethoxy silane, diisopropyl dimethoxy silane, dimethyldiethoxysilane, the diethyl diethoxy silane, the diη-propyl diethoxy silane, the di-isopropyl diethoxy silane, dimethyl diisopropoxy silane, diethyl diisopropoxy silane, diη-propyl diisopropoxy silane, di-isopropyl diisopropoxy silane, dimethyl di-secondary butoxy silane, diethyl di-secondary butoxy silane, diη-propyl di-secondary butoxy silane, di-isopropyl di-secondary butoxy silane etc.,

j is that 3 compound for example can be enumerated the trimethylammonium methoxy silane, the triethyl methoxy silane, three n-propyl methoxy silane, the triisopropyl methoxy silane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane, three n-propyl Ethoxysilanes, the triisopropyl Ethoxysilane, trimethylammonium positive propoxy silane, triethyl positive propoxy silane, three n-propyl positive propoxy silane, triisopropyl positive propoxy silane, trimethylammonium isopropoxy silane, triethyl isopropoxy silane, three n-propyl isopropoxy silane, triisopropyl isopropoxy silane, trimethylammonium sec-butoxy silane, triethyl sec-butoxy silane, three n-propyl sec-butoxy silane, triisopropyl sec-butoxy silane etc., preferred use be selected from these compounds more than a kind.

R in formula (a4) ⁸Be preferably carbon number and be 1～3 alkyl or phenyl.It is 0 or 1 compound that silane compound (a4) more preferably uses in above-mentioned formula (a4) j, further more preferably use more than a kind of group that selects free ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, tetramethoxy-silicane and tetraethoxysilane to consist of, particularly preferably using in above-mentioned formula (a4) j is 0 compound, wherein particularly preferably uses more than a kind of group that selects free tetramethoxy-silicane and tetraethoxysilane to consist of.

The contained organopolysiloxane in making crystal aligning agent of the present invention in the situation that utilize manufacturing process 1, for silane compound is all, the silane compound that uses as its raw material preferably comprises the silane compound as above (a1) more than 1mol%, more preferably comprises 1mol%～20mol%.In manufacturing process 1, preferably also also use silane compound (a4) except silane compound (a1).For silane compound is all, be preferably below 80mol% as the usage ratio of silane compound (a4), more preferably 20mol%～70mol%.Contained organopolysiloxane in making crystal aligning agent of the present invention, preferably do not use silane compound (a1) and silane compound (a4) silane compound in addition in the situation that utilize manufacturing process 1.

Make organopolysiloxane in the situation that utilize manufacturing process 2, the silane compound that uses as its raw material preferably comprises the silane compound as above (a2) more than 10mol%, more preferably comprises 20mol%～60mol%.In manufacturing process 2, preferably also also use silane compound (a4) except silane compound (a2).For silane compound was all, the usage ratio of silane compound (a4) was preferably below 80mol%, more preferably 1mol%～50mol%.Contained organopolysiloxane in making crystal aligning agent of the present invention, preferably do not use silane compound (a2) and silane compound (a4) silane compound in addition in the situation that utilize manufacturing process 2.

In the situation that utilize manufacturing process 3 to make organopolysiloxane, the silane compound that uses as its raw material preferably comprises the silane compound as above (a3) more than 20mol%, more preferably comprises 30mol%～100mol%.In manufacturing process 3, also can and use silane compound (a2) and silane compound (a4) except silane compound (a3).When this situation, for silane compound was all, the usage ratio of silane compound (a2) was preferably below 80mol%, more preferably 50mol%～70mol%;

For silane compound was all, the usage ratio of silane compound (a4) was preferably below 50mol%, more preferably below 30mol%.Contained organopolysiloxane in making crystal aligning agent of the present invention, preferably do not use silane compound (a2)～silane compound (a4) silane compound in addition in the situation that utilize manufacturing process 3.

By silane compound as above or its mixture are carried out polycondensation, can synthesize respectively organopolysiloxane contained in crystal aligning agent of the present invention or as forerunner's organopolysiloxane (A1) or forerunner's organopolysiloxane (A2) of its presoma.

Below, the polycondensation method of silane compound or its mixture is illustrated.

Forerunner's organopolysiloxane (A2) in organopolysiloxane in above-mentioned manufacturing process 1, the forerunner's organopolysiloxane (A1) in manufacturing process 2 or manufacturing process 3 can be made by silane compound as above (or its mixture) is carried out polycondensation.The polycondensation of silane compound for example can utilize respectively following method and make:

Make under the existence of dicarboxylic acid and alcohol silane compound as above reaction method (condensation methods 1),

To silane compound as above be hydrolyzed, the method (condensation methods 2) of condensation etc.

Below, in turn condensation methods 1 and condensation methods 2 are illustrated.

[condensation methods 1]

Condensation methods 1 is the method for silane compound reaction as above that makes under the existence of dicarboxylic acid and alcohol.

Dicarboxylic acid as used herein can be oxalic acid, propanedioic acid, be that on 2～4 alkylidene group, bond has compound that 2 carboxyls form, phthalic acid etc. at carbon number.Particularly, such as can enumerate oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid, terephthalic acid etc., preferred use be selected from these compounds more than a kind.Be particularly preferably oxalic acid.

The usage ratio of dicarboxylic acid, the alkoxyl group that has with respect to the silane compound that uses as raw material and aryloxy (below, in the explanation of condensation methods, these bases are generically and collectively referred to as " alkoxyl group ") 1 mole of total, the amount of carboxyl preferably becomes the amount of 0.2 mole～2.0 moles, more preferably becomes the amount of 0.5 mole～1.5 moles.

Above-mentioned alcohol can suitable use primary alconol.As its concrete example, for example can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, uncle-butanols, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, uncle-amylalcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, 3-enanthol, n-Octanol, 2-Ethylhexyl Alcohol, nonanol-, 2,6-2,6-dimethyl-4-heptanol, nonylcarbinol, phenol, hexalin, methyl-cyclohexanol, 3,3,5-cyclonol, phenylcarbinol, diacetone alcohol etc., preferred use be selected from these compounds more than a kind.It is 1～4 aliphatic primary alcohol that alcohol as used herein is preferably carbon number, more preferably use more than a kind of group that selects free methyl alcohol, ethanol, Virahol, n-propyl alcohol, isopropylcarbinol, sec-butyl alcohol and uncle-butanols to consist of, particularly preferably use more than a kind of group that selects free methyl alcohol and ethanol to consist of.

As the usage ratio of the alcohol in condensation methods 1, it is to make silane compound and dicarboxylic acid shared ratio in the total amount of reaction soln preferably become the ratio of 3 % by weight～80 % by weight, more preferably becomes the ratio of 25 % by weight～70 % by weight.

Temperature of reaction is preferably 1 ℃～100 ℃, more preferably 15 ℃～80 ℃.Reaction times is preferably 0.5 hour～and 24 hours, more preferably 1 hour～8 hours.

In condensation methods 1, preferably do not use other solvents except alcohol as above.

Supposition is worked by the intermediate that reaction pure and by silane compound and dicarboxylic acid is generated in condensation methods 1 as above, thereby generates the organopolysiloxane as (being total to) condenses of silane compound.

[condensation methods 2]

Condensation methods 2 be to silane compound as above (or its mixture) be hydrolyzed, the method for condensation.

This hydrolysis, condensation reaction can be carried out in the following way: preferably under the existence of catalyzer, preferably make the reaction of silane compound and water in suitable organic solvent.

In for the amount of 1 mole of the total of the alkoxyl group that silane compound was had that uses as raw material, the ratio of water as used herein is preferably 0.5 mole～2.5 moles.

Above-mentioned catalyzer can be enumerated acid, alkali, metallic compound etc.As the concrete example of this kind catalyzer, acid is such as enumerating hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, toxilic acid etc.

Alkali can use any number of of mineral alkali and organic bases, and mineral alkali is such as enumerating ammonia, sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate etc.;

Organic bases for example can be enumerated the trimethylamine as triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine; Tetramethyl ammonium hydroxide etc.

Metallic compound is such as enumerating titanium compound, zirconium compounds etc.

For total 100 weight parts of the silane compound that uses as raw material, the usage ratio of catalyzer is preferably below 10 weight parts, 0.001 weight part～10 weight parts more preferably, further 0.001 weight part～1 weight part more preferably.

Above-mentioned organic solvent for example can be enumerated alcohol, ketone, acid amides, ester and other non-proton property compounds.Above-mentioned alcohol can use alcohol with 1 hydroxyl, have the alcohol of a plurality of hydroxyls and have part ether any number of of the alcohol of a plurality of hydroxyls.Above-mentioned ketone can preferably use single ketones and beta-diketon.

Concrete example as this kind organic solvent, alcohol with 1 hydroxyl for example can be enumerated methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, uncle-butanols, Pentyl alcohol, primary isoamyl alcohol, 2-methyl butanol, uncle-amylalcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl amyl alcohol, 2-ethyl butanol, 3-enanthol, n-Octanol, 2-Ethylhexyl Alcohol, nonanol-, 2,6-2,6-dimethyl-4-heptanol, nonylcarbinol, phenol, hexalin, methyl-cyclohexanol, 3,3,5-cyclonol, phenylcarbinol, diacetone alcohol etc.;

Alcohol with a plurality of hydroxyls for example can be enumerated ethylene glycol, 1,2-PD, 1,3 butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexylene glycol, 2,4-heptanediol, 2-ethyl-1,3-hexylene glycol, Diethylene Glycol, dipropylene glycol, triethylene glycol, tripropylene glycol etc.;

part ether with alcohol of a plurality of hydroxyls for example can be enumerated ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol ether, the glycol monomethyl phenyl ether, glycol monomethyl-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, the Diethylene Glycol monohexyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list propyl ether etc.,

Single ketones for example can be enumerated acetone, butanone, methyl n-propyl ketone, methyl n-butyl ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, ethyl normal-butyl ketone, methyl n hexyl ketone, diisobutyl ketone, trimethylammonium nonanone, pimelinketone, methyl-n-butyl ketone, methylcyclohexanone, 2,4-diacetylmethane, acetonyl-acetone, methyl phenyl ketone, fenchone etc.;

Above-mentioned beta-diketon for example can be enumerated methyl ethyl diketone, 2,4-hexanedione, 2,4-heptadione, 3,5-heptadione, 2,4-acetyl caproyl, 3,5-acetyl caproyl, 2,4-diketone in the ninth of the ten Heavenly Stems, 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 for example can be enumerated 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-ethanoyl morpholine, N-ethanoyl piperidines, N-acetyl-pyrrolidine etc.;

ester for example can be enumerated diethyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetic acid-3-methoxyl group butyl ester, methyl amyl acetate, acetic acid-2-ethyl butyl ester, 2-ethyl hexyl ethanoate, the acetic acid benzyl ester, ethyl cyclohexyl base ester, acetic acid methylcyclohexyl ester, n-nonyl acetate, methyl acetoacetate, methyl aceto acetate, acetic acid ethylene glycol monomethyl ether ester, the ethylene glycol monoethyl ether acetate ester, acetic acid diethylene glycol monomethyl ether ester, the acetic acid diethylene glycol monoethyl ether ester, acetic acid Diethylene Glycol mono-n-butyl ether ester, acetic acid propylene glycol monomethyl ether ester, acetic acid dihydroxypropane single-ether ester, acetic acid propylene glycol monopropyl ether ester, acetic acid propylene glycol monobutyl ether ester, acetic acid dipropylene glycol monomethyl ether ester, acetic acid DPE ester, diacetate glycol ester, 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, the lactic acid n-pentyl ester, diethyl malonate, dimethyl phthalate, diethyl phthalate etc.,

Other non-protonic solvents for example can be enumerated acetonitrile, dimethyl sulfoxide (DMSO), N, N, N ', N '-tetraethyl-sulphamide, 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., can use be selected from these solvents more than a kind.

As the usage ratio of organic solvent, total weight shared ratio in the total amount of reaction soln of the composition beyond the organic solvent in reaction soln preferably becomes the ratio of 1 % by weight～90 % by weight, more preferably becomes the ratio of 10 % by weight～70 % by weight.

The water that adds when making organopolysiloxane in condensation methods 2 can be intermittently or is made an addition to continuously as in the solution that forms in being dissolved in organic solvent in the silane compound of raw material or with silane compound.

Catalyzer can make an addition in advance as being dissolved in the solution that forms in organic solvent in the silane compound of raw material or with silane compound, perhaps also can be dissolved or dispersed in advance in the water that adds.

In the situation that as the manufacture method of organopolysiloxane, can carrying out as described above, employing manufacturing process 1 obtains organopolysiloxane contained in crystal aligning agent of the present invention.

In the situation that adopt manufacturing process 2 as the manufacture method of organopolysiloxane, can make forerunner's organopolysiloxane (A1) of carrying out as described above and obtaining further with the nucleophilicity compound that contains the LCD alignment base or contain the nucleophilicity compound and the mixture reaction that contains the nucleophilicity compound of carboxyl of LCD alignment base, obtain therefrom organopolysiloxane contained in crystal aligning agent of the present invention.As forerunner's organopolysiloxane (A1), forerunner's organopolysiloxane (A1) of making except utilizing aforesaid method, such as also using the commercially available products such as AC-SQ TA-100 (Toagosei Co., Ltd's manufacturing).

In the situation that adopt manufacturing process 3 as the manufacture method of organopolysiloxane, can make forerunner's organopolysiloxane (A2) of carrying out as described above and obtaining further with the carboxylic acid reaction that contains the LCD alignment base, obtain therefrom organopolysiloxane contained in crystal aligning agent of the present invention.

[nucleophilicity compound]

The nucleophilicity compound that contains the LCD alignment base that uses in manufacturing process 2 and the nucleophilicity compound that contains carboxyl that at random uses are respectively at least a kind of nucleophilicity compounds that selects the group that free amine and mercaptan consists of, and wherein this nucleophilicity compound has LCD alignment base or carboxyl.

LCD alignment nucleophilicity compound is preferably the nucleophilicity compound with the represented base of above-mentioned formula (D ').

In the situation that LCD alignment nucleophilicity compound is for having the amine (hereinafter referred to as " compound (c1-1) ") of the represented base of above-mentioned formula (D '), the R in above-mentioned formula (D ') ^IBe preferably carbon number and be 4～20 alkyl or carbon number and be 4～20 fluoroalkyl.

Compound (c1-1) preferably uses primary amine or secondary amine.As the compound (c1-1) of primary amine such as enumerating amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, nonadecyl amine, 4-(4-amyl group cyclohexyl)-phenyl amine, 4-octyloxyphenyl amine etc.;

As the compound (c1-1) of secondary amine such as can enumerate dibutylamine, diamyl amine, dihexyl amine, diheptyl amine, dioctylamine, dinonyl amine, didecylamine, two (undecyl) amine, two (dodecyl) amine, two (tridecyl) amine, two (tetradecyl) amine, two (pentadecyl) amine, two (hexadecyl) amine, two (heptadecyl) amine, two (octadecyl) amine, two (nonadecyl) amine etc., can preferably use be selected from these compounds more than a kind.

R in formula (D ') in compound (c1-1) ^IBe preferably carbon number and be 4～12 alkyl or carbon number and be 4～12 fluoroalkyl.

In above-claimed cpd (c1-1); be difficult to gelation when particularly certainly reacting with the forerunner's organopolysiloxane (A1) with (methyl) acryl, reach easily synthetic viewpoint consideration, preferably use is as the compound (c1-1) of secondary amine.

Usage ratio as compound (c1-1), the ratio of the mole number of the two keys of the polymerizability that is had with respect to forerunner's organopolysiloxane (A1) with compound (c1-1) is preferably 5mol% above and not enough 100mol%, more preferably 10mol%～40mol%.

As the amine (hereinafter referred to as " compound (c1-2) ") of the nucleophilicity compound that contains carboxyl such as can enumerate glycine, α-alanine, Beta-alanine, butyrine, beta-aminobutyric acid, γ-aminobutyric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 7-aminoheptylic acid etc., can use be selected from these compounds more than a kind.

As the usage ratio of compound (c1-2), the ratio of the mole number of the two keys of the polymerizability that compound (c1-2) has with respect to forerunner's organopolysiloxane (A1) is preferably below 80mol%, more preferably 30mol%～70mol%.

Amine as the nucleophilicity compound in the present invention can reach the compound (c1-2) of at random use together also with other amine beyond these compounds with compound as above (c1-1).Other amine of this kind, are preferably the following scope of 40mol% and use at least a kind that is selected from these compounds with for the total of amine such as enumerating methylamine, dimethyl amine, diethylamide, dipropylamine, phenyl amine etc.In the situation that also use other amine, for the two keys of polymerizability that forerunner's organopolysiloxane (A1) has, the usage ratio of the total of all amine is preferably below 40mol%.

In manufacturing process 2 of the present invention, preferably only use compound as above (c1-1) as amine or only use compound (c1-1) and compound (c1-2) as amine.

In the situation that LCD alignment nucleophilicity compound is for having the mercaptan (hereinafter referred to as " compound (c2-1) ") of the represented base of above-mentioned formula (D '), the R in above-mentioned formula (D ') ^IBe preferably carbon number and be 4～20 alkyl or carbon number and be 4～20 fluoroalkyl, be preferably perhaps that to have carbon number be that 2～12 alkyl or carbon number are the phenyl that is substituted of 2～12 fluoroalkyl, be preferably perhaps that to have carbon number be that 2～12 alkyl or carbon number are the base with polynuclear plane of 2～12 fluoroalkyl.This polynuclear plane is such as enumerating connection cyclohexane structure, biphenyl structural, phenylcyclohexane based structures etc.

compound (c2-1) for example can be enumerated butyl sulfhydryl, pentan-thiol, hexylmercaptan, heptanthiol, spicy thioalcohol, the ninth of the ten Heavenly Stems mercaptan, decyl mercaptan, undecyl mercaptan, lauryl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, hexadecyl mercaptan, heptadecyl mercaptan, 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-tridecyl phenyl mercaptan, 4-tetradecyl phenyl mercaptan, 4-pentadecyl phenyl mercaptan, 4-hexadecyl phenyl mercaptan, 4-heptadecyl phenyl mercaptan, 4-octadecyl phenyl 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-undecane oxygen base phenyl mercaptan, 4-dodecyloxy phenyl mercaptan, 4-(4 '-the butyl cyclohexyl) phenyl mercaptan, 4-(4 '-the amyl group cyclohexyl) phenyl mercaptan, 4-(4 '-the hexyl cyclohexyl) phenyl mercaptan, 4-(4 '-the heptyl cyclohexyl) phenyl mercaptan, 4-(4 '-octyl group cyclohexyl) phenyl mercaptan etc., can preferably use be selected from these compounds more than a kind.

Usage ratio as compound (c2-1), the ratio of the mole number of the two keys of the polymerizability that compound (c2-1) has with respect to forerunner's organopolysiloxane (A2) is preferably 5mol% above and not enough 100mol%, more preferably 10mol%～40mol%.

As the mercaptan (hereinafter referred to as " compound (c2-2) ") of the nucleophilicity compound that contains carboxyl such as can enumerate Thiovanic acid, 3-thiohydracrylic acid, 4-sulfydryl butyric acid, 5-mercaptopentanoic acid, 3-mercaptopyruvate, captopril (captopril), 3-Thiosalicylic acid, 4-Thiosalicylic acid etc., can use be selected from these compounds more than a kind.

As the usage ratio of compound (c2-2), the ratio of the mole number of the two keys of the polymerizability that compound (c1-2) has with respect to forerunner's organopolysiloxane (A1) is preferably below 80mol%, more preferably 30mol%～70mol%.

In the situation that also with compound (c1-1) and compound (c1-2), add up to usage ratio as it, the ratio of the total mole number of the two keys of polymerizability that compound (c1-1) and compound (c1-2) have with respect to forerunner's organopolysiloxane (A1) is preferably below 70mol%.

As the mercaptan of the nucleophilicity compound in the present invention, can reach the compound (c2-2) of at random use together also with other mercaptan beyond these compounds with compound as above (c2-1).Other mercaptan of this kind are such as enumerating thiomethyl alcohol, sulfur alcohol, propylmercaptan, phenyl mercaptan etc., with for the total of mercaptan, can be preferably the following scope of 40mol% and use at least a kind that is selected from these compounds.In the situation that also use other mercaptan, for the two keys of polymerizability that forerunner's organopolysiloxane (A1) has, the total usage ratio of all mercaptan is preferably below 40mol%.

In manufacturing process 2 of the present invention, mercaptan preferably only uses compound as above (c2-1) or only uses compound (c2-1) and compound (c2-2).

[reaction of forerunner's organopolysiloxane (A1) and nucleophilicity compound]

About the reaction of forerunner's organopolysiloxane (A1) and nucleophilicity compound, be divided into situation that the nucleophilicity compound is amine and nucleophilicity compound and be the situation of mercaptan and be illustrated in turn.

{ the nucleophilicity compound is the situation of amine }

In the situation that the nucleophilicity compound is can carrying out in the following way with forerunner's organopolysiloxane (A1) reaction of amine: preferably under the existence of organic solvent, under the existence of catalyzer arbitrarily, both are reacted.

The organic solvent that can use in the reaction of forerunner's organopolysiloxane A1 and amine can preferably use polar compound, such as enumerating nitrile, sulfoxide, ether, ester, alcohol etc.As the concrete example of these compounds, above-mentioned nitrile is such as enumerating acetonitrile etc.;

Above-mentioned sulfoxide is such as enumerating dimethyl sulfoxide (DMSO) etc.;

Above-mentioned ether is such as enumerating diethyl ether, dipropyl ether etc.;

Above-mentioned ester is such as enumerating ethyl acetate, butylacetate etc.;

Above-mentioned alcohol is such as enumerating trifluoroethanol, five fluoroethanols etc.The viewpoint of self-reacting stability is considered, preferred nitrile or the sulfoxide of using in these compounds.The viewpoint of autoreaction speed is considered, preferably become the ratio more than 40 % by weight and use solvent with solid concentration (the total weight of the composition beyond the solvent in reaction soln in the gross weight of solution shared ratio), more preferably become the ratio of 50 % by weight～90 % by weight.

The catalyzer that can at random use in the reaction of forerunner's organopolysiloxane (A1) and amine is such as enumerating aluminum chloride, formic acid etc.

Temperature of reaction is preferably 10 ℃～100 ℃, more preferably 60 ℃～100 ℃.Reaction times is preferably 0.5 hour～and 8 hours, more preferably 1 hour～6 hours.

{ the nucleophilicity compound is the situation of mercaptan }

On the other hand, the nucleophilicity compound is that the reaction with forerunner's organopolysiloxane (A1) in the situation of mercaptan can be carried out in the following way: be preferable under the existence of organic solvent and catalyzer both are reacted.

The organic solvent that can use in the reaction of forerunner's organopolysiloxane and mercaptan for example can preferably use polar compound, such as enumerating nitrile, sulfoxide, ether, ester etc.As the concrete example of these compounds, above-mentioned nitrile is such as enumerating acetonitrile etc.;

Above-mentioned ester is such as enumerating ethyl acetate, butylacetate etc.Preferably become the ratio use solvent 40 % by weight more than with solid concentration (the total weight of the composition beyond the solvent in reaction soln in the gross weight of solution shared ratio), more preferably become the ratio of 50 % by weight～90 % by weight.

The preferred catalyzer that uses is such as enumerating organic bases etc. in the reaction of forerunner's organopolysiloxane (A1) and mercaptan, be more specifically tertiary amine, particularly can enumerate Trimethylamine, diethylmethyl amine, ethyl dimethyl amine, triethylamine, tripropylamine etc.For mercaptan 100 weight parts, the usage ratio of catalyzer is preferably below 50 weight parts, more preferably 10 weight parts～30 weight parts.

Temperature of reaction is preferably 10 ℃～100 ℃, more preferably 40 ℃～80 ℃.Reaction times is preferably 0.5 hour～and 8 hours, more preferably 1 hour～6 hours.

In manufacturing process 2, can carry out as described above and obtain organopolysiloxane contained in crystal aligning agent of the present invention.

[carboxylic acid]

The carboxylic acid that contains the LCD alignment base that uses in above-mentioned manufacturing process 3 is the compound (hereinafter referred to as " carboxylic acid (3-1) ") with LCD alignment base and carboxyl.The LCD alignment base that has about carboxylic acid (3-1), with about organopolysiloxane the LCD alignment base that can at random have and in above-mentioned illustrated identical.

The carboxylic acid that uses in manufacturing process 3 (3-1) is preferably the carboxylic acid with the represented base of above-mentioned formula (D '), more preferably the represented compound of following formula (3-1).

D′-COOH(3-1)

(in formula (3-1), D ' is the represented base of above-mentioned formula (D '))

This kind carboxylic acid (3-1) such as can enumerate longer chain fatty acid, have chain alkyl benzoic acid derivative, have the long-chain alkoxy base benzoic acid derivative, have steroid skeleton benzoic acid derivative, have steroid skeleton other carboxylic acids, have polynuclear plane benzoic acid derivative, have polynuclear plane other carboxylic acids, have the carboxylic acid of fluoroalkyl etc.As the concrete example of these compounds,

Longer chain fatty acid is such as enumerating caproic acid, n-caprylic acid, n-capric acid, dodecanoic acid, Palmiticacid, stearic acid etc.;

Has the benzoic acid derivative of chain alkyl such as enumerating 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.;

Has the benzoic acid derivative of long-chain alkoxy base such as enumerating the positive hexyloxybenzoate of 4-, 4-n-octyloxy phenylformic acid, 4-n-decyloxy phenylformic acid, 4-n-dodecane aminobenzoic acid, 4-n-hexadecane aminobenzoic acid, 4-stearyl aminobenzoic acid etc.; Has the benzoic acid derivative of steroid skeleton such as enumerating cholestane base aminobenzoic acid, cholesteryl aminobenzoic acid, lanostane base aminobenzoic acid, cholestane base oxygen base carbonyl benzoic acid, cholesteryl oxygen base carbonyl benzoic acid, lanostane base oxygen base carbonyl benzoic acid, succsinic acid-5 ξ-cholestane-3-base ester, succsinic acid-5 ξ-cholestene-3-base, succsinic acid-5 ξ-lanostane-3-base etc.;

Other carboxylic acids with steroid skeleton such as can enumerate following formula (1) and formula (2) the compound etc. of expression respectively;

benzoic acid derivative with polynuclear plane for example can be enumerated 4-(4-amyl group-cyclohexyl) phenylformic acid, 4-(4-hexyl-cyclohexyl) phenylformic acid, 4-(4-heptyl-cyclohexyl) phenylformic acid, 4 '-amyl group-Lian hexanaphthene-4-formic acid, 4 '-hexyl-Lian hexanaphthene-4-formic acid, 4 '-heptyl-Lian hexanaphthene-4-formic acid, 4 '-amyl group-biphenyl-4-formic acid, 4 '-hexyl-biphenyl-4-formic acid, 4 '-heptyl-biphenyl-4-formic acid, 4-(4 '-amyl group-Lian hexanaphthene-4-yl) phenylformic acid, 4-(4 '-hexyl-Lian hexanaphthene-4-yl) phenylformic acid, 4-(4 '-heptyl-Lian hexanaphthene-4-yl) phenylformic acid etc.,

Other carboxylic acids with polynuclear plane for example can be enumerated 6-(4 '-cyanobiphenyl-4-base oxygen base) caproic acid, 3-carboxyl

(chrysene) etc.;

Carboxylic acid with fluoroalkyl such as can enumerate following formula (3-1-1) and formula (3-1-2) the compound etc. of expression respectively, can use be selected from these compounds more than a kind.

CF ₃-(CF ₂) _k-(CH ₂) _n-COOH (3-1-1)

(in formula (3-1-1) and formula (3-1-2), k is respectively 0～2 integer, and n is respectively 3～18 integer.)

As the carboxylic acid that uses in manufacturing process 3 (3-1), be preferably benzoic acid derivative that choosing freely has polynuclear plane, have the benzoic acid derivative of steroid skeleton and have more than a kind of group that other carboxylic acids of steroid skeleton consist of.

In above-mentioned manufacturing process 3, can only use carboxylic acid as above (3-1), perhaps also can be except carboxylic acid (3-1) and with other carboxylic acid (hereinafter referred to as " carboxylic acid (3-2) ").This carboxylic acid (3-2) is not have a carboxylic acid of LCD alignment base; such as can enumerate formic acid, acetic acid, propionic acid, anthraquinone-2-formic acid, 2-(4-diethylamino-2-hydroxyl-benzoyl)-phenylformic acid etc., can use be selected from these compounds more than a kind.

For 1 mole of the epoxy group(ing) that has with respect to forerunner's organopolysiloxane (A2), usage ratio as the carboxylic acid in manufacturing process 3 (3-1) is preferably 0.1 mole～0.9 mole, more preferably 0.2 mole～0.8 mole, further more preferably 0.25 mole～0.75 mole.Herein, in the situation that together use carboxylic acid (2-2) with carboxylic acid (2-1), it is desirable to:

For 1 mole of the epoxy group(ing) that has with respect to forerunner's organopolysiloxane (A2), the usage ratio of the total of carboxylic acid (3-1) and carboxylic acid (3-2) is preferably 0.1 mole～0.9 mole, and more preferably 0.1 mole～0.6 mole, and

Carboxylic acid (3-1) is preferably with respect to the usage ratio of the total of carboxylic acid (3-1) and carboxylic acid (3-2) that 60mol% is above, the above and not enough 100mol% of 70mol% more preferably.

[reaction of forerunner's organopolysiloxane (A2) and carboxylic acid]

The reaction of forerunner's organopolysiloxane (A2) and carboxylic acid is preferably carried out under the existence of suitable catalyzer and suitable organic solvent.

The catalyzer that uses in reaction as forerunner's organopolysiloxane (A2) and carboxylic acid for example can suitable use organic bases, also the so-called hardening accelerator that promotes epoxy compounds with the reaction of acid anhydrides can be used as in addition the catalyzer in this reaction.Above-mentioned organic bases is such as enumerating organic primary amine or organic secondary amine, trimethylamine, organic quaternary amine etc.;

Above-mentioned hardening accelerator for example can be enumerated respectively tertiary amine (wherein as the trimethylamine of organic bases except), imdazole derivatives, organo phosphorous compounds, quaternary alkylphosphonium salt, diazabicyclo alkene, organometallic compound, quaternary ammonium halides, metal halogen compound, potentiality hardening accelerator etc.Above-mentioned potentiality hardening accelerators etc. are such as enumerating high-melting-point decentralized potentiality hardening accelerator (such as amine add-on type promotor etc.), microcapsule-type potentiality hardening accelerator, amine salt type potentiality hardening accelerator, the hot cationic polymerization type potentiality of high temperature dissociative type hardening accelerator etc.

As the concrete example of this catalyzer, above-mentioned organic primary amine or organic secondary amine are such as enumerating ethamine, diethylamide, piperazine, piperidines, tetramethyleneimine, pyrroles etc.;

Above-mentioned trimethylamine is such as enumerating triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine, diazabicyclo undecylene etc.;

Above-mentioned organic quaternary amine is such as enumerating Tetramethylammonium hydroxide etc.;

Above-mentioned tertiary amine (wherein as the trimethylamine of organic bases except) for example can be enumerated dimethyl benzylamine, 2,4,6-three (dimethylaminomethyl) phenol, cyclohexyl dimethyl amine, trolamine etc.;

above-mentioned imdazole derivatives for example can be enumerated glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-glyoxal ethyline, 1-(2-cyanoethyl)-2-n-undecane base imidazoles, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazoles, 2-phenyl-4,5-two (hydroxymethyl) imidazoles, 1-(2-cyanoethyl)-2-phenyl-4,5-two [(2 '-the cyano group oxyethyl group) methyl] imidazoles, 1-(2-cyanoethyl)-2-n-undecane base imidazoles trimellitic acid salt, 1-(2-cyanoethyl)-2-phenylimidazole trimellitic acid salt, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole trimellitic acid salt, 2,4-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 tricarbimide affixture of glyoxal ethyline, the tricarbimide affixture of 2-phenylimidazole, 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')] the tricarbimide affixture etc. of ethyl-s-triazine,

Above-mentioned organo phosphorous compounds is such as enumerating diphenylphosphine, triphenylphosphine, triphenyl phosphite etc.;

Above-mentioned quaternary alkylphosphonium salt for example can be enumerated benzyl base triphenyl phosphonium chloride, four normal-butyl bromination Phosphonium, first base three phenyl phosphonium bromides, ethyl triphenyl phosphonium bromide, normal-butyl three phenyl phosphonium bromides, 4-phenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, second base triphenyl phosphonium acetate, 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 diazabicyclo alkene for example can be enumerated 1,8-diazabicyclo [5.4.0] undecylene-7, its organic acid salt etc.;

Above-mentioned organometallic compound is such as enumerating zinc octoate, hot sour Tin, methyl ethyl diketone aluminium complex etc.;

Above-mentioned quaternary ammonium halides is such as enumerating tetraethylammonium bromide, tetra-n-butyl ammonium bromide, etamon chloride, tetrabutylammonium chloride etc.;

Above-mentioned metal halogen compound for example can be enumerated the boron compound as boron trifluoride, triphenyl borate; Zinc chloride, tin tetrachloride etc.;

Above-mentioned high-melting-point decentralized potentiality hardening accelerator such as the affixture that can enumerate Dyhard RU 100 or amine and epoxy resin etc.;

Potentiality hardening accelerator that above-mentioned microcapsule-type potentiality hardening accelerator forms such as the surface that can enumerate with hardening accelerators such as above-mentioned polymer overmold imdazole derivatives, organo phosphorous compounds, quaternary alkylphosphonium salts etc.;

The hot cationic polymerization type potentiality of above-mentioned high temperature dissociative type hardening accelerator such as can enumerate lewis acid, Bronsted hydrochlorate etc., can use be selected from these catalyzer more than a kind.

Preferred organic quaternary amine or the quaternary ammonium halides used in these catalyzer.

For forerunner's organopolysiloxane (A2) 100 weight parts, the usage ratio of catalyzer is preferably 0.01 weight part～100 weight parts, more preferably 0.1 weight part～20 weight parts.

The organic solvent that uses in the reaction of forerunner's organopolysiloxane (A2) and carboxylic acid is such as enumerating ketone, ether, ester, acid amides, alcohol etc.As the concrete example of this organic solvent, above-mentioned ketone is such as enumerating butanone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, metacetone, pimelinketone etc.;

Above-mentioned ether is such as enumerating glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), diox etc.;

Above-mentioned ester is such as enumerating ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, acetic acid-3-methoxyl group butyl ester, ethyl lactate etc.;

Above-mentioned acid amides for example can be enumerated 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-ethanoyl morpholine, N-ethanoyl piperidines, N-acetyl-pyrrolidine etc.;

Above-mentioned alcohol such as can enumerate 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether etc., can use be selected from these compounds more than a kind.

The usage ratio of organic solvent with the total weight of the composition beyond the organic solvent in reaction soln shared ratio in the total amount of reaction soln, preferably becomes the ratio of 0.1 % by weight～50 % by weight, more preferably becomes the ratio of 5 % by weight～50 % by weight.

The reaction of forerunner's organopolysiloxane (A2) and carboxylic acid is being preferably at the temperature of 0 ℃～200 ℃, more preferably 50 ℃～150 ℃, preferably carry out 0.1 hour～50 hours, more preferably carried out 0.5 hour～20 hours.

In manufacturing process 3, can carry out as described above and obtain organopolysiloxane contained in crystal aligning agent of the present invention.

＜solvent 〉

In crystal aligning agent of the present invention, contained solvent contains the represented compound of following formula (S1).

R ¹⁰O-((CR ¹¹ ₂) _m1-O) _m2-H (S1)

(in formula (S1), R ¹⁰Be phenyl or benzyl, wherein these phenyl or benzyl can be also 1～4 alkyl replacement through halogen atom, cyano group, carbon number,

R ¹¹That hydrogen atom or carbon number are 1～8 alkyl,

M1 is 2～8 integer,

M2 is 1～4 integer,

Wherein, a plurality of R ¹¹Can be identical also can be mutually different,

In the situation that there are a plurality of m1, a plurality of m1 can be identical also can be mutually different)

In above-mentioned formula (S1)-(CR ¹¹ ₂) _m1Ethylene, dimethylated methylene base, propylene, trimethylene, 1,1-dimethyl-ethylene, tetramethylene, hexamethylene etc. for example can be enumerated in-represented unit.Preferred ethylene or propylene in these unit.M2 in above-mentioned formula (S1) is preferably 1 or 2, and more preferably 1.

The represented compound of above-mentioned formula (S1) such as can enumerate glycol monomethyl phenyl ether, glycol monomethyl benzylic ether, propylene glycol list phenyl ether, propylene glycol single-benzyl ether, Diethylene Glycol list phenyl ether, Diethylene Glycol single-benzyl ether, dipropylene glycol list phenyl ether, dipropylene glycol single-benzyl ether, butyleneglycol list phenyl ether, butyleneglycol single-benzyl ether, dibutylene glycol list phenyl ether, dibutylene glycol single-benzyl ether, pentanediol list phenyl ether, pentanediol single-benzyl ether, two pentanediol list phenyl ethers, two pentanediol single-benzyl ethers etc., can use be selected from these compounds more than a kind.In these compounds, preferred more than a kind of group that selects free glycol monomethyl phenyl ether, glycol monomethyl benzylic ether and propylene glycol list phenyl ether to consist of that uses.

Solvent contained in crystal aligning agent of the present invention also can contain other solvents except the represented compound of above-mentioned formula (S1).

Spendable other solvents in this place for example can be enumerated the represented compound of following formula (S2), glycol and other solvents.

R ¹²O-((CR ¹³ ₂) _m3-O) _m4-H (S2)

(in formula (S1), R ¹²That carbon number is 1～6 alkyl,

R ¹³That hydrogen atom or carbon number are 1～8 alkyl,

M3 is 2～8 integer,

M4 is 1～4 integer,

Wherein, a plurality of R ¹³Can be identical also can be mutually different,

In the situation that there are a plurality of m3, a plurality of m1 can be identical also can be mutually different)

In above-mentioned formula (S2)-(CR ¹³ ₂) _m3Ethylene, dimethylated methylene base, propylene, trimethylene, 1,1-dimethyl-ethylene, tetramethylene, hexamethylene etc. for example can be enumerated in-represented unit.Preferred ethylene or propylene in these unit.M4 in above-mentioned formula (S2) is preferably 1 or 2, and more preferably 1.

The represented compound of above-mentioned formula (S2) such as can enumerate ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether (ethylene glycol butyl ether), glycol monomethyl uncle butyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, propylene glycol list uncle butyl ether etc., can use be selected from these compounds more than a kind.These compounds are preferably more than a kind of group that selects free ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether and glycol monomethyl uncle butyl ether to consist of.

Above-mentioned glycol for example be preferably carbon number be 2～10 alkylidene group both sides respectively bond the compound of hydroxyl is arranged, for example can enumerate ethylene glycol, 1,3-PD, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol etc., can use be selected from these compounds more than a kind.

above-mentioned other solvents are the above-mentioned polar solvent in addition of illustration preferably, for example can enumerate METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, DMF, N,N-dimethylacetamide, the 4-hydroxy-4-methyl-2-pentanone, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the Diethylene Glycol dipropyl ether, dibutyl ethylene glycol ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, the Diethylene glycol monopropyl ether acetic ester, butyl carbitol acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol, acetone, butanone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, ethyl lactate, dimethyl sulfoxide (DMSO), tetramethyl-urea, HMPA, meta-cresol etc., can use be selected from these compounds more than a kind.

In crystal aligning agent of the present invention, contained solvent preferably together contains glycol with the represented compound of above-mentioned formula (S 1).

In crystal aligning agent of the present invention in contained solvent, the preferable range of the ratio that above-mentioned each solvent phase occupies for the total amount of solvent is as described below respectively.

The represented compound of above-mentioned formula (S 1): be preferably 1 % by weight above, more preferably 3 % by weight～98 % by weight, further more preferably 10 % by weight～85 % by weight, be particularly preferably 20 % by weight～75 % by weight;

The represented compound of above-mentioned formula (S2): be preferably that 80 % by weight are following, more preferably 3 % by weight～60 % by weight, further 10 % by weight～50 % by weight more preferably;

Glycol: be preferably that 60 % by weight are following, more preferably 5 % by weight～50 % by weight, further 10 % by weight～40 % by weight more preferably; And

Other solvents: be preferably 10 % by weight following, more preferably 5 % by weight following, particularly preferably do not contain other solvents.

＜other compositions 〉

Crystal aligning agent of the present invention preferably contain as mentioned above and the organopolysiloxane made or its mixture and solvent as above as essential composition, only otherwise reduce effect of the present invention, also can optionally contain other compositions.These other compositions can be enumerated polymkeric substance (hereinafter referred to as " other polymkeric substance "), polymerizable unsaturated compound, Photoepolymerizationinitiater initiater, radical scavenger beyond organopolysiloxane, have the compound of at least one epoxy group(ing) in molecule that (wherein, above-mentioned organopolysiloxane has except the situation of epoxy group(ing).Hereinafter referred to as " epoxy compounds "), functional silanes compound, tensio-active agent, potentiality stiffening agent etc., can use be selected from these compounds more than a kind.

[other polymkeric substance]

Above-mentioned other polymkeric substance can with so that the electrical specification of the solution properties of the crystal aligning agent of gained and formed liquid crystal orienting film and LCD alignment further improve.These other polymkeric substance are the polymkeric substance beyond organopolysiloxane as above, such as can enumerate polyamic acid, polyimide, poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyoxymethylene, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc., can use be selected from these compounds more than a kind.

Use in the present invention in the situation of other polymkeric substance preferred more than a kind of group that selects free polyamic acid and polyimide to consist of that uses.

-polyamic acid and polyimide-

Above-mentioned polyamic acid can be made in the following way: use tetracarboxylic dianhydride and the diamines put down in writing in patent documentation 9 (Japanese Patent Laid-Open 2010-97188 communique) for example, utilize known method to make these compounds reactions.

Polyimide can be made in the following way: utilize known method above-mentioned polyamic acid to be carried out dehydration closed-loop and with its imidization.

In the situation that crystal aligning agent of the present invention contains the polymkeric substance more than a kind that selects the group that free polyamic acid and polyimide consist of, in for the total amount of the polyamic acid of organopolysiloxane 100 weight parts and polyimide, it contains proportional being preferably below 60 weight parts, more preferably below 30 weight parts.

[polymerizable unsaturated compound]

In the present invention arbitrarily used polymerizable unsaturated compound be preferably the unsaturated compound that comprises following compound: the compound (hereinafter referred to as " compound (B-1) ") that has 1 represented valency base of the represented divalent base of at least 1 following formula (B-I) and at least 2 following formulas (B-II) in molecule.This unsaturated compound can only use compound (B-1), also can be with compound (B-1) and other unsaturated compounds and use.

-X ¹-Y ¹-X ²- (B-I)

(in formula (B-I), X ¹And X ²Independent respectively is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, Y ¹Be singly-bound, carbon number be 1～4 divalent alkyl, Sauerstoffatom, sulphur atom or-COO-, wherein above-mentioned X ¹And X ²Can be also that 1～4 alkyl, carbon number are that 1～4 alkoxyl group, fluorine atom or cyano group replace through one or more carbon numbers.)

(in formula (B-II), R is hydrogen atom or methyl, Y ²And Y ³Independent respectively is Sauerstoffatom or sulphur atom.)

1 represented valency radix of above-mentioned formula (B-II) in compound (B-1) is preferably 2.

Carbon number in above-mentioned formula (B-I) is that 1～4 divalent alkyl is such as enumerating methylene radical, dimethylated methylene base etc.The represented divalent base of above-mentioned formula (B-I) such as can enumerate following formula (B-I-1)～formula (B-I-6) the base etc. of expression respectively.

Phenyl ring in above-mentioned formula (B-I-1)～formula (B-I-6) and cyclohexane ring also can be respectively is that 1～4 alkyl, carbon number are that 1～4 alkoxyl group, fluorine atom or cyano group replace through carbon number.

Y in above-mentioned formula (B-II) ²Be preferably Sauerstoffatom.

The compound that uses in the present invention (B-1) can be enumerated:

(the represented divalent base of above-mentioned formula (B-I) is the represented base of above-mentioned formula (B-I-1), the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of biphenyl structural ²And Y ³Be respectively Sauerstoffatom),

(the represented divalent base of above-mentioned formula (B-I) is the represented base of above-mentioned formula (B-I-2), the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of phenyl-cyclohexyl structure ²And Y ³Be respectively Sauerstoffatom),

(the represented divalent base of above-mentioned formula (B-I) is the represented base of above-mentioned formula (B-I-3), the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of 2,2-diphenylprop alkyl structure ²And Y ³Be respectively Sauerstoffatom),

(the represented divalent base of above-mentioned formula (B-I) is the represented base of above-mentioned formula (B-I-4), the Y in above-mentioned formula (B-II) to have two (methyl) acrylate of diphenylmethyl alkyl structure ²And Y ³Be respectively Sauerstoffatom),

(the represented divalent base of above-mentioned formula (B-I) is the represented base of above-mentioned formula (B-I-5), the Y in above-mentioned formula (B-II) to have dithio (methyl) acrylate of diphenylsulfide structure ²Be Sauerstoffatom, Y ³Be sulphur atom) and

Other compounds (B-1).

As the concrete example of these compounds, two (methyl) acrylate with biphenyl structural for example can be enumerated: vinylformic acid-4 '-acryloxy-biphenyl-4-base ester,

Methacrylic acid-4 '-methacryloxy-biphenyl-4-base ester,

Vinylformic acid-2-[4 '-(2-acryloxy-oxyethyl group)-biphenyl-4-base oxygen base]-ethyl ester,

Methacrylic acid-2-[4 '-(2-methacryloxy-oxyethyl group)-biphenyl-4-base oxygen base]-ethyl ester,

Two hydroxyl-oxethyl biphenyl diacrylates,

Two hydroxyl-oxethyl biphenyl dimethacrylate fat,

Vinylformic acid-2-(2-{4 '-[2-(2-acryloxy-oxyethyl group)-oxyethyl group]-biphenyl-4-base oxygen base }-oxyethyl group)-ethyl ester,

Methacrylic acid-2-(2-{4 '-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-biphenyl-4-base oxygen base }-oxyethyl group)-ethyl ester,

The diacrylate of the ethylene oxide adduct of biphenyl,

The dimethacrylate fat of the ethylene oxide adduct of biphenyl,

The diacrylate of the propylene oxide adduct of biphenyl,

The dimethacrylate fat of the propylene oxide adduct of biphenyl,

Vinylformic acid-2-(4 '-acryloxy-biphenyl-4-base oxygen base)-ethyl ester,

Methacrylic acid-2-(4 '-methacryloxy-biphenyl-4-base oxygen base)-ethyl ester etc.;

Two (methyl) acrylate with phenyl-cyclohexyl structure for example can be enumerated: vinylformic acid-4-(4-acryloxy-phenyl)-cyclohexyl,

Methacrylic acid-4-(4-methacryloxy-phenyl)-cyclohexyl,

Vinylformic acid-2-{4-[4-(2-acryloxy-oxyethyl group)-phenyl]-cyclohexyloxy }-ethyl ester,

Methacrylic acid-2-{4-[4-(2-methacryloxy-oxyethyl group)-phenyl]-cyclohexyloxy }-ethyl ester,

Vinylformic acid-2-[2-(4-{4-[2-(2-acryloxy-oxyethyl group)-oxyethyl group]-phenyl }-cyclohexyloxy)-oxyethyl group]-ethyl ester,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-phenyl }-cyclohexyloxy)-oxyethyl group]-ethyl ester etc.;

Two (methyl) acrylate with 2,2-diphenylprop alkyl structure for example can be enumerated: vinylformic acid-4-[1-(4-acryloxy-phenyl)-1-methyl-ethyl]-phenyl ester,

Methacrylic acid-4-[1-(4-methacryloxy-phenyl)-1-methyl-ethyl]-phenyl ester,

Vinylformic acid-2-(4-{1-[4-(2-acryloxy-oxyethyl group)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethyl ester,

Methacrylic acid-2-(4-{1-[4-(2-methacryloxy-oxyethyl group)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethyl ester, two hydroxyl-oxethyl-bisphenol a diacrylate,

Two hydroxyl-oxethyls-dihydroxyphenyl propane dimethacrylate fat,

Vinylformic acid-2-{2-[4-(1-{4-[2-(2-acryloxy-oxyethyl group)-oxyethyl group]-phenyl }-1-methyl-ethyl)-phenoxy group]-oxyethyl group }-ethyl ester,

Methacrylic acid-2-{2-[4-(1-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-phenyl }-1-methyl-ethyl)-phenoxy group]-oxyethyl group }-ethyl ester,

The diacrylate of the ethylene oxide adduct of dihydroxyphenyl propane,

The dimethacrylate fat of the ethylene oxide adduct of dihydroxyphenyl propane,

The diacrylate of the propylene oxide adduct of dihydroxyphenyl propane,

The dimethacrylate fat of the propylene oxide adduct of dihydroxyphenyl propane,

Vinylformic acid-2-(4-{1-[4-(2-acryloxy-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl ester,

Methacrylic acid 2-(4-{1-[4-(2-methacryloxy-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl ester,

Vinylformic acid-2-{2-[4-(1-{4-[2-(2-acryloxy-propoxy-)-propoxy-]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-oxyethyl group }-1-methyl-ethyl ester,

Methacrylic acid-2-{2-[4-(1-{4-[2-(2-methacryloxy-propoxy-)-propoxy-]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-oxyethyl group }-1-methyl-ethyl ester,

Vinylformic acid-3-{4-[1-(3-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(3-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl ester,

Vinylformic acid-3-(4-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl ester,

Methacrylic acid-3-(4-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl ester,

Vinylformic acid-3-(5-{1-[6-(3-acryloxy-2-hydroxyl-propoxy-)-biphenyl-3-yl]-1-methyl-ethyl }-biphenyl-2-base oxygen base)-2-hydroxyl-propyl ester,

Methacrylic acid-3-(5-{1-[6-(3-methacryloxy-2-hydroxyl-propoxy-)-biphenyl-3-yl]-1-methyl-ethyl }-biphenyl-2-base oxygen base)-2-hydroxyl-propyl ester,

Vinylformic acid-3-{4-[1-(4-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-3-methyl-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxy group }-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(4-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-3-methyl-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxy group }-2-hydroxyl-propyl ester, vinylformic acid-3-(4-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl ester,

Methacrylic acid-3-(4-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl ester,

Vinylformic acid-3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl ester,

Methacrylic acid-3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl ester,

Vinylformic acid-3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxyl-propoxy-)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl ester etc.;

Two (methyl) acrylate with diphenylmethyl alkyl structure for example can be enumerated: vinylformic acid-4-(4-acryloxy-benzyl)-phenyl ester,

Methacrylic acid-4-(4-methacryloxy-benzyl)-phenyl ester,

Vinylformic acid-2-{4-[4-(2-acryloxy-oxyethyl group)-benzyl]-phenyl }-ethyl ester,

Methacrylic acid-2-{4-[4-(2-methacryloxy-oxyethyl group)-benzyl]-phenyl }-ethyl ester,

The diacrylate of the ethylene oxide adduct of Bisphenol F,

The dimethacrylate fat of the ethylene oxide adduct of Bisphenol F,

The diacrylate of the propylene oxide adduct of Bisphenol F,

The dimethacrylate fat of the propylene oxide adduct of Bisphenol F,

Vinylformic acid-2-[2-(4-{4-[2-(2-acryloxy-oxyethyl group)-oxyethyl group]-benzyl }-phenoxy group)-oxyethyl group]-ethyl ester,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-oxyethyl group)-oxyethyl group]-benzyl }-phenoxy group)-oxyethyl group]-ethyl ester,

Vinylformic acid-2-{4-[4-(2-acryloxy-propoxy-)-benzyl-phenoxy group }-1-methyl-ethyl ester,

Methacrylic acid 2-{4-[4-(2-methacryloxy-propoxy-)-benzyl-phenoxy group }-1-methyl-ethyl ester,

Vinylformic acid-2-[2-(4-{4-[2-(2-acryloxy-propoxy-)-propoxy-]-benzyl }-phenoxy group)-1-methyl-oxyethyl group]-1-methyl-diethyl acetamidomalonate,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-propoxy-)-propoxy-]-benzyl }-phenoxy group)-1-methyl-oxyethyl group]-1-methyl-ethyl diethyldithiocarbamate ester etc.;

Dithio (methyl) acrylate with diphenylsulfide structure for example can be enumerated: dithio vinylformic acid-4-(4-sulfo-acryl sulfanyl-phenyl sulfanyl)-phenyl ester,

Dithio methacrylic acid-4-(4-sulphomethyl acryl sulfanyl-phenyl sulfanyl)-phenyl ester, two (4-methacryloyl thienyl) thioether etc.;

Other compounds (B-1) for example can be enumerated two { 4-(3-acryloxy-propoxy-)-phenylformic acid } toluene of 2,5-etc.

This compound (B-1) is except can be by in addition proper combination synthesize with vitochemical common method, form acquisition that can also commercially available product.The commercially available product of compound (B-1) for example can be enumerated: two hydroxyl-oxethyl BP diacrylates, two hydroxyl-oxethyl Bis-A diacrylate (Honshu Chemical Ind's manufacturing);

Aronix M-208, M-210 (Toagosei Co., Ltd's manufacturing);

SR-349, SR-601, SR-602 (Sartomer (Sartomer) company make);

KAYARAD R-712, R-551 (Nippon Kayaku K. K's manufacturing);

NK Ester BPE-100, NK Ester BPE-200, NK Ester BPE-500, NK EsterBPE-1300, NK Ester A-BPE-4 (Xin Zhong village chemical industry Co., Ltd. make), Actilane420 (Japanese Waja Co., Ltd. (Nihon SiberHegner K.K.) manufacturing);

Light ester BP-2EM, Light acrylate BP-4EA, Light acrylate BP-4PA, epoxy ester 3000M, epoxy ester 3000A (Kyoeisha Chemical Co., Ltd.'s manufacturing);

V#540, V#700 (Osaka Organic Chemical Industry Co., Ltd.'s manufacturing);

FA-321M (Hitachi Chemical Co., Ltd.'s manufacturing);

MPSMA (the Sumitomo company that refines makes);

Lipoxy VR-77 (Showa Highpolymer Co., Ltd's manufacturing) etc.

As the compound that uses in the present invention (B-1), preferred freely at least a kind of the above-mentioned illustrated compound group that consists of of choosing that uses.

Can make tilt angle more near 90 °, show more efficiently therefrom the purpose of the desired effect of the present invention, and contain above-mentioned other unsaturated compounds in crystal aligning agent of the present invention.Other unsaturated compounds of this kind are preferably the compound with 1 carbon-to-carbon double bond, more preferably have the compound of 1 carbon-to-carbon double bond and LCD alignment base as explained above.The concrete example of other unsaturated compounds of this kind is such as enumerating methacrylic acid-5 ξ-cholestane-3-base ester, methacrylic acid-4-(4 '-phenyl-Lian hexanaphthene-4-yl) phenylester, methacrylic acid-4-octyloxyphenyl ester, methacrylic acid-4-(4-amyl group cyclohexyl) phenylester etc.

For total 100 weight parts of organopolysiloxane and other polymkeric substance, the usage ratio of the polymerizable unsaturated compound in crystal aligning agent of the present invention (the total usage ratios of compound (B-1) and (if use) other unsaturated compounds) is preferably 1 weight part～100 weight parts, more preferably 5 weight parts～50 weight parts.

As polymerizable unsaturated compound, in the situation that together use other unsaturated compounds with compound (B-1), for the total amount of unsaturated compound, its usage ratio is preferably below 50 weight parts, more preferably below 25 weight parts.By use other unsaturated compounds more than 5 weight parts with respect to the total amount of polymerizable unsaturated compound, can show its desired effect.

[Photoepolymerizationinitiater initiater]

Above-mentioned Photoepolymerizationinitiater initiater is such as enumerating α-diketone, alcohol ketone, pure ether ketone, benzophenone cpd, acetophenone compound, naphtoquinone compounds, halogen compounds, acylphosphine oxide, organo-peroxide etc.As the concrete example of these compounds, α-diketone is such as enumerating benzil, di-acetyl ketone etc.;

Alcohol ketone is such as enumerating st-yrax etc.;

The alcohol ether ketone is such as enumerating benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether etc.;

Benzophenone cpd for example can be enumerated thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, phenyl-(4-p-methylphenyl sulfenyl-phenyl)-ketone etc.;

Acetophenone compound for example can enumerate methyl phenyl ketone, to dimethylamino benzoylformaldoxime, 4-(α, α '-dimethoxy acetoxyl group) benzophenone, 2,2 '-dimethoxy-2-phenyl methyl phenyl ketone, p-methoxy-acetophenone, 2-methyl-2-morpholino-1-(4-thiotolene base)-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone etc.;

Naphtoquinone compounds is such as enumerating anthraquinone, 1,4-naphthoquinone etc.;

Halogen compounds is such as enumerating chloroacetophenone, trisbromomethyl phenyl sulfone, three (trichloromethyl)-s-triazine etc.;

Acylphosphine oxide for example can be enumerated 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide, two (2,4,6-trimethylbenzoyl) phenylphosphine oxide etc.;

Organo-peroxide be such as enumerating ditertiary butyl peroxide etc., can use be selected from these compounds more than a kind.

the commercially available product of Photoepolymerizationinitiater initiater for example can be enumerated: IRGACURE-124, IRGACURE-149, IRGACURE-184, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-1000, IRGACURE-1700, IRGACURE-1800, IRGACURE-1850, IRGACURE-2959, Darocur-1116, Darocur-1173, Darocur-1664, Darocur-2959, Darocur-4043 (above by Ciba company limited make),

KAYACURE-BMS, KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (above by Nippon Kayaku K. K's manufacturing);

LUCIRIN TPO (BASF AG's manufacturing);

VICURE-10, VICURE-55 (above by Shi Duofu (STAUFFER) company make);

TRIGONALP1 (manufacturing of Aksu (AKZO) company);

SANDORAY 1000 (manufacturing of Shandeshi (SANDOZ) company);

DEAP (APJOHN company make);

QUANTACURE-PDO, QUANTACURE-ITX, QUANTACURE-EPD (above by WARD BLENKINSOP company make) etc.

As Photoepolymerizationinitiater initiater, consider from the viewpoint that thermostability is high, preferably use benzophenone cpd.

For total 100 weight parts of organopolysiloxane and (if existence) polymerizable unsaturated compound, the usage ratio of the Photoepolymerizationinitiater initiater in crystal aligning agent of the present invention is preferably below 30 weight parts, more preferably 0.5 weight part～30 weight parts, be particularly preferably 1 weight part～20 weight parts.

[radical scavenger]

Above-mentioned radical scavenger can be in the situation that crystal aligning agent of the present invention contains the organopolysiloxane with the two keys of polymerizability preferably uses.Radical scavenger has the function of avoiding following phenomenon: owing to making the heating that institute preferably carries out when filming on substrate crystal aligning agent of the present invention is coated, cause the not good enough reaction of the two keys generation of polymerizability.

concrete example as this kind radical scavenger, [3-(3 for example can to enumerate tetramethylolmethane four, 5-two-tert-butyl-hydroxy phenyl) propionic acid] ester, [3-(3 for the sulphur di ethylene bis, 5-two-tert-butyl-hydroxy phenyl) propionic acid] ester, octadecyl-3-(3, 5-two-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-three (3, 5-two-tertiary butyl-4-hydroxy benzyl) benzene, N, N '-hexane-1, 6-two bases are two, and [3-(3, 5-two-tert-butyl-hydroxy phenyl propionic acid amide), 3, 3 ', 3 ", 5 ', 5 " five-tertiary butyl-α, α ', α " (sym-trimethylbenzene-2, 4, 6-three bases) three p-cresol, 4, two (hot sulfenyl the methyl)-ortho-cresols of 6-, 4, two (dodecyl sulfenyl the methyl)-ortho-cresols of 6-, two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters of ethylenebis (oxyethylene group), hexa-methylene is two, and [3-(3, 5-two-tert-butyl-hydroxy phenyl) propionic acid] ester, 1, 3, 5-three (3, 5-two-tertiary butyl-4-hydroxy benzyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 1, 3, 5-three [(the 4-tertiary butyl-3-hydroxyl-2, 6-dimethylbenzene) methyl]-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 2, 6-two-tertiary butyl-4-(4, two (the hot sulfenyls)-1 of 6-, 3, 5-triazine-2-base amine) phenol etc., can use be selected from these compounds more than a kind.

Commercially available product as these compounds can be enumerated: Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330 that Ai Dike (ADEKA) company makes; SumilizerGM, sumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizerGA-80 that Sumitomo Chemical Co makes;

IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295 that Japan vapour bar Co., Ltd. makes;

Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 etc. that API company makes.

For total 100 mass parts of organopolysiloxane and (if existence) polymerizable unsaturated compound, the usage ratio of the radical scavenger in crystal aligning agent of the present invention is preferably below 10 mass parts, more preferably 0.1 mass parts～5 mass parts.

[epoxy compounds]

Above-mentioned epoxy compounds is the compound that has at least one epoxy group(ing) in molecule (wherein, in crystal aligning agent of the present invention, contained organopolysiloxane has except the situation of epoxy group(ing)).

This epoxy compounds for example can be enumerated: 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, 2,2-dibromoneopentyl glycol diglycidylether etc. and have N, the compound of N-diglycidyl amino.

Epoxy compounds in the present invention preferably has N, the compound of N-diglycidyl amino, as its concrete example, for example can enumerate N, 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-benzene methanamine, N, N-diglycidyl-amino methyl hexanaphthene, N, N-diglycidyl-hexahydroaniline etc., can use be selected from these compounds more than a kind.

For organopolysiloxane 100 weight parts, the allotment ratio of these epoxy compoundss is preferably below 40 weight parts, more preferably below 30 weight parts.

[functional silanes compound]

above-mentioned functional silanes compound for example can be enumerated the 3-TSL 8330, APTES, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-three azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, 9-triethoxysilicane alkyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, the glycidoxypropyl methyltrimethoxy silane, the glycidoxypropyl Union carbide A-162, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane etc.

For organopolysiloxane 100 weight parts, the allotment ratio of these functional silanes compounds is preferably below 2 weight parts, more preferably below 0.2 weight part.

[tensio-active agent]

Above-mentioned tensio-active agent is such as enumerating nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.

In the situation that crystal aligning agent of the present invention contains tensio-active agent, for all 100 weight parts of crystal aligning agent, it contains proportional being preferably below 10 weight parts, more preferably below 1 weight part.

[potentiality stiffening agent]

Above-mentioned potentiality stiffening agent is not have hardening in the preservation of crystal aligning agent, but obtains to bring into play the composition of the function of Hardenability by the heating after coating of liquid crystalline orientation agent.Liquid crystal orienting film and excellent storage stability that crystal aligning agent of the present invention becomes and can form thermotolerance and excellent in light-resistance by containing this kind potentiality hardening thing, thereby preferred the use.

Potentiality stiffening agent in the present invention for example can preferably use the compound of at least a kind of structure that has the group that more than 2, the free following structure of choosing consists of in molecule: the 1-alkyl-cycloalkyl ester structure of the acetal ester structure of carboxylic acid, the ketal ester structure of carboxylic acid, carboxylic acid and the tert-butyl ester structure of carboxylic acid.The potentiality stiffening agent can be to have the homostructural compound in these structures more than 2, can also be to add up to have the not homostructural compound in these structures more than 2.

The base that forms the acetal ester structure of above-mentioned carboxylic acid can enumerate following formula (E-1) and formula (E-2) the base of expression respectively.

(in formula (E-1), R ^αAnd R ^βRespectively that carbon number is that 1～20 alkyl, carbon number are that 3～10 alicyclic group, carbon number are that 6～10 aryl or carbon number are 7～10 aralkyl,

In formula (E-2), k1 is 2～10 integer.)

Herein, the R in above-mentioned formula (E-1) ^αAlkyl be preferably methyl;

Alicyclic group is preferably cyclohexyl;

Aryl is preferably phenyl;

Aralkyl is preferably benzyl,

R ^βAlkyl to be preferably carbon number be 1～6 alkyl;

It is 6～10 alicyclic group that alicyclic group is preferably carbon number;

Aryl is preferably phenyl;

Aralkyl is preferably benzyl or 2-phenylethyl,

K1 in formula (E-2) is preferably 3 or 4.

the represented base of above-mentioned formula (E-1) for example can be enumerated 1-methoxy ethoxy carbonyl, 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-isopropoxy ethoxy carbonyl, 1-n-butoxy ethoxy carbonyl, 1-isobutoxy ethoxy carbonyl, 1-sec-butoxy ethoxy carbonyl, 1-tert.-butoxy ethoxy carbonyl, 1-cyclopentyloxy ethoxy carbonyl, 1-cyclohexyloxy ethoxy carbonyl, 1-norcamphyl oxygen base oxethyl carbonyl, 1-bornyl oxygen base oxethyl carbonyl, 1-phenoxy group ethoxy carbonyl, 1-(1-naphthyloxy) ethoxy carbonyl, 1-benzyloxy ethoxy carbonyl, 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.,

The represented base of above-mentioned formula (E-2) is such as enumerating 2-tetrahydrofuran base oxygen base carbonyl, 2-THP trtrahydropyranyl oxygen base carbonyl etc.Preferred 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-cyclohexyloxy ethoxy carbonyl, 2-THP trtrahydropyranyl oxygen base carbonyl, 2-THP trtrahydropyranyl oxygen base carbonyl etc. in these bases.

The base that forms the ketal ester structure of above-mentioned carboxylic acid for example can enumerate following formula (E-3)～formula (E-5) the base of expression respectively.

(in formula (E-3), R ^γThat carbon number is 1～12 alkyl, R ^δAnd R ^εRespectively that carbon number is that 1～12 alkyl, carbon number are that 3～20 alicyclic group, carbon number are that 6～20 aryl or carbon number are 7～20 aralkyl,

In formula (E-4), R ^ΦBe that carbon number is 1～12 alkyl, k2 is 2～8 integer,

In formula (E-5), R ^ηBe that carbon number is 1～12 alkyl, k3 is 2～8 integer.)

Herein, the R in above-mentioned formula (C-3) ^γAlkyl be preferably methyl,

R ^δAlkyl be preferably methyl;

Alicyclic group is preferably cyclohexyl;

Aryl is preferably phenyl;

Aralkyl is preferably benzyl,

R ^εAlkyl to be preferably carbon number be 1～6 alkyl;

It is 6～10 alicyclic group that alicyclic group is preferably carbon number;

Aryl is preferably phenyl;

Aralkyl is preferably benzyl or 2-phenylethyl,

R in formula (E-4) ^ΦAlkyl be preferably methyl;

K2 is preferably 3 or 4,

R in formula (E-5) ^ηAlkyl be preferably methyl;

K3 is preferably 3 or 4.

the represented base of above-mentioned formula (E-3) for example can be enumerated 1-methyl isophthalic acid-methoxy ethoxy carbonyl, 1-methyl isophthalic acid-ethoxy ethoxy carbonyl, 1-methyl isophthalic acid-positive propoxy ethoxy carbonyl, 1-methyl isophthalic acid-isopropoxy ethoxy carbonyl, 1-methyl isophthalic acid-n-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-isobutoxy ethoxy carbonyl, 1-methyl isophthalic acid-sec-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-tert.-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-cyclopentyloxy ethoxy carbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxy carbonyl, 1-methyl isophthalic acid-norcamphyl oxygen base oxethyl carbonyl, 1-methyl isophthalic acid-bornyl oxygen base oxethyl carbonyl, 1-methyl isophthalic acid-phenoxy group ethoxy carbonyl, 1-methyl isophthalic acid-(1-naphthyloxy) ethoxy carbonyl, 1-methyl isophthalic acid-benzyloxy ethoxy carbonyl, 1-methyl isophthalic acid-benzene ethoxy ethoxy carbonyl, 1-cyclohexyl-1-methoxy ethoxy carbonyl, 1-cyclohexyl-1-ethoxy ethoxy carbonyl, 1-cyclohexyl-1-positive propoxy ethoxy carbonyl, 1-cyclohexyl-1-isopropoxy ethoxy carbonyl, 1-cyclohexyl-1-cyclohexyloxy ethoxy carbonyl, 1-cyclohexyl-1-phenoxy group ethoxy carbonyl, 1-cyclohexyl-1-benzyloxy ethoxy carbonyl, 1-phenyl-1-methoxy ethoxy carbonyl, 1-phenyl-1-ethoxy ethoxy carbonyl, 1-phenyl-1-positive propoxy ethoxy carbonyl, 1-phenyl-1-isopropoxy ethoxy carbonyl, 1-phenyl-1-cyclohexyloxy ethoxy carbonyl, 1-phenyl-1-phenoxy group ethoxy carbonyl, 1-phenyl-1-benzyloxy ethoxy carbonyl, 1-benzyl-1-methoxy ethoxy carbonyl, 1-benzyl-1-ethoxy ethoxy carbonyl, 1-benzyl-1-positive propoxy ethoxy carbonyl, 1-benzyl-1-isopropoxy ethoxy carbonyl, 1-benzyl-1-cyclohexyloxy ethoxy carbonyl, 1-benzyl-1-phenoxy group ethoxy carbonyl, 1-benzyl-1-benzyloxy ethoxy carbonyl etc.,

The represented base of above-mentioned formula (E-4) is such as enumerating 2-(2-methyltetrahydrofuran base) oxygen base carbonyl, 2-(2-methyl THP trtrahydropyranyl) oxygen base carbonyl etc.;

The represented base of above-mentioned formula (E-5) is such as enumerating 1-methoxyl group cyclopentyloxy carbonyl, 1-methoxyl group cyclohexyloxy carbonyl etc.Preferred 1-methyl isophthalic acid-methoxy ethoxy carbonyl, 1-methyl isophthalic acid-cyclohexyloxy ethoxy carbonyl etc. in these bases.

The base that forms the 1-alkyl-cycloalkyl ester structure of above-mentioned carboxylic acid for example can be enumerated the represented base of following formula (E-6).

(in formula (E-6), R ^κBe that carbon number is 1～12 alkyl, k4 is 1～8 integer)

Herein, the R in above-mentioned formula (E-6) ^κAlkyl to be preferably carbon number be 1～10 alkyl.

the represented base of above-mentioned formula (E-6) for example can be enumerated 1-methyl ring propoxycarbonyl, 1-methyl cyclobutoxy group carbonyl, 1-methyl cyclopentyloxy carbonyl, 1-methyl cyclohexane oxygen base carbonyl, 1-methyl ring oxygen in heptan base carbonyl, 1-methyl ring carbonyl octyloxy, 1-methyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-methyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-ethyl ring propoxycarbonyl, 1-ethyl cyclobutoxy group carbonyl, 1-ethyl cyclopentyloxy carbonyl, 1-ethyl cyclohexyloxy carbonyl, 1-ethyl ring oxygen in heptan base carbonyl, 1-ethyl ring carbonyl octyloxy, 1-ethyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-ethyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) propyl group ring propoxycarbonyl, 1-(different) propyl group cyclobutoxy group carbonyl, 1-(different) propyl group cyclopentyloxy carbonyl, 1-(different) propyl group cyclohexyloxy carbonyl, 1-(different) propyl group ring oxygen in heptan base carbonyl, 1-(different) propyl group ring carbonyl octyloxy, 1-(different) propyl group ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) propyl group ring oxygen in last of the ten Heavenly stems base carbonyl,

1-(different) butyl ring propoxycarbonyl, 1-(different) butyl cyclobutoxy group carbonyl, 1-(different) butyl cyclopentyloxy carbonyl, 1-(different) butyl cyclohexyloxy carbonyl, 1-(different) butyl ring oxygen in heptan base carbonyl, 1-(different) butyl ring carbonyl octyloxy, 1-(different) butyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) butyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) amyl group ring propoxycarbonyl, 1-(different) amyl group cyclobutoxy group carbonyl, 1-(different) amyl group cyclopentyloxy carbonyl, 1-(different) amyl group cyclohexyloxy carbonyl, 1-(different) amyl group ring oxygen in heptan base carbonyl, 1-(different) amyl group ring carbonyl octyloxy, 1-(different) amyl group ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) amyl group ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) hexyl ring propoxycarbonyl, 1-(different) hexyl cyclobutoxy group carbonyl, 1-(different) hexyl cyclopentyloxy carbonyl, 1-(different) hexyl cyclohexyloxy carbonyl, 1-(different) hexyl ring oxygen in heptan base carbonyl, 1-(different) hexyl ring carbonyl octyloxy, 1-(different) hexyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) hexyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) heptyl ring propoxycarbonyl, 1-(different) heptyl cyclobutoxy group carbonyl, 1-(different) heptyl cyclopentyloxy carbonyl, 1-(different) heptyl cyclohexyloxy carbonyl, 1-(different) heptyl ring oxygen in heptan base carbonyl, 1-(different) heptyl ring carbonyl octyloxy, 1-(different) heptyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) heptyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) octyl group ring propoxycarbonyl, 1-(different) octyl group cyclobutoxy group carbonyl, 1-(different) octyl group cyclopentyloxy carbonyl, 1-(different) octyl group cyclohexyloxy carbonyl, 1-(different) octyl group ring oxygen in heptan base carbonyl, 1-(different) octyl group ring carbonyl octyloxy, 1-(different) octyl group ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) octyl group ring oxygen in last of the ten Heavenly stems base carbonyl etc.

The so-called base that forms the tert-butyl ester structure of above-mentioned carboxylic acid is tert-butoxycarbonyl.

Potentiality stiffening agent in the present invention is preferably the represented compound of following formula (E).

Bl _mR(E)

(in formula (E), Bl is represented base or the tert-butoxycarbonyl of any formula of above-mentioned formula (E-1)～formula (E-5), m be 2 and R be singly-bound, perhaps m is 2～10 integer and R for being that to remove the base of m valency hydrogen gained or carbon number be 1～18 m valency alkyl for 3～10 heterogeneous ring compound from carbon number)

M is preferably 2 or 3.

Concrete example as the R in above-mentioned formula (E), in the situation that m is 2, can enumerate singly-bound, methylene radical, carbon number and be 2～12 alkylidene group, 1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene, 2,6-naphthylidene, 5-sodium sulfo group-1,3-phenylene, 5-4-butyl-phosphonium sulfo group-1,3-phenylene etc.;

In the situation that m is 3, can enumerate the represented base of following formula, benzene-1,3,5-three bases etc.

Above-mentioned alkylidene group is preferably straight-chain alkyl-sub-.

For organopolysiloxane 100 weight parts, the usage ratio of the potentiality stiffening agent in crystal aligning agent of the present invention is preferably below 40 weight parts, more preferably 5 weight parts～20 weight parts.

The potentiality stiffening agent in the situation that in crystal aligning agent of the present invention contained organopolysiloxane have epoxy group(ing) and can bring into play to greatest extent its desired effect.Preferred usage ratio as in such cases potentiality stiffening agent, for 1 mole of the epoxy group(ing) that has with respect to organopolysiloxane, the total mole number of at least a kind of structure of the group that the 1-alkyl-cycloalkyl ester structure of the acetal ester structure of the free carboxylic acid of choosing that the potentiality stiffening agent has, the ketal ester structure of carboxylic acid, carboxylic acid and the tertiary butyl ester structure of carboxylic acid consist of preferably becomes the ratio of 0.1 mole～10 moles, more preferably become the ratio of 0.4 mole～4 moles, further more preferably become the ratio of 1.5 moles～2 moles.Therefore, state in the use in the represented situation of compound as the potentiality stiffening agent of formula (E), for 1 mole of the epoxy group(ing) that has with respect to organopolysiloxane (E), the usage ratio of the compound that this above-mentioned formula (E) is represented is preferably and is 0.1/m mole～10/m mole, more preferably 0.4/m mole～4/m mole, further 1.5/m mole～2/m mole more preferably.Wherein, with upper, the m synonym in m and above-mentioned formula (E).

＜crystal aligning agent 〉

Crystal aligning agent of the present invention can constitute organopolysiloxane as above and other compositions dissolvings of at random using contain the aqueous constituent that forms in above-mentioned illustrated solvent.

Solid concentration in crystal aligning agent of the present invention (the total weight of the composition beyond the solvent of crystal aligning agent in the gross weight of crystal aligning agent shared ratio) can be considered viscosity, volatility etc. and suitable selection, is preferably the scope of 1 % by weight～10 % by weight.That is, crystal aligning agent of the present invention can be by coating on substrate surface as described later, preferably heat and form and become filming of liquid crystal orienting film, in the situation that solid concentration less than 1 % by weight, this thickness of filming becomes too small and can't obtain good liquid crystal orienting film, in the situation that solid concentration surpasses 10 % by weight, the thickness of filming becomes excessive and can't obtain good liquid crystal orienting film on the other hand.

The method that the scope of particularly preferred solid concentration is used when coating crystal aligning agent on substrate is different.For example in the situation that utilize spin-coating method, solid concentration is the scope of 1.5 % by weight～7.5 % by weight particularly preferably.In the situation that utilize print process, particularly preferably solid concentration is made as the scope of 6 % by weight～15 % by weight, making therefrom soltion viscosity is the scope of 8mPas～50mPas.In the situation that utilize ink jet method, particularly preferably solid concentration is made as the scope of 3 % by weight～10 % by weight, making therefrom soltion viscosity is the scope of 3mPas～15mPas.

Temperature when modulating crystal aligning agent of the present invention is preferably 10 ℃～50 ℃, more preferably 20 ℃～30 ℃.

The manufacture method of＜liquid crystal display device 〉

Liquid crystal display device of the present invention comprises the liquid crystal orienting film that is formed by crystal aligning agent of the present invention as above.

Liquid crystal display device of the present invention for example can utilize following any means and make.

The liquid crystal display device of known operational mode for example can pass through following steps (1) and make (manufacture method 1 of liquid crystal display device) to step (3) since before:

(1) use crystal aligning agent of the present invention and form on substrate the step of filming,

(2) optionally to coated surface implement friction treatment step, and

(3) holding liquid crystal and consist of the step of liquid crystal cells between a pair of substrate.

Can be by as mentioned above and two faces of the liquid crystal cells of gained configuration Polarizers are made liquid crystal display device.

And the liquid crystal display device of the new display format of replacement PSA pattern for example can pass through following steps (1 ') and make (manufacture method 2 of liquid crystal display device) to step (3 '):

(1 ') be coated with respectively crystal aligning agent of the present invention on this conducting film of a pair of substrate with conducting film and form the step of filming,

(2 ') will be formed with described a pair of substrate of filming, be situated between carry out the subtend configuration every layer of liquid crystal molecule in the described relative mode of filming and consist of liquid crystal cells step, and (3 ') described liquid crystal cells is carried out light-struck step executing under alive state between the conducting film that described a pair of substrate was had.

And, can be by as mentioned above and two faces of the liquid crystal cells after the rayed of gained configuration Polarizers are made liquid crystal display device.

Below, in turn above-mentioned each manufacture method is illustrated.

[manufacture method 1 of liquid crystal display device]

Step (1) in the manufacture method 1 of liquid crystal display device is used different substrates according to desired operational mode.Step (2) and step (3) are common in each operational mode.

Secondly (1) at first, coating crystal aligning agent of the present invention on substrate heats coated face and forms on substrate and film.

(1-1) when making the situation of TN type, STN type or VA type liquid crystal display device, be made as two pieces of substrates that are provided with the nesa coating of patterning a pair of, preferably utilize offset printing method, spin-coating method or ink jet printing method and crystal aligning agent of the present invention is coated respectively on its each transparent conducting film formation face, secondly each coated face is heated, form therefrom and film.Herein, substrate is such as using the glass such as float glass, soda glass; The transparency carrier that comprises polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics such as (alicyclic olefins).As a nesa coating that face is set at substrate, can use to comprise stannic oxide (SnO ₂) NESA film (registered trademark of U.S. PPG company), comprise Indium sesquioxide-stannic oxide (In ₂O ₃-SnO ₂) ITO film etc., in order to obtain the nesa coating of patterning, for example can utilize following method: after forming patternless nesa coating, utilize photoetch and form the method for pattern; Use the method for the mask with desired pattern etc. when forming nesa coating.When coating of liquid crystalline orientation agent, for the then property that makes substrate surface and nesa coating and film becomes better, also can form the pre-treatment that the face of filming implements to be coated with in advance functional silanes compound, functionality titanium compound etc. to the need in substrate surface.

After coating of liquid crystalline orientation agent, for orientation agent sagging of preventing from being coated with etc., preferably implement preheating (preliminary drying).The preliminary drying temperature is preferably 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, is particularly preferably 40 ℃～100 ℃.The preliminary drying time is preferably 0.25 minute～and 10 minutes, more preferably 0.5 minute～5 minutes., solvent fully removed, further in the situation that adopt manufacturing process 1 to implement calcining (rear baking) step to remove remaining dicarboxylic acid as purpose in the manufacturing of organopolysiloxane thereafter.This calcining (rear baking) temperature is preferably 80 ℃～300 ℃, more preferably 120 ℃～250 ℃.The rear baking time is preferably 5 minutes～and 200 minutes, more preferably 10 minutes～100 minutes.The thickness of the film that forms as mentioned above is preferably 0.001 μ m～1 μ m, more preferably 0.005 μ m～0.5 μ m.

(1-2) on the other hand, when making the situation of IPS type liquid crystal display device, crystal aligning agent of the present invention is coated respectively on the conducting film formation face of the substrate that is provided with the nesa coating that is patterned as interdigitated electrode structure, with a face of the subtend substrate that is not provided with conducting film on, secondly each coated face is heated, form therefrom and film.

About substrate and the material of nesa coating, the patterning method of nesa coating, the pre-treatment of substrate, the coating process of crystal aligning agent and heating means and the formed preferred thickness of filming after coating that uses this moment, identical with above-mentioned (1-1).

(2) liquid crystal display device of making utilizing method of the present invention is during for the situation of VA type liquid crystal display device, can be with filming directly as liquid crystal orienting film of forming as mentioned above, also can carry out as required after hereinafter described friction treatment in.

On the other hand, during the situation of the liquid crystal display device beyond making the VA type, by the enforcement friction treatment of filming that forms is as mentioned above made liquid crystal orienting film.

Friction treatment can be carried out in the following way: utilize be wound with such as the roller of the cloth that comprises the fibers such as nylon, artificial silk, cotton and on fixed-direction to as mentioned above and the coated surface of formation rubs.Give therefrom the orientation ability of liquid crystal molecule to filming, thereby become liquid crystal orienting film.

in addition, the liquid crystal orienting film that forms is as mentioned above for example carried out the processing that tilt angle that a part of irradiation ultraviolet radiation to liquid crystal orienting film makes the part zone of liquid crystal orienting film changes of passing through shown in patent documentation 6 (Japanese patent laid-open 6-222366 communique) and patent documentation 7 (Japanese patent laid-open 6-281937 communique), shown in patent documentation 8 (Japanese patent laid-open 5-107544 communique) after forming etchant resist on the part on liquid crystal orienting film surface, carry out friction treatment on the direction different from before friction treatment, then remove the processing of etchant resist, can improve the visual field characteristic of the liquid crystal display device that obtains so that each zone of liquid crystal orienting film has the mode of different LCD alignment abilities.

(3) prepare 2 pieces and be formed with as mentioned above the substrate of liquid crystal orienting film, configure liquid crystal between 2 pieces of substrates of subtend configuration, make therefrom liquid crystal cells.Herein, when carrying out the situation of friction treatment to filming, 2 pieces of substrates become angle, for example quadrature or the antiparallel mode of regulation and the subtend configuration mutually with the frictional direction in respectively filming.

When making liquid crystal cells, for example can enumerate 2 kinds of following methods.

First method has been method known since before.At first, with each liquid crystal orienting film relatively to be situated between septal space (cell gap) and with the configuration of 2 pieces of substrate subtends of mode, use sealing agent that the periphery of 2 pieces of substrates is fitted, inject filling liquid crystal in the cell gap of being divided by substrate surface and sealing agent after, with the filling orifice sealing, can make liquid crystal cells thus.

Second method is the gimmick that is called as instillation (One Drop Fill, ODF) mode.Prescribed position on wherein one piece of substrate in being formed with 2 pieces of substrates of liquid crystal orienting film is coated with for example ultraviolet light photopolymerization sealing material, further after dripping liquid crystal on the LCD alignment face, with liquid crystal orienting film relatively to the mode other one piece of substrate of fitting, secondly whole irradiating ultraviolet light of substrate made hardening seal, can make liquid crystal cells thus.In addition, in the situation that crystal aligning agent of the present invention contains the organopolysiloxane with LCD alignment base, even this crystal aligning agent in the situation that adopt the ODF mode in the manufacturing of VA type liquid crystal display device, also can not produce the ODF inequality, therefore be particularly suitable for being applicable in the manner.

Herein, sealing agent contains stiffening agent and as epoxy resin of the alumina balls of spacer etc. such as using.

Described liquid crystal is such as using nematic liquid crystal, smectic liquid crystal etc., preferred nematic liquid crystal in these.In the situation that VA type liquid crystal cells, the nematic liquid crystal that preferably has negative dielectric anisotropy is such as using dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.In the situation that TN type liquid crystal cells or STN type liquid crystal cells, the nematic liquid crystal that preferably has positive dielectric anisotropy is such as using biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.Use such as can further adding following compound in these liquid crystal: the cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate; As trade(brand)name C-15, B-15 (Merck ﹠ Co., Inc.'s manufacturing) and commercially available chirality agent; To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.

When utilizing the situation of any means, it is desirable to the liquid crystal cells made as mentioned above, the liquid crystal that further is heated to use becomes the temperature of isotropic phase, and then slow cooling is to room temperature, the mobile orientation when removing therefrom liquid crystal and filling.

Secondly, can obtain liquid crystal display device by the outer surface applying Polarizer at liquid crystal cells.This Polarizer can be enumerated light polarizing film (described H film is that one side makes polyvinyl alcohol extension orientation simultaneously absorb the light polarizing film that iodine forms) Polarizer that forms or the Polarizer that comprises H film self that is called as " H film " with the clamping of rhodia protective membrane.

[manufacture method 2 of liquid crystal display device]

(1 ') at first is coated with respectively crystal aligning agent of the present invention and forms and film on this conducting film of a pair of substrate with conducting film.After forming film can be with it directly for to step (2 ') thereafter, but also can at random implement the friction treatment as the step in manufacture method 1 (2).

(2 ') will be formed with described a pair of substrate of filming, and be situated between to carry out the subtend configuration and consist of liquid crystal cells in the described relative mode of filming every layer of liquid crystal molecule.

These steps can with manufacture method 1 in step (1) to step (3) similarly carry out.Liquid crystal molecule as used herein preferably has the nematic liquid crystal of negative dielectric anisotropy, such as using dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.The thickness of layer of liquid crystal molecule is preferably 1 μ m～5 μ m.And

(3 ') are executed under alive state between the conducting film that described a pair of substrate has described liquid crystal cells are carried out rayed.

The light that shines for example can use ultraviolet ray and the visible rays of the light of the wavelength that comprises 150nm～800nm, preferably comprises the ultraviolet ray of light of the wavelength of 300nm～400nm.The light source of irradiation light is such as using Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, Metal-halogen lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet ray of described preferred wavelength region may can by with described light source with obtain such as the method for spectral filter, diffraction grating etc. and use etc.The irradiation dose of light is preferably 1,000J/m ²Above and less than 100,000J/m ², more preferably 1,000J/m ²～50,000J/m ²In the manufacturing of the liquid crystal display device of known before PSA pattern, must irradiation 100,000J/m ²The light of left and right, but in the method for the invention, even the rayed amount is being made as 50,000J/m ²Below, be made as 10,000J/m furthermore ²In following situation, also can obtain desired liquid crystal display device, help to cut down the manufacturing cost of liquid crystal display device, can avoid in addition because the caused electrical specification of irradiation high light reduces, long-term reliability reduces.

And, can obtain liquid crystal display device by the outer surface applying Polarizer of the liquid crystal cells after having implemented processing as above.This Polarizer can use with manufacture method 1 in identical Polarizer.

[example]

Below, to the present invention's more specific description in addition, but the present invention is not restricted to these examples by example.

In following example, weight average molecular weight Mw utilizes the gel permeation chromatography of following condition and the polystyrene conversion value measured.

Tubing string: eastern Cao (Tosoh) Co., Ltd. makes, TSKgelGRCXLII

Solvent: tetrahydrofuran (THF)

Temperature: 40 ℃

Pressure: 68kgf/cm ²

Synthetic (1) of＜organopolysiloxane 〉

Synthesis example S-1-1

At the AC-SQ TA100 that packs in the there-necked flask of the 200mL with thermometer (hydrolytic condensate of 3-acryloxy propyl trimethoxy silicane, Toagosei Co., Ltd make) 33.0g, Thiovanic acid 9.2g (being equivalent to 50mol% for the Siliciumatom that AC-SQ TA100 has), acetonitrile 42.3g and triethylamine 20.2g, carry out the reaction of 1 hour under 50 ℃.After reaction finished, with the solvent in ethylene glycol butyl ether (BC) exchange system, acquisition contained the solution 195g of the organopolysiloxane (S-1-1) of 20 % by weight of having an appointment therefrom.

The Mw of this organopolysiloxane (S-1-1) is 5,200.

Synthesis example S-1-2 and synthesis example S-1-3

In above-mentioned synthesis example S-1-1, such as in table 2 set the usage quantity of Thiovanic acid record, the stearylmercaptan of the amount of putting down in writing in further interpolation table 2 when packing into similarly carries out with synthesis example S-1-1 in addition and obtains respectively organopolysiloxane (S-1-2) and organopolysiloxane (S-1-3).

The Mw of these organopolysiloxane is shown in table 2 in the lump.

Synthetic (1) of table 2. organopolysiloxane

In above-mentioned table 2, " AC-SQ " expression with organopolysiloxane one hurdle of two keys is the AC-SQ TA100 that Toagosei Co., Ltd makes.

The numerical value on " mol% " hurdle in table 2 is the usage ratio of the Siliciumatom that has with respect to AC-SQ TA100.

Synthesizing of＜forerunner organopolysiloxane (A2) 〉

Synthesis example E-1

Pack in the reaction vessel with stirrer, thermometer, dropping funnel and reflux condensing tube as the 2-(3 of silane compound, 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane (ECETS) 250g (being equivalent to 50mol%) and 3-methacryloxypropyl trimethoxy silane (MTMS) 252g (being equivalent to 50mol%), as the methyl iso-butyl ketone (MIBK) 502g of solvent and as the triethylamine 50g of catalyzer, at room temperature mix.Secondly, after dripping deionized water 402g with dropping funnel with 30 minutes, carry out the reaction of 6 hours stirring under 80 ℃, under refluxing.After reaction finishes, organic layer is taken out, aqueous ammonium nitrate solution with 0.2 % by weight cleans until the water after cleaning becomes neutrality, then under reduced pressure solvent and water distillation is removed, and obtains therefrom the organopolysiloxane EPS-1 with epoxy construction as the transparent liquid of thickness.

The Mw of this organopolysiloxane EPS-1 is 2,900.

Synthesis example E-2～synthesis example E-4

In above-mentioned synthesis example E-1, respectively such as table 3 set kind and the amount of silane compound record, utilize the gimmick identical with synthesis example E-1 in addition and obtain to have the organopolysiloxane EPS-2 of epoxy construction～organopolysiloxane EPS-4.

The Mw of these organopolysiloxane is shown in table 3 in the lump.

Synthesizing of table 3. forerunner organopolysiloxane (A2)

In above-mentioned table 3, the abbreviation of silane compound is respectively following implication.

ECETS:2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane

The MTMS:3-methacryloxypropyl trimethoxy silane

ATMS:3-acryloxy propyl trimethoxy silicane

Synthetic (2) of＜organopolysiloxane 〉

Synthesis example S-2-1

Organopolysiloxane EPS-123g, the methyl iso-butyl ketone (MIBK) 148g that synthesize in packing into as the above-mentioned synthesis example E-1 of organopolysiloxane with epoxy construction in the there-necked flask of 400mL and as 4-(4-n-pentyl cyclohexyl) phenylformic acid (PCPA) 7.08g (being equivalent to 20mol% for the Siliciumatom that organopolysiloxane EPS-1 has) and Tetrabutyl amonium bromide 2.3g with carboxylic acid of LCD alignment base is under 90 ℃, react under stirring in 8 hours.After reaction finishes, add methyl alcohol and generate precipitation in reaction mixture,, after the solution of gained carries out 3 washings the solvent distillation is removed this throw out being dissolved in ethyl acetate, obtain therefrom the white powder 20.3g of organopolysiloxane (S-2-1).

The weight average molecular weight of this organopolysiloxane (S-2-1) is 4,800.

Synthesis example S-2-2～synthesis example S-2-9

In above-mentioned synthesis example S-2-1, respectively such as table 4 kind and the amount setting the kind of the organopolysiloxane with epoxy construction and have the carboxylic acid of LCD alignment base record, utilize the gimmick identical with synthesis example S-2-1 in addition and obtain to have the organopolysiloxane (S-2-2) of epoxy construction～organopolysiloxane (S-2-9).

In addition, in synthesis example S-2-3 and synthesis example S-2-7, and with 2 kinds of compounds as the carboxylic acid with LCD alignment base.

The Mw of these organopolysiloxane is shown in table 4 in the lump.

Synthetic (2) of table 4. organopolysiloxane

In above-mentioned table 4, the abbreviation of carboxylic acid is respectively following implication.

PCPA:4-(4-n-pentyl cyclohexyl) phenylformic acid

HCSA: mono succinate cholestane base ester

OCTBA:4-n-octyloxy phenylformic acid

PCCA:4-carboxyl-4 '-n-pentyl-Lian hexanaphthene

The numerical value on " mol% " hurdle in table 4 is the usage ratio of the Siliciumatom that has with respect to the organopolysiloxane with epoxy construction.

Synthetic (3) of＜organopolysiloxane 〉

Synthesis example S-3-1

Drop into 2-methyl-2 in having the 1L four-hole boiling flask of thermometer, return line, 4-pentanediol 23.0g, butoxy ethanol 7.7g, tetraethoxysilane 40.4g and Octadecane ethyl triethoxy silicane alkane 0.8g stir and modulate the solution of organoalkoxysilane monomer.

In this solution, at room temperature comprise 2-methyl-2 with what dripped in advance modulation separately in 30 minutes, the oxalic acid solution of 4-pentanediol 11.5g, butoxy ethanol 3.8g, water 10.8g and oxalic acid (catalyzer) 0.2g further at room temperature stirred 30 minutes after dripping end.Under refluxing further carry out the heating of 30 minute thereafter.

Add 92 % by weight methanol solution 1.15g, 2-methyl-2 that comprise 3-urea groups propyl-triethoxysilicane in above-mentioned reaction mixture, the solution of 4-pentanediol 0.48g and butoxy ethanol 0.16g further carries out the heating of 30 minutes under refluxing.After placement is cooling, add methyl alcohol and generate precipitation in the reaction mixture of gained, to this throw out being dissolved in ethyl acetate and the solution of gained carries out 3 washings, then the solvent distillation is removed, obtain therefrom the white powder 30.2g of organopolysiloxane (S-3-1).

The Mw of this organopolysiloxane (S-3-1) is 20,500.

Gather the Mw of the organopolysiloxane of gained in above-mentioned each synthesis example and the functional group who has in following table 5.

What table 5. organopolysiloxane was synthetic gathers

Example 1

＜printing evaluation the modulation of crystal aligning agent 〉

Add ethylene glycol butyl ether (BC) as solvent and propylene glycol list phenyl ether (PPh) in the organopolysiloxane of gained (S-2-1) and with its dissolving, making solvent composition is BC: PPh=40: 60 (weight ratios), solid concentration are the solution of 8.0 % by weight in above-mentioned synthesis example S-2-1.The use aperture is that the strainer of 1 μ m filters this solution, modulates therefrom crystal aligning agent.

For this crystal aligning agent, to use E type viscometer and measure viscosity under 25 ℃, result is 12.4mPas.

＜liquid crystal cells manufacturing the modulation of crystal aligning agent 〉

With in the modulation of crystal aligning agent, the solid concentration of the solution before filtering is made as 4.0 % by weight in above-mentioned printing evaluation, similarly carries out with the modulation of crystal aligning agent with the printing evaluation in addition and obtain liquid crystal cells manufacturing crystal aligning agent.

The evaluation of＜offset printing 〉

With the above-mentioned printing evaluation crystal aligning agent of modulating, use hectograph formula liquid crystal orienting film printing press (Nissha Printing Co., Ltd's manufacturing),, coat on the transparent electrical pole-face of the glass substrate of having the transparency electrode that comprises the ITO film under the condition of the dripping quantity on anilox roll (anilox roll) for round 15 (approximately 0.15g) at crystal aligning agent.Herein, Comparatively speaking amount of liquid is few, is stricter printing condition for the dripping quantity that usually adopts of above-mentioned crystal aligning agent dripping quantity and institute in the printing press of model of the same race (round 30, approximately 0.3g).With the substrate after crystal aligning agent coating after being set as the heating (preliminary drying) of carrying out 5 minutes on the hot plate of 80 ℃, carry out the heating (rear baking) of 30 minutes in the heat-circulation type cleaning oven, under 180 ℃, form therefrom approximately film (liquid crystal orienting film) of 100nm of thickness.

Be the above-mentioned state of filming of observation by light microscope of 20 times with visual and multiplying power, estimate printing (internal homogeneity and edge line) with following benchmark.

[internal homogeneity]

Good: the surface of film is homogeneous very

Well: the surface of film is homogeneous roughly, but produces orange peel shape inequality or wire inequality slightly

Bad: at least one party in high frequency ground generation orange peel shape inequality and wire inequality

[edge line]

Good: the outer edge of filming is linearity, the situation that its rectilinearity is very good

Well: the outer edge of filming is linearity, the situation that its rectilinearity is good

Bad: the situation that the outer edge of filming is fuzzy

The manufacturing of＜liquid crystal cells and evaluation 〉

(1) manufacturing of liquid crystal cells

By spin-coating method, above-mentioned liquid crystal cells manufacturing of modulating being coated Pixel Dimensions with crystal aligning agent is 100 μ m * 300 μ m, forms the ito surface side of ITO electrode base board that wired/gap width is respectively the ITO electrode pattern of 5 μ m.Substrate after crystal aligning agent coating is carried out the heating (preliminary drying) of 5 minutes being set as on the hot plate of 80 ℃, then in the heat-circulation type cleaning oven, carry out the heating (rear baking) of 30 minutes under 180 ℃, thereby form approximately film (liquid crystal orienting film) of 100nm of thickness.Will be with this substrate of filming as " substrate A ".

Secondly, by spin-coating method, liquid crystal cells manufacturing same as described above is coated to be formed with crystal aligning agent and do not have an ito surface side of substrate of ITO film of pattern.For the substrate after crystal aligning agent coating, similarly carrying out the heating of 5 minutes on hot plate, under 80 ℃ and carry out the heating of 30 minutes in cleaning oven, under 180 ℃, form approximately film (liquid crystal orienting film) of 100nm of thickness with above-mentioned.Will be with this substrate of filming as " substrate B ".

Scattering diameter on the coated surface of the substrate A of above-mentioned gained is the set pearl shape spacer of 3 μ m, and next heats and this pearl shape spacer is fixed on coated surface.Secondly, sealing agent is coated the peripheral part of substrate B, the number place of the regulation on coated surface drips liquid crystal MLC-6608 (trade(brand)name, Merck (Merck) company make).Make coated surface for the inboard substrate A that will be fixed with pearl shape spacer be coated with sealing agent, drip the substrate B that liquid crystal is arranged and fit after, from substrate A side, whole irradiating ultraviolet light of substrate made hardening seal, after forming liquid crystal cells, carry out the heating of 60 minutes on hot plate, under 120 ℃, forming therefrom the liquid crystal cells before the rayed that applies voltage status.

(2) apply the evaluation of the response speed of the liquid crystal cells before the rayed of voltage status

Liquid crystal cells with 2 pieces of Polarizers before with the rayed that applies voltage status of the above-mentioned gained of state clamping that becomes cross-polarized light, with camera take apply square-wave voltage (frequency be 1kHz, ± time of the brightness of liquid crystal cells 4V) time changes.Brightness settings when not applying voltage is 0%, will apply ± brightness settings during 4V is 100%, and brightness was changed to for 90% needed time as response speed from 10%.This response speed is expressed as the response speed before rayed in table 6.

(3) estimate the manufacturing of the liquid crystal cells of use

For the liquid crystal cells before the above-mentioned rayed that applies voltage status, be that the voltage of the alternating-current 10V of 60Hz drives under the state of liquid crystal applying frequency under 25 ℃, use UV irradiation equipment (it uses Metal-halogen lamp as light source) and with 100,000J/m ²The irradiation dose irradiation ultraviolet radiation.This irradiation dose is the value of using the quantorecorder measured as the benchmark of 365nm with wavelength to measure.

(4) evaluation of vertical orientation

With the above-mentioned evaluation liquid crystal cells of the state clamping that becomes cross-polarized light, utilize visual and microscope and be confirmed whether the vertical orientation bad position, with following benchmark evaluation vertical orientation with 2 pieces of Polarizers.

Good: the situation of vertical orientation bad position unconfirmed

Well: confirm the situation of vertical orientation bad position slightly

Bad: the situation of confirming a plurality of vertical orientation bad positions

Evaluation result is shown in table 6.

(5) evaluation of response speed

Use above-mentioned evaluation liquid crystal cells, utilize the gimmick identical with above-mentioned " (2) apply the evaluation of the response speed of the front liquid crystal cells of the rayed of voltage status " and measure response speed.This response speed is expressed as the response speed after rayed in table 6.

In the situation that compare with the response speed that above-mentioned (2) are measured, the response speed of estimating with liquid crystal cells more becomes shorter, more can be evaluated as the operational mode that this crystal aligning agent is suitable for this liquid crystal cells.

Example 2～example 6, example 13～example 15 and comparative example 1 and comparative example 2

In above-mentioned example 1, respectively such as table 6 set the organopolysiloxane that uses and kind and the amount of solvent record, similarly carry out from example 1 in addition and modulate 2 kinds of different crystal aligning agents of concentration, use these crystal aligning agents and estimate.

Evaluation result is shown in table 6.

In example 4～example 6 and example 13～example 15, except BC and PPh also and with the glycol of the kind of putting down in writing in table 6 and ratio as solvent.Only use BC as solvent in comparative example 1, only use BC and 2-methyl-2 in comparative example 2,4-pentanediol (HG) is as solvent.

Example 7

＜printing evaluation the modulation of crystal aligning agent 〉

In containing above-mentioned synthesis example S-1-1 in the solution of the organopolysiloxane of gained (S-1-1), the organopolysiloxane (S-2-1) that adds gained in above-mentioned synthesis example S-2-1 with the amount ratio of being put down in writing in table 6, further add ethylene glycol butyl ether (BC), propylene glycol list phenyl ether (PPh) and 2-methyl-2,4-pentanediol (HG) is as solvent, and making solvent composition is BC: PPh: HG=40: 30: 30 (weight ratio), solid concentration are the solution of 8.0 % by weight.The use aperture is that the strainer of 1 μ m filters this solution, modulates therefrom crystal aligning agent.

For this crystal aligning agent, to use E type viscometer and measure viscosity under 25 ℃, result is 16.9mPas.

＜estimate

Use 2 kinds of crystal aligning agents of above-mentioned modulation and similarly carry out various evaluations with example 1.

Evaluation result is shown in table 6.

Example 8～example 12

In above-mentioned example 7, the such organopolysiloxane (comprising the organopolysiloxane that uses with solution state) that uses and kind and amount of solvent set as shown in table 6 respectively, similarly carry out from example 7 in addition and modulate 2 kinds of different crystal aligning agents of concentration, use these crystal aligning agents and estimate.

Evaluation result is shown in table 6.

In addition, in example 8 and example 10 respectively with the ratio of mixture put down in writing in table 6 and with 2 kinds of organopolysiloxane, in example 9, example 11 and example 12 respectively with the ratio of mixture put down in writing in table 6 also with 3 kinds of organopolysiloxane.

In the crystal aligning agent of example 2 and example 13～example 15, contained polymkeric substance does not have the two keys of polymerizability, is not suitable for the manufacturing of the liquid crystal cells of the operational mode in example 1, does not therefore carry out manufacturing and the evaluation of the liquid crystal cells of model identical.In comparative example 1, produce significantly and shrink, can't form and film.Therefore, can't carry out the evaluation of vertical orientation, manufacturing and the evaluation of liquid crystal cells.

The modulation of table 6. crystal aligning agent

The evaluation of table 7. crystal aligning agent

The abbreviation of the solvent in table 6 is respectively following implication.

BC: ethylene glycol butyl ether

PPh: propylene glycol list phenyl ether

HG:2-methyl-2, the 4-pentanediol

BD:1, the 4-butyleneglycol

Claims

1. MATERIALS FOR DISPLAY, it is the MATERIALS FOR DISPLAY that contains at least polysiloxane and solvent, it is characterized in that:

Described solvent contains the represented compound of following formula (S1),

R ¹⁰O-((CR ¹¹ ₂) _m1-O) _m2-H(S1)

In formula (S1), R ¹⁰Be phenyl or benzyl, wherein, described phenyl or benzyl can be also 1～4 alkyl replacement through halogen atom, cyano group, carbon number,

R ¹¹That hydrogen atom or carbon number are 1～8 alkyl,

M1 is 2～8 integer,

M2 is 1～4 integer,

Wherein, a plurality of R ¹¹Can be identical also can be mutually different,

2. crystal aligning agent, it is the crystal aligning agent that contains at least polysiloxane and solvent, it is characterized in that:

Described solvent contains the represented compound of following formula (S1),

R ¹⁰O-((CR ¹¹ ₂) _m1-O) _m2-H(S1)

R ¹¹That hydrogen atom or carbon number are 1～8 alkyl,

M1 is 2～8 integer,

M2 is 1～4 integer,

Wherein, a plurality of R ¹¹Can be identical also can be mutually different,

3. crystal aligning agent according to claim 2 is characterized in that:

The represented compound of described formula (S1) is at least a kind that selects in the group that free glycol monomethyl phenyl ether, glycol monomethyl benzylic ether and propylene glycol list phenyl ether form.

4. according to claim 2 or 3 described crystal aligning agents is characterized in that:

With respect to the Siliciumatom in described polysiloxane is scaled SiO ₂Value 100 weight parts, the allotment ratio of the compound that described formula (S1) is represented is 20 weight parts～18,000 weight parts.

5. according to claim 2 or 3 described crystal aligning agents is characterized in that:

Described solvent further contains glycol.

6. crystal aligning agent according to claim 5 is characterized in that:

With respect to the Siliciumatom in described polysiloxane is scaled SiO ₂Value 100 weight parts, the allotment ratio of described glycol is 2 weight parts～17,500 weight parts.

7. crystal aligning agent according to claim 2 is characterized in that:

Described organopolysiloxane comprises the base of the function with the LCD alignment of making.

8. crystal aligning agent according to claim 7 is characterized in that:

Described organopolysiloxane further comprises the base with the two keys of polymerizability.

9. crystal aligning agent according to claim 7 is characterized in that:

Described organopolysiloxane further comprises carboxyl.

10. the formation method of a liquid crystal orienting film is characterized in that through following steps:

In coating according to claim 2 to 9, the described crystal aligning agent of any one and forming is filmed on substrate, secondly described filming is heated.

11. the manufacture method of a liquid crystal display device is characterized in that through following steps:

On the described conducting film of a pair of substrate that comprises conducting film respectively in coating according to claim 2 to 9 the described crystal aligning agent of any one and forming film;

Make to be formed with described described a pair of substrate Jie who films every layer of liquid crystal molecule, and with described mode subtend configuration of filming relative, thereby liquid crystal cells formed; And

Execute under alive state between the described conducting film that described a pair of substrate has, described liquid crystal cells is carried out rayed.