KR20120081552A - Process for producing liquid crystal display device, the liquid crystal display device, and liquid crystal aligning agent - Google Patents

Abstract

(Problem) It is an object of the present invention to provide a method for producing a liquid crystal display device having a wide viewing angle, fast response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability.
(Solution means) The present invention provides a liquid crystal aligning agent containing (1) a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymers. Forming a coating film on the conductive film of the pair of substrates having the conductive film, (2) the pair of substrates on which the coating film is formed so that the pair of coating films face each other, and through the liquid crystal layer. By arrange | positioning, it is a manufacturing method of the liquid crystal display element which has the process of forming a liquid crystal cell, and (3) the process of irradiating light to the said liquid crystal cell in the state which applied the voltage between the conductive films of the said pair of board | substrates.

Description

The manufacturing method of a liquid crystal display element, a liquid crystal display element, and a liquid crystal aligning agent {PROCESS FOR PRODUCING LIQUID CRYSTAL DISPLAY DEVICE, THE LIQUID CRYSTAL DISPLAY DEVICE, AND LIQUID CRYSTAL ALIGNING AGENT}

This invention relates to the manufacturing method of a liquid crystal display element, a liquid crystal display element, and a liquid crystal aligning agent. More specifically, the present invention relates to a novel method for producing a liquid crystal display device having a wide viewing angle and a fast response speed, a liquid crystal display device produced by the method, and a liquid crystal aligning agent suitably used in the method.

Among the liquid crystal display elements, a multi-domain vertical alignment (MVA) panel, which is conventionally known as a vertical alignment mode, forms projections in the liquid crystal panel, thereby restricting the falling direction of the liquid crystal molecules, thereby enlarging the viewing angle. have. However, according to this system, the lack of transmittance and contrast derived from the projections is inevitable, and there is a problem that the response speed of the liquid crystal molecules is slow.

Recently, in order to solve the problems of the aforementioned MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed. PSA mode is a polymerizable compound in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film not having a pattern, or a gap of a pair of substrates formed of two substrates with a patterned conductive film. It is a technique which controls the orientation direction of a liquid crystal by sandwiching the liquid crystal composition containing and polymerizing a polymeric compound by irradiating an ultraviolet-ray in the state which applied the voltage between electrically conductive films, and expressing a pretilt angle characteristic accordingly. According to this technique, by setting the conductive film in a specific configuration, it is possible to increase the viewing angle and to speed up the liquid crystal molecular response, thereby eliminating the problem of lack of transmittance and contrast, which is inevitable in the MVA panel. However, for the polymerization of the polymerizable compound, irradiation of a large amount of ultraviolet light, such as 100,000 J / m 2, is required, which causes a problem in that the liquid crystal molecules are decomposed. It is evident that unreacted compounds remain in the liquid crystal layer, and these interact with each other to cause display unevenness, adversely affecting voltage preservation characteristics, or causing problems in long-term reliability of the panel.

On the other hand, Nonpatent literature 1 discloses the method of using the liquid crystal aligning film formed from the polyimide-type liquid crystal aligning agent containing a reactive mesogen. According to the nonpatent literature 1, the liquid crystal display element provided with the liquid crystal aligning film formed by such a method says that the response of a liquid crystal molecule is high speed. However, in Non-Patent Document 1, there are no guidelines on what kind of reactive mesogen should be used in what amount, and the amount of ultraviolet irradiation required is still large, and there is no concern about display characteristics, especially voltage preservation characteristics. .

 Y.-J.Lee et al., SID 09 DIGEST, p.666 (2009)

This invention is made | formed in view of the said situation, Comprising: It aims at providing the manufacturing method of the liquid crystal display element which has a wide viewing angle, quick response speed of liquid crystal molecules, and excellent display property and long-term reliability.

The invention made to solve the above problems,

(1) [A] A polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymers (hereinafter, may be referred to as "[A] polymer component"). Process of forming a coating film on the conductive film of a pair of board | substrates which have a conductive film using the liquid crystal aligning agent (henceforth may be called a "liquid crystal aligning agent (A)") containing,

(2) forming a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so that the pair of coating films face each other and through the liquid crystal layer;

(3) It is a manufacturing method of the liquid crystal display element which has a process of irradiating light to the said liquid crystal cell in the state which applied the voltage between the conductive films of the said pair of board | substrates.

(In formula (A1), R <^1> is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group; some or all of the hydrogen atoms which these groups have may be substituted; R <^2> is a double bond. , A linking group comprising any of a triple bond, an ether bond, an ester bond and an oxygen atom, R ³ is a group having at least two monocyclic structures; a is 0 or 1).

According to the manufacturing method of the liquid crystal display element of this invention, in (1) process, while forming a coating film using the liquid crystal aligning agent containing the [A] polymer component which has the said specific structure, In this case, by irradiating a liquid crystal cell with a voltage applied between a conductive film of a pair of substrates, a liquid crystal display device having a wide viewing angle, a fast response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability can be manufactured. .

[A-1] The polymer component may be referred to as a polymer having a group containing the [A-1] polymerizable carbon-carbon double bond and a group represented by the formula (A1) (hereinafter referred to as "[A-1] polymer"). It is preferable to include).

According to the manufacturing method of the said liquid crystal display element, when the [A] polymer component contains a polymer [A-1], the viewing angle of the liquid crystal display element obtained, the response speed of a liquid crystal molecule, display characteristics, and long-term reliability can be improved.

[A-2] The polymer component is a polymer having a group containing a polymerizable carbon-carbon double bond (hereinafter sometimes referred to as "[A-2] polymer"), and the above-mentioned [A-3] It is also preferable to include the polymer (henceforth a "[A-3] polymer" may be called hereafter) which has group represented by Formula (A1).

According to the manufacturing method of the said liquid crystal display element, a liquid crystal display element can be manufactured more simply because [A] polymer component contains a [A-2] polymer and a [A-3] polymer.

It is preferable that R <^3> in said Formula (A1) is represented by following formula (A2).

(In formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a bivalent heterocyclic group; Some or all of them may be substituted; R ⁵ is a linking group including at least one of a methylene group which may have a substituent, an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond, and a heterocyclic group; R ⁶ is a (c + 1) valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene, or a heterocyclic compound; some or all of the hydrogen atoms of the group May be substituted; R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group; b is 0 or 1 C is an integer of 1 to 9, d is 1 or 2, and when R ⁴ , R ⁵ and R ⁷ each are plural, a plurality of R ⁴ , R ⁵ and R ⁷ may be the same or different, respectively)

According to the manufacturing method of the said liquid crystal display element, when R < ³ > in the [A] polymer component of a liquid crystal aligning agent (A) has the said specific structure, the viewing angle of the liquid crystal display element obtained, the response speed of a liquid crystal molecule, and a display characteristic And long-term reliability can be further improved.

It is preferable that the polymer component (A) has a polyorganosiloxane structure. According to the manufacturing method of the said liquid crystal display element, the light resistance of the liquid crystal display element obtained can be improved when a liquid crystal aligning agent (A) has a polyorganosiloxane structure.

It is preferable that the polymer component (A) further contains at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid and a polyimide.

According to the manufacturing method of the said liquid crystal display element, the solution characteristic of the liquid crystal aligning agent (A) obtained can be improved by further including the said specific polymer as [A] polymer component, and also of the liquid crystal display element obtained Improve electrical properties.

The liquid crystal display element manufactured by the manufacturing method of the said liquid crystal display element is also suitably contained in this invention.

The liquid crystal aligning agent of this invention,

[A] A liquid crystal aligning agent containing a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymer.

(In formula (A1), R <^1> is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group; some or all of the hydrogen atoms which these groups have may be substituted; R <^2> is a double bond. , A linking group comprising any of a triple bond, an ether bond, an ester bond and an oxygen atom, R ³ is a group having at least two monocyclic structures; a is 0 or 1).

Since the said liquid crystal aligning agent contains the polymer component which has the said specific structure, it can use suitably in the manufacturing method of the liquid crystal display element mentioned above.

The liquid crystal display device manufactured by the manufacturing method of the present invention has a wide viewing angle, a fast response speed of liquid crystal molecules, a sufficient transmittance and contrast, excellent display characteristics, and a case where display characteristics are impaired even after continuous driving for a long time. none.

Moreover, according to the manufacturing method of this invention, since the quantity of light required for irradiation becomes at least, it contributes to the reduction of the manufacturing cost of a liquid crystal display element.

Therefore, the liquid crystal display element manufactured by the manufacturing method of this invention is superior to the liquid crystal display element conventionally known in both a performance aspect and a cost aspect, and is various, including the liquid crystal television of a two-dimensional display and a three-dimensional display. It can apply suitably to the use of.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured by the Example and the comparative example.
It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the patterned transparent conductive film manufactured by the Example and the comparative example.

(Mode for carrying out the invention)

<Method of Manufacturing Liquid Crystal Display Element>

The manufacturing method of the liquid crystal display element of this invention,

(1) [A] A pair having a conductive film using a liquid crystal aligning agent containing a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymers: Forming a coating film on the conductive film of the substrate of

(2) forming a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so that the pair of coating films face each other and through the liquid crystal layer;

(3) The process of irradiating light to the said liquid crystal cell in the state which applied the voltage between the conductive films of the said pair of board | substrates.

And a liquid crystal display element can be manufactured by arrange | positioning a polarizing plate on both surfaces of the liquid crystal cell after light irradiation obtained as mentioned above. Hereinafter, each process is demonstrated.

[(1) process]

In this process, a coating film is formed on the conductive film of a pair of board | substrates which have a conductive film using the liquid crystal aligning agent (A) containing a [A] polymer component. This liquid crystal aligning agent (A) is mentioned later.

When manufacturing a TN type, STN type, or VA type liquid crystal display element, two board | substrates with which the patterned transparent conductive film is formed are made into a pair, and the liquid crystal aligning agent (A) is formed on each transparent conductive film formation surface. Preferably, it is applied by an offset printing method, a spin coating method or an inkjet printing method, and then the coating film is formed by heating each application surface. Here, as a board | substrate, for example, glass, such as float glass and soda glass, is formed. ; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film formed on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by a photo-etching method after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when forming a transparent conductive film, or the like You can. At the time of application | coating of a liquid crystal aligning agent (A), in order to make adhesiveness of a board | substrate surface and a transparent conductive film and a coating film more favorable, a functional silane compound and a functional titanium on the surface which should form a coating film in the board | substrate surface. You may perform the pretreatment which apply | coats a compound etc. previously.

After the application of the liquid crystal aligning agent (A), preliminary heating (prebaking) is preferably performed for the purpose of preventing liquid flow of the applied liquid crystal aligning agent (A). Prebaking temperature becomes like this. Preferably it is 30 to 200 degreeC, More preferably, it is 40 to 150 degreeC, Especially preferably, it is 40 to 100 degreeC. Prebaking time becomes like this. Preferably it is 0.25 minutes-10 minutes, More preferably, it is 0.5 minutes-5 minutes. Thereafter, the solvent is completely removed, and in the production of the polyorganosiloxane compound (A) described later, in the case of employing Production Method 1, firing (postbaking) is performed for the purpose of removing the remaining dicarboxylic acid. It is preferable to perform a process. As this baking (postbaking) temperature, Preferably it is 80 degreeC-300 degreeC, More preferably, it is 120 degreeC-250 degreeC. The postbaking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. Thus, the film thickness of the film | membrane formed becomes like this. Preferably it is 0.001 micrometer-1 micrometer, More preferably, it is 0.005 micrometer-0.5 micrometer.

On the other hand, when manufacturing an IPS type liquid crystal display element, the liquid crystal aligning agent (A) is made to the conductive film formation surface of the board | substrate in which the transparent conductive film patterned by the comb-tooth shape is formed, and the one surface of the counter substrate in which the conductive film is not formed. It coats, respectively, and then forms a coating film by heating each coating surface. At this time, the material of the substrate and the transparent conductive film, the patterning method of the transparent conductive film, the pretreatment of the substrate, the coating method of the liquid crystal aligning agent (A), the heating method after coating, and the preferable film thickness of the formed coating film are the TN type and the STN type. Or it is the same as the case of manufacturing a VA type liquid crystal display element.

Although the coating film after formation can provide this to the next (2) process as it is, you may perform a rubbing process arbitrarily.

The rubbing treatment can be performed by rubbing in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton and the like on the coating film surface formed as described above. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

Further, the liquid crystal alignment film formed as described above is irradiated with a part of the liquid crystal alignment film with ultraviolet rays, as shown in, for example, Japanese Patent Application Laid-Open No. 6-222366 and Japanese Patent Application Laid-open No. Hei 6-281937. A treatment for changing the pretilt angle of a portion of the liquid crystal alignment film and a rubbing treatment in a direction different from the preceding rubbing treatment after forming a resist film on a part of the surface of the liquid crystal alignment film as shown in JP-A-5-107544. After performing the process of removing a resist film, and making a liquid crystal aligning film have the liquid crystal aligning ability different for every area | region, it is possible to improve the viewing characteristic of the liquid crystal display element obtained.

[(2) process]

In this process, a liquid crystal cell is formed by arrange | positioning a pair of board | substrate which provided the said coating film so that these pair of coating films may oppose, and through a liquid crystal layer.

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. Here, when the rubbing process is performed with respect to a coating film, two board | substrates are arrange | positioned so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

As a method of manufacturing a liquid crystal cell, the following two methods are mentioned, for example.

The first method is a conventionally known method. First, two substrates are arranged to face each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent, and the substrate surface and the sealing agent are partitioned. After injecting and filling a liquid crystal in a cell gap, a liquid crystal cell can be manufactured by sealing an injection hole.

The second method is a method called the ODF (One Drop Drop) method. An ultraviolet-ray curable sealing compound is apply | coated to predetermined | prescribed place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, for example, after dropping a liquid crystal on the liquid crystal aligning film surface, the other so that a liquid crystal aligning film may oppose. A liquid crystal cell can be manufactured by bonding one board | substrate, then irradiating an ultraviolet-ray to the whole surface of a board | substrate, and hardening a sealing compound.

As said sealing agent, the epoxy resin etc. containing a hardening agent and aluminum oxide sphere as a spacer can be used, for example.

As said liquid crystal, the nematic liquid crystal which has negative dielectric anisotropy is preferable, For example, a dicyano benzene liquid crystal, a pyridazine-type liquid crystal, a siphon base liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenylcyclo Hexane type liquid crystal etc. can be used. It is preferable that the thickness of the layer of a liquid crystal shall be 1 micrometer-5 micrometers.

In any case, the liquid crystal cell produced as described above is further heated to a temperature at which the used liquid crystal takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation during liquid crystal filling. desirable

[(3) process]

In this step, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example. As an irradiation amount of light, Preferably it is 1,000 J / m <2> or more and less than 100,000 J / m <2>, More preferably, it is 1,000 J / m <2> -50,000 J / m <2>. In the manufacture of the liquid crystal display element of the conventionally known PSA mode, although it was necessary to irradiate about 100,000 J / m <2> light, in the method of this invention, the light irradiation amount is 50,000 J / m <2> or less, Furthermore, 10,000 J / m <2> or less Even if it is set as desired, a desired liquid crystal display element can be obtained, and it can contribute to the reduction of the manufacturing cost of a liquid crystal display element, and can lower the electrical characteristic resulting from strong light irradiation, and the fall of long-term reliability.

And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the said process. As this polarizing plate, the polarizing plate which consists of a polarizing plate or H film itself which sandwiched the polarizing film called "H film | membrane" which absorbed iodine, and extended | stretched polyvinyl alcohol by the cellulose acetate protective film is mentioned.

<Liquid crystal aligning agent>

The liquid crystal aligning agent (A) used in the method of this invention,

[A] The same or different polymers contain a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the formula (A1). In addition, this liquid crystal aligning agent (A) is an [A] polymer component, At least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid and a polyimide (henceforth a "polymer (B)", etc.) It may contain the "other polymer" mentioned later. Moreover, you may contain other components in the range which does not impair the effect of this invention. Hereinafter, each component is explained in full detail.

<[A] polymer component>

The polymer component (A) has a group containing a polymerizable carbon-carbon double bond and a group represented by the formula (A1) in the same or different polymers.

[Group containing a polymerizable carbon-carbon double bond]

As group containing a polymerizable carbon-carbon double bond, group etc. which are represented by following formula (A) are mentioned, for example.

In said formula (A), R ^<A> is a hydrogen atom or a methyl group.

^XI and ^XII each independently represent a 1,4-phenylene group, a methylene group, a 1,2-ethylene group, a 1,2-propylene group, or a 1,3-propylene group.

A, B, C and D are each independently 0 or 1.

Provided that when C is 0 and D is 1, X ^II is a 1,4-phenylene group.

In addition, when B is 0, D is 0.

As a specific example of group represented by said formula (A), a vinyl group, an allyl group, p-styryl group, (meth) acryloxymethyl group, 2-((meth) acryloxy) ethyl group, 3-((meth), for example Acryloxy) propyl group, 4-((meth) acryloxy) butyl group, 5-((meth) acryloxy) pentyl group, 6-((meth) acryloxy) hexyl group, 7-((meth) acryloxy ) Heptyl group, 8-((meth) acryloxy) octyl group, 9-((meth) acryloxy) nonyl group, 10-((meth) acryloxy) decyl group, 4- (2-((meth) acryl) Oxy) ethyl) phenyl group, 2-((4- (meth) acryloxy) phenyl) ethyl group, 4-((meth) acryloxymethyl) phenyl group, 4- (meth) acryloxyphenylmethyl group, 4- (3- ( (Meth) acryloxy) propyl) phenyl group, 3- (4- (meth) acryloxyphenyl) propyl group, 4-((meth) acryloxymethoxy) phenyl group, 4- (2-((meth) acryloxy) Ethoxy) phenyl group, 4- (3-((meth) acryloxy) propoxy) phenyl group, (meth) acryloxymethoxymethyl group, 2-((meth) acryloxymethok ) Ethyl group, 2- (2-((meth) acryloxy) ethoxy) ethyl group, 2- (2- (2-((meth) acryloxy) ethoxy) ethoxy) ethyl group, 3- (3-(( Meta) acryloxy) propoxy) propyl group, acryloxymethyl group and the like. Among these, vinyl group, allyl group, p-styryl group, (meth) acryloxymethyl group, 2-((meth) acryloxy) ethyl group, and 3-((meth) acryloxy) propyl group are preferable.

As group containing the said polymerizable carbon-carbon double bond, Preferably, the group represented by said formula (A), More preferably, 1 or more types chosen from the specific group illustrated above is preferable.

[Group Represented by Formula (A1)]

R <^1> of the said Formula (A1) is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group. Some or all of the hydrogen atoms which these groups have may be substituted.

As a C2-C30 alkylene group represented by said R <^1> , an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, tetrade Silenyl group, hexadecylene group, octadecylene group, nonadecylene group, eicosylene group, Henicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, A heptacosylene group, an octacosylene group, a nonacosylene group, a triaconthylene group, etc. are mentioned. Among these, in order to express liquid crystal orientation stably, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group An alkylene group having 5 or more and 20 or less carbon atoms, such as a group, a nonadecylene group, and an eicoylene group, is preferable.

R ² is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. Examples of R ² include ethendiyl group, ethyndiyl group, ester group, methanediyloxy group, fluoromethanediyloxy group, difluoromethanediyloxy group and the like. In addition, although R <^2> should just contain any of the said bond, you may contain combining each bond. In addition, R When ¹ is a phenylene group or cyclohexylene group is, in view of the solubility to the orientation or the solvent of the alignment film is formed, R ² is preferably containing an alkylene group of a methylene group or a C 2? 30. A is 0 or 1;

R ³ is a group having at least two monocyclic structures, and is preferably a group showing positive or negative dielectric anisotropy. A monocyclic structure is a structure which does not have what is called a condensed ring structure in which one ring structure exists independently from other ring structure, and the bond of one ring structure is shared with the other ring structure. In addition, as a monocyclic structure, any of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure may be sufficient, and you may have it in combination.

R ³ is not particularly limited as long as it is a group having at least two monocyclic structures, but R ³ is preferably a group represented by the following formula (A2).

In said formula (A2), R <^4> is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylene phenylene group, or a bivalent heterocyclic group. Some or all of the hydrogen atoms which these groups have may be substituted. R ⁵ is a linking group including at least any one of a methylene group which may have a substituent, an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group. R ⁶ is a (c + 1) valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene, or a heterocyclic compound. Some or all of the hydrogen atoms of this group may be substituted. R ⁷ is a hydrogen atom, cyano group, fluorine atom, trifluoromethyl group, alkoxycarbonyl group, alkyl group, alkoxy group, trifluoromethoxy group or alkylcarbonyloxy group. b is 0 or 1; c is an integer of 1-9. d is 1 or 2. R ^4, R ⁵ and R ⁷ is, if a plurality of each, a plurality of R ^4, R ⁵ and R ⁷ may may be the same or different, respectively.

By introducing the structure represented by said formula (A2), the electro-optical responsiveness of the liquid crystal display element obtained can be speeded up further. In formula (A2), R <^4> is a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylene phenylene group, or a bivalent heterocyclic group. As a bivalent heterocyclic group, a pyridinylene group, a pyridazinylene group, a pyrimidinylene group, etc. are mentioned, for example.

In the formula (A2), R ⁵ includes at least any one of a methylene group which may have a substituent, an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic group. ^{It is} a coupling group which connects ⁴ and R <^6> , It can select suitably according to the orientation or induced anisotropy required for [A] polymer component. As R ⁵ , methanediyl group, ethanediyl group, propanediyl group, ethenediyl group, ethyndiyl group, ether group, ester group, methanediyloxy group, ethanediyloxy group, fluoromethanediyloxy group, difluoro Methanediyloxy group etc. are mentioned. Among these, ethanediyl group, ethyndiyl group, ester group, methanediyloxy group, and difluoromethanediyl ox group are preferable. Further, b is 0 or 1, R ⁵ may or may not be included may be included in the design of branched structure.

In said Formula (A2), R <^6> is a (c + 1) valent group remove | excluding (c + 1) hydrogen atom from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene, or a heterocyclic compound. c is an integer of 1-9. As R <^6> , when c is 1, the group similar to the bivalent ��� illustrated as said R <^4> , etc. are mentioned, for example.

In said formula (A2), R <^7> is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group, or an alkylcarbonyloxy group. As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group etc. are mentioned, for example, As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, isobutyl group, etc. are mentioned, for example. C1-C20 linear or branched alkyl group etc. are mentioned, As alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

In the formula (A2), when R ⁶ is having a plurality of substituents (R ⁷⁾ is or may be respectively used in combination of different things. As a combination in the case where R ⁶ has a plurality of substituents, in order to stably express desired dielectric anisotropy, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable. In addition, c is an integer of 1-9.

<Polymer [A-1], [A-2], [A-3]>

[A] As the polymer component,

[A-1] It is preferable to include a polymer having a group containing a polymerizable carbon-carbon double bond and a group represented by the formula (A1).

Moreover, it is also preferable to contain the polymer which has a group containing a polymerizable carbon-carbon double bond as the polymer component [A-2], and the polymer which has a group represented by the said Formula (A1). .

These polymers can be appropriately selected from known polymer backbones as long as they have the specific group, but polyorganosiloxane, polyimide, polyamic acid, polyacrylate, polymethacrylate, poly (styrenephenylmaleimide) derivative, cellulose It is preferable to have a derivative, polyester, polyamide, polystyrene derivative, and polyamic acid ester as the main chain structure in terms of electrical properties, and polyorganosiloxane (hereinafter referred to as "polyorganosiloxane compound (A)") in terms of light resistance. May be referred to).

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) of a polyorganosiloxane compound (A) is 500-1,000,000, It is more preferable that it is 1,000-100,000, Furthermore, it is 1,000? It is preferable that it is 50,000.

Such polyorganosiloxane compound (A) may be manufactured by any method as long as it has the above characteristics.

The polyorganosiloxane compound (A) is, for example, a silane compound having a group containing a polymerizable carbon-carbon double bond and an alkoxy group (hereinafter sometimes referred to as "silane compound (a1)"), or a silane compound A mixture of (a1) with other alkoxysilane compounds (hereinafter sometimes referred to as "silane compound (a2)"),

Reacting in the presence of dicarboxylic acid and alcohol (manufacturing method 1), or

It can manufacture by the method of hydrolysis and condensation (manufacturing method 2).

In the above production method 1 or 2, a silane compound (a2) other than the silane compound (a1) is used, and a silane compound having a group represented by the formula (A1) and an alkoxy group as a part of the silane compound (a2) (hereinafter, The polyorganosiloxane compound (A) which has an airway which has a structure represented by said formula (A1) other than the group containing a polymerizable carbon-carbon double bond by using "the silane compound (a2-1)" may be called). ) Can be obtained.

Polyorganosiloxane compound (A) is,

In the said manufacturing method 1 or 2, the silane compound (a2) other than a silane compound (a1) is used, and the silane compound (a2) has an epoxy group and an alkoxy group as at least one part (Hereinafter, a "silane compound (a2- 2) ”may be used, and a polyorganosiloxane having a group containing a polymerizable carbon-carbon double bond and an epoxy group (hereinafter also referred to as“ bulb polyorganosiloxane (A ′) ”). A method of synthesizing and subsequently reacting with a carbonic acid containing a compound having a group represented by the above formula (A1) and a carboxyl group (hereinafter sometimes referred to as "specific carbonic acid 2") (manufacturing method 3); Or in the manufacturing method 1 or 2, the polyorganosiloxane which has an epoxy group first using the silane compound (a2) containing a silane compound (a2-1) as a raw material silane compound (henceforth "a precursor polyorganosiloxane (A"). ), And then a compound having a group containing a specific carbonic acid 2 and / or a polymerizable carbon-carbon double bond and a carboxyl group (hereinafter referred to as "specific carbonic acid 1"). It can also be produced by the method (reaction method 4) to react with the carboxylic acid containing.

In any of the above cases, as the silane compound (a2), silane compounds (a2) other than the silane compound (a2-1) and the silane compound (a2-2) (hereinafter also referred to as "silane compound (a2-3)") You may use together.

As said silane compound (a1), the compound etc. which are represented by following formula (a-1) are mentioned, for example.

In said formula (a-1), R ^<A> , X <^I> , X <^II> , A, B, C, and D have the same meaning as said Formula (A). R ^B is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. E is an integer of 1-3.

Examples of the formula (a-1) a C1? 12 alkyl group represented by R ^B in, C 1? 4 alkyl group, and that the preferred, for example methyl group, ethyl group, n- propyl group and as a specific example, n -Butyl group, sec-butyl group, tert-butyl group, etc. are mentioned, Preferably it is a methyl group, an ethyl group, or n-propyl group, Especially preferably, it is an ethyl group. As a C6-C12 aryl group represented by R <^1> , a phenyl group, p-methylphenyl group, etc. are mentioned, for example.

It is preferable that E in said Formula (a1) is 1 or 2, Especially preferably, it is 1.

As a specific example of a silane compound (a1), for example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tri-n-butoxy silane, vinyl triisobutoxy Silane, vinyltri-tert-butoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, allyltriisopropoxysilane, allyltri-n-butoxysilane, allyltriisobutoxysilane , Allyltri-tert-butoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltripropoxysilane, p-styryltriisopropoxysilane, p-sty Reyl tri-n-butoxysilane, p-styryl triisobutoxysilane, p-styryl tri-tert-butoxysilane, (meth) acryloxymethyl trimethoxysilane, (meth) acryloxymethyl triethoxy Silane, (meth) acryloxymethyl tri-n-propoxy silane, (meth) acryloxymethyl tri-iso-propoxy Column, (meth) acryloxymethyltri-n-butoxysilane, (meth) acryloxymethylpropyltri-sec-butoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acrylic Oxyethyltriethoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (meth) acryloxyethyltri-iso-propoxysilane, 2- (meth) acryloxyethyltri-n -Butoxysilane, 2- (meth) acryloxyethylpropyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropyl tri-n-propoxysilane, 3- (meth) acryloxypropyl tri-iso-propoxysilane, 3- (meth) acryloxypropyl tri-n-butoxysilane, 3- (meth ) Acryloxypropyl tri-sec-butoxysilane,

4- (meth) acryloxybutyl trimethoxysilane, 4- (meth) acryloxybutyl triethoxysilane, 4- (meth) acryloxybutyl tri-n-propoxysilane, 4- (meth) acryloxybutyl Tri-iso-propoxysilane, 4- (meth) acryloxybutyl tri-n-butoxysilane, 4- (meth) acryloxybutylpropyl tri-sec-butoxysilane, 5- (meth) acryloxypentyl Limethoxysilane, 5- (meth) acryloxypentyltriethoxysilane, 5- (meth) acryloxypentyl tri-n-propoxysilane, 5- (meth) acryloxypentyl tri-iso-propoxysilane , 5- (meth) acryloxypentyltri-n-butoxysilane, 5- (meth) acryloxypentylpropyltri-sec-butoxysilane, 6- (meth) acryloxyhexyltrimethoxysilane, 6- (Meth) acryloxyhexyl triethoxysilane, 6- (meth) acryloxyhexyl tri-n-propoxysilane, 6- (meth) acryloxyhexyl tri-iso-propoxysilane, 6- (meth) acryloxy Hexyltri-n-butoxysilane, 6- (Meth) acryloxyhexylpropyl tri-sec-butoxysilane, acryloxymethyl trimethoxysilane, etc. are mentioned, It is preferable to use 1 or more types chosen from these. More preferably, vinyl trimethoxysilane, vinyl triethoxysilane, allyl trimethoxysilane, allyl triethoxysilane, p-styryl trimethoxysilane, p-styryl triethoxysilane, and (meth) acryl It is 1 or more types chosen from the group which consists of an oxymethyl trimethoxysilane, 2- (meth) acryloxyethyl trimethoxysilane, and 3- (meth) acryloxypropyl trimethoxysilane.

The said silane compound (a2-1) is a silane compound which has a group represented by said formula (A1) and an alkoxy group, and can also use together the silane compound represented by a following formula (a2-1a).

(R ^C ) _f (R ^D ) _g Si (OR ^E ) _4-fg (a2-1a)

In said formula (a2-1a), R <^C> is a C4-C30 alkyl group, a C1-C30 fluorinated alkyl group, or the alkoxy which has a C17-C50 hydrocarbon group and a C2-C24 alkoxy group which have a steroid skeleton It is a C12-30 hydrocarbon group which has a phenyl group or a bicyclohexane skeleton.

R ^D is an alkyl group having 1 to 3 carbon atoms.

R ^E is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.

f is an integer of 1 to 3. g is an integer of 0-2. However, f + g ≤ 3.

About R <^C> in said Formula (a2-1a), it is the same as what was mentioned above about the group represented by said Formula (A1) which a polyorganosiloxane compound (A) can have arbitrarily. As R ^{D, a} methyl group is preferable. About R ^E , it is the same as described above with respect to R ^B in the formula (a-1). It is preferable that f is 1, and it is preferable that g is 0 or 1.

As a silane compound represented by said formula (a2-1a),

As the silane compound having an alkyl group having 4 to 30 carbon atoms, for example,

n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n -Butyl tri-sec-butoxysilane, n-butyl tri-n-pentoxysilane, n-butyl tri-sec-pentoxysilane, n-butyl triphenoxysilane, n-pentyl trimethoxysilane, n- Pentyltriethoxysilane, n-pentyltriphenoxysilanehexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, n-octyltrimethoxysilane, n-decyltri Methoxysilane, n-dodecyl trimethoxysilane, n-octadecyl trimethoxysilane, etc. are mentioned.

Moreover, as a silane compound which has a C1-C30 fluorinated alkyl group, it is, for example,

3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- (perfluoro -n-propyl) ethyltrimethoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltrimethoxysilane, and the like.

As a silane compound which has a C17-51 hydrocarbon group which has a steroid structure, for example,

3-cholestanyltrimethoxysilane, 3-cholestanyltriethoxysilane, 3-cholestanyltri-n-propoxysilane, 3-cholestanyltri-iso-propoxysilane, 3-cholesta Neyl tri-n-butoxysilane, 3-cholestanyl tri-sec-butoxysilane, 3-cholesteryl trimethoxysilane, etc. are mentioned.

As a silane compound which has an alkoxyphenyl group which has a C2-C24 alkoxy group, for example,

4-pentoxyphenyltrimethoxysilane, 4-pentoxyphenyltriethoxysilane, 4-hexyloxyphenyltrimethoxysilane, 4-octyloxyphenyltrimethoxysilane, 4-dodecyloxyphenyltrimethoxysilane Etc. can be mentioned.

The said silane compound (a2-2) is a silane compound which has an epoxy group and an alkoxy group, Preferably it is a compound represented by a following formula (a2-2).

(R ^F ) _h (R ^G ) _i Si (OR ^H ) _4-hi (a2-2)

(In Formula (a2-2), R ^F is a monovalent group having an epoxy group; R ^G is an alkyl group having 1 to 3 carbon atoms; R ^H is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms). h is an integer of 1 to 3, i is an integer of 0 to 2, provided that h + i ≦ 3.

As R <^F> in a formula (a2-2), 3-glycidoxy propyl group, 2- (3, 4- epoxy cyclohexyl) ethyl group, etc. are mentioned, for example. As R ^G , a methyl group is preferable. About R ^H , it is the same as described above with respect to R ^B in the formula (a-1). It is preferable that h is 1, and it is preferable that i is 0 or 1.

As a specific example of a silane compound (a2-2), for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, One or more types selected from these can be used.

The said silane compound (a2-3) is a silane compound (a2) other than a silane compound (a2-1) and (a2-2), For example, the silane compound etc. which are represented by a following formula (a2-3) are mentioned. have.

(R ^P ) _j Si (OR ^Q ) _4-j (a2-3)

In said formula (a2-3), R ^P is a C1-C3 alkyl group or a phenyl group.

R ^Q is a C1-C12 alkyl group or a C6-C12 allyl group. j is an integer of 0-3.

R for ^Q in the formula (a2-3), the same meanings as those defined above for the R ^B in the formula (a-1).

As a specific example of a silane compound (a2-3),

As the compound whose j is 0, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-sec-propoxysilane, tetra-n-part Oxysilane, tetra-sec-butoxysilane, etc. are mentioned.

As the compound j is 1, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyl Tri-sec-butoxysilane, methyltri-n-pentoxysilane, methyltri-sec-pentoxysilane, methyltriphenoxysilane, methyltri-p-methylphenoxysilane, ethyltrimethoxysilane, n- Propyltrimethoxysilane, phenyltrimethoxysilane, and the like.

As the compound of j is 2, for example, dimethyldimethoxysilane, diethyldimethoxysilane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane Etc. can be mentioned.

As the compound j is 3, for example, trimethylmethoxysilane, triethylmethoxysilane, tri-n-propylmethoxysilane, tri-iso-propylmethoxysilane, trimethylethoxysilane, triethylethoxysilane Etc. can be mentioned. Among these, More preferably, it is a compound whose j is 0 or 1 in the said Formula (a2-3), Furthermore, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Tetramethoxysilane and tetraethoxysilane are preferable, especially the compound whose j is 0 in said Formula (a2-3) is preferable, and especially tetramethoxysilane and tetraethoxysilane are preferable.

When manufacturing a polyorganosiloxane compound (A) by the manufacturing method 1 or 2, it is preferable that the silane compound used as a raw material contains 1 mol% or more of the said silane compound (a1) with respect to the whole of a silane compound. It is more preferable to contain 1 mol%-60 mol%, It is more preferable to contain 2 mol%-50 mol%, It is preferable to contain 2 mol%-30 mol% especially.

When manufacturing the polyorganosiloxane compound (A) which has an airway represented by said formula (A1) other than the group containing a polymerizable carbon-carbon double bond by the manufacturing method 1 or 2 together with a silane compound (a1), Silane compound (a2-1) is used. In this case, the use ratio of the silane compound (a2-1) is preferably 60 mol% or less, more preferably 5 mol% to 50 mol% with respect to the entire silane compound, particularly 10 mol% It is preferable to set it as -40 mol%.

In the manufacturing method 1 or 2, it is preferable to use a silane compound (a2-3) together in addition to said silane compound. It is preferable to make it 60 mol% or less with respect to the whole silane compound, It is more preferable to set it as 0 mol%-40 mol%, It is preferable to set it as 0 mol%-20 mol% especially.

When manufacturing a polyorganosiloxane compound (A) by the manufacturing method 3, it is preferable that the silane compound used as the raw material contains 1 mol% or more of the said silane compound (a1) with respect to the whole of a silane compound. It is more preferable to contain 1 mol%-60 mol%, It is still more preferable to contain 2 mol%-50 mol%, It is preferable to contain 2 mol%-30 mol% especially.

When manufacturing a polyorganosiloxane compound (A) by the manufacturing method 3, a silane compound (a2-2) other than the said silane compound (a1) is used. It is preferable to use this silane compound (a2-2) as 10 mol% or more with respect to the whole silane compound, It is more preferable to set it as 20 mol%-90 mol%, Especially it is 30 mol%-70 It is preferable to set it as mol%.

When manufacturing a polyorganosiloxane compound (A) by the manufacturing method 4, the silane compound used as the raw material contains 20 mol% or more of the said silane compound (a2-2) with respect to the whole of a silane compound. It is preferable, and it is more preferable to contain 40 mol%.

In the manufacturing methods 3 and 4, it is preferable not to use a silane compound (a2-3).

A polyorganosiloxane compound (A), a precursor polyorganosiloxane (A '), or a precursor polyorganosiloxane (A ") is the said silane compound,

Reacting in the presence of dicarboxylic acid and alcohol (manufacturing method 1), or

It can manufacture respectively by the method of hydrolysis and condensation (manufacturing method 2).

Hereinafter, the manufacturing method 1 and the manufacturing method 2 are demonstrated in order.

[Production Method 1]

Production method 1 is a method in which the silane compound is reacted in the presence of dicarboxylic acid and alcohol.

Examples of the dicarboxylic acid used herein include oxalic acid, malonic acid, a compound in which two carboxyl groups are bonded to an alkylene group having 2 to 4 carbon atoms, benzenedicarboxylic acid, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned, It is preferable to use 1 or more types chosen from these. Particularly preferably oxalic acid.

The use ratio of dicarboxylic acid is preferably such that the amount of the carboxyl group to the total of 1 mole of the alkoxyl group of the silane compound used as the starting material is 0.2 mole to 2.0 mole, and is 0.5 mole to 1.5 mole. It is more preferable to.

As said alcohol, primary alcohol can be used suitably. Specific examples thereof include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-ethylbutanol, 3-heptanol, n-octanol, 2-ethylhexanol, n-nonyl alcohol, 2, 6-dimethyl-4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, and the like. It is preferable to use one or more selected from. The alcohol used herein is preferably an aliphatic primary alcohol having 1 to 4 carbon atoms and is selected from the group consisting of methanol, ethanol, iso-propanol, n-propanol, iso-butanol, sec-butanol and tert-butanol. It is more preferable to use 1 or more types, and it is especially preferable to use 1 or more types chosen from the group which consists of methanol and ethanol.

It is preferable to make the ratio of the silane compound and dicarboxylic acid which occupy the whole amount of the reaction solution into the ratio which the use ratio of the alcohol in the manufacturing method 1 become 3 mass%-80 mass%, and 25 mass%-70 mass% It is more preferable to set it as the ratio which becomes.

It is preferable that reaction temperature is 1 degreeC-100 degreeC, More preferably, it is 15 degreeC-80 degreeC. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

In the manufacturing method 1, it is preferable not to use other solvent other than the said alcohol.

In Production method 1, the alcohol acts on the intermediate produced by the reaction between the silane compound and the dicarboxylic acid, so that the poly is a condensate of the silane compound (a1) or a cocondensate of the silane compound (a1) and the silane compound (a2). It is inferred that an organosiloxane will be produced.

[Manufacturing Method 2]

The manufacturing method 2 is a method of hydrolyzing and condensing the said silane compound.

This hydrolysis-condensation reaction can be performed by making a silane compound and water react in presence of a catalyst preferably in a suitable organic solvent.

It is preferable that the ratio of the water used here is 0.5 mol-2.5 mol as the quantity with respect to the total of 1 mol of the alkoxyl groups which the silane compound used as a raw material has.

As said catalyst, an acid, a base, a metal compound, etc. are mentioned. As an example of such a catalyst, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, etc. are mentioned, for example.

As the base, both an inorganic base and an organic base can be used, and examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like;

Examples of the organic base include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Tetramethylammonium hydroxide etc. are mentioned, respectively.

As a metal compound, a titanium compound, a zirconium compound, etc. are mentioned, for example.

It is preferable to set it as 10 mass parts or less with respect to a total of 100 mass parts of the silane compound used as a raw material, It is more preferable to set it as 0.001 mass part-10 mass parts, More preferably, 0.001 mass part-1 mass It is preferable to make it negative.

Examples of the organic solvent include alcohols, ketones, amides, esters and other non-protic compounds. As said alcohol, both the alcohol which has one hydroxyl group, the alcohol which has two or more hydroxyl groups, and the partial ester of the alcohol which has two or more hydroxyl groups can be used. As the ketone, monoketone and β-diketone can be preferably used.

Specific examples of such organic solvents include alcohols having one hydroxyl group, for example methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-ethylbutanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, di Acetone alcohol, etc. are mentioned,

Examples of the alcohol having a plurality of hydroxyl groups include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, and 2,5-hexane Diol, 2,4-heptane diol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and the like.

As partial ester of the alcohol which has two or more hydroxyl groups, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol Mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like.

As the monoketone, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, and ethyl-n- Butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, fenchon Etc.,

As said β-diketone, for example, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4 Nonanodione, 3,5-nonandadione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5, 5-hexafluoro-2,4-pentanedione, etc. are mentioned,

As the amide, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpi Rollidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. are mentioned.

As ester, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-acetic acid Butyl, iso-acetic acid acetate, see-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cycloacetic acid Hexyl, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl acetate acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate N-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. Can be mentioned.

As other aprotic solvents, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N -Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone , N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, and the like Can be mentioned.

As a usage ratio of an organic solvent, as a ratio which the total mass of components other than the organic solvent in a reaction solution occupies for the total amount of reaction solution, it is preferable to set it as the ratio used as 1 mass%-90 mass%, and 10 mass%-70 It is more preferable to set it as the ratio used as mass%.

In the manufacturing method 2, the water added at the time of manufacture of polyorganosiloxane can be added intermittently or continuously in the silane compound which is a raw material, or in the solution which melt | dissolved a silane compound in the organic solvent.

The catalyst may be added in advance in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

It is preferable that reaction temperature is 1 degreeC-100 degreeC, More preferably, it is 15 degreeC-80 degreeC. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

When manufacturing method 1 or 2 is employ | adopted as a manufacturing method of a polyorganosiloxane compound (A), a polyorganosiloxane compound (A) can be obtained as mentioned above.

When manufacturing method 3 is employ | adopted as a manufacturing method of a polyorganosiloxane compound (A), it is made by making the precursor polyorganosiloxane (A ') obtained as mentioned above react with the carbonic acid containing specific carbonic acid 2 further, The organosiloxane compound (A) can be obtained.

When manufacturing method 4 is employ | adopted as a manufacturing method of a polyorganosiloxane compound (A), the precursor polyorganosiloxane (A ") obtained by making it above is made into specific carbonic acid 1, and / or specific carbonic acid 2, The polyorganosiloxane compound (A) can be obtained by reacting with the carboxylic acid to contain.

[Reaction of Light Bulb Polyorganosiloxane (A ') and Carbonic Acid]

The specific carboxylic acid 2 used in the manufacturing method 3 is a compound which has group and carboxyl group represented by said formula (A1).

As specific carboxylic acid 2 used in the manufacturing method 3, the compound which has a carboxyl group represented by a following formula (A1-C) is mentioned.

In said formula (A1-C), R <^1> is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group. Some or all of the hydrogen atoms which these groups have may be substituted. R ² is a linking group comprising any of a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. R ³ is a group having at least two monocyclic structures. a is 0 or 1;

By utilizing the reactivity between the epoxy group and the carboxyl group, a structure having dielectric anisotropy represented by the formula (A1-C) as a side chain in the polyorganosiloxane as a main chain can be easily introduced.

As specific carbonic acid 2, the compound etc. which are represented by following formula (D-1) (D-25)-are mentioned, for example.

R <^3> is the same as said Formula (A1-C) in said Formula (D-1) (D-25). m is an integer of 1-30.

As group represented by said formula (A2), group represented by following formula (E-1)-(E-123) is mentioned, for example.

In said formula (E-1)-(E-123), R is a C1-C20 alkyl group. Or an alkoxy group having 1 to 20 carbon atoms. X is each independently a hydrogen atom or a fluorine atom.

As a C1-C20 alkyl group represented by said R, a (methyl group, an ethyl group, a propyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, etc.) are mentioned, for example, As an alkoxy group of -20, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, butoxy group etc. are mentioned, for example.

[Synthesis method of specific carbonic acid]

The synthesis procedure of specific carbon acid is not specifically limited, It can carry out combining a conventionally well-known method. As a typical synthesis sequence, for example, (1) a compound having a phenol skeleton and a compound in which an alkyl chain portion of a higher fatty acid ester is substituted with halogen are reacted under alkaline conditions, and the hydroxyl group of the phenol skeleton is substituted with carbon substituted with halogen. A bond is formed, and then the ester is reduced to form a specific carboxylic acid; (2) a compound having a phenol skeleton and ethylene carbonate are reacted to produce a terminal alcohol compound, and the hydroxyl group and the halogenated benzenesulfonyl chloride are reacted. Activating, then reacting methyl benzoate containing hydroxyl group to the activating moiety, together with desorption of the sulfonyl moiety to form a bond of the hydroxyl group of the terminal alcohol compound with the hydroxyl group of methyl benzoate containing the hydroxyl group as a substituent, followed by ester The method of reducing | reducing to specific carbonic acid etc. is illustrated. However, the synthesis | combination order of specific carbonic acid is not limited to these.

In the manufacturing method 3, only carbonic acid 2 may be used as carbonic acid, or a part of specific carbonic acid may be substituted and used by the compound represented by following formula (4) in the range which does not impair the effect of this invention. . In this case, the synthesis | combination of a polyorganosiloxane compound (A) is performed by making the polyorganosiloxane which has an epoxy group, and the mixture of the specific carboxylic acid 2 and the compound represented by following formula (4) react.

In said formula (4),

A ¹ is a C17-C10 cycloalkyl group or a C17-C15 hydrocarbon group which may be substituted with a C1-C30 linear or branched alkyl group, a C1-C20 alkyl group, or an alkoxyl group . However, one part or all part of the hydrogen atom of the said alkyl group and the alkoxy group may be substituted by substituents, such as a cyano group, a fluorine atom, and a trifluoromethyl group.

L ⁰ is a single bond, -O-, -COO- or -OCO-.

L ¹ is a single bond, a methylene group, an alkylene group having 2 to 20 carbon atoms, a phenylene group, a biphenylene group, a cyclohexylene group, a bicyclohexylene group, or the following formula (L ¹ -1) or (L ¹ -2) Is represented by.

Z is a monovalent organic group which can react with the epoxy group in the polyorganosiloxane compound (A) to form a bonding group.

Provided that when L ¹ is a single bond, L ⁰ is a single bond.

In the formulas (L ¹ -1) and (L ¹ -2), the bonding hand with "*" is bonded to Z, respectively.

Z is preferably a carboxyl group.

As a C1-C30 linear or branched alkyl group which A <^1> represents in said Formula (4), a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group is mentioned, for example. , tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3- Methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methyl hexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group , 1-methylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3 -Dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3 , 3-trimethylbutyl group, 1,2,3-t Methylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl group , n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n- tetradecyl group, n-heptadecyl group, n-hexadecyl group, n-heptadecyl group , n-octadecyl group, n-nonadecyl group and the like.

As a C3-C10 cycloalkyl group which may be substituted by the C1-C20 alkyl group or the alkoxy group, For example, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononanyl group, cyclodecyl group, cyclo Dodecyl group etc. are mentioned.

As a C17-51 hydrocarbon group which has a steroid skeleton, group represented by following formula (H-1)? (H-3) is mentioned, for example.

As A <^1> in said Formula (4), the group chosen from a C1-C20 alkyl group, a C1-C20 fluorinated alkyl group, and said Formula (H-1) or (H-3) is preferable.

As a compound represented by said formula (4), the compound represented by following formula (4-1)-(4-6) is preferable.

In said formula (4-1)-(4-6), u is an integer of 1-5. v is an integer of 1-18. w is an integer of 1-20. k is an integer of 1-5. p is 0 or 1. q is an integer of 0-18. r is an integer of 0-18. s and t are each independently an integer of 0-2.

Among these compounds, compounds represented by the following formulas (5-1) to (5-7) are more preferable.

The compound represented by said formula (4) is a compound which becomes a site | part which provides pretilt angle expression property to the liquid crystal aligning film obtained by reacting with the polyorganosiloxane which has an epoxy group with specific carbonic acid. In this specification, the compound represented by said formula (4) may be called "other pretilt angle expressing compound" below.

In the present invention, when the other pretilt-angle expressing compound is used together with the specific carbon acid, the ratio of the sum of the specific carbon acid and the other pretilt-expressing compound is 1 mole of the epoxy group of the polyorganosiloxane. Preferably it is 0.001 mol-1.5 mol, More preferably, it is 0.01 mol-1 mol, More preferably, it is 0.05 mol-0.9 mol. In this case, the other pretilt-angle expressing compound is preferably used in a range of 75 mol% or less, more preferably 50 mol% or less, based on the total amount with the specific carbonic acid. When the use ratio of the other pretilt-angle expressing compound exceeds 75 mol%, adverse effects may appear on the high-speed response of the liquid crystal.

The reaction of the precursor polyorganosiloxane (A ') with the carbonic acid is preferably performed in the presence of a suitable catalyst and a suitable organic solvent.

As a catalyst used in reaction of precursor polyorganosiloxane (A ') and a carbonic acid, an organic base can be used suitably, for example, what is called a hardening accelerator which promotes reaction of an epoxy compound and an acid anhydride is used. It can be used as a catalyst in this reaction. As said organic base, primary or secondary organic amine, tertiary organic amine, quaternary organic amine salt, etc. are mentioned, for example.

Examples of the curing accelerator include tertiary amines (excluding tertiary organic amines as organic bases), imidazole derivatives, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and halogenated quaternary Ammonium, metal halide compounds, latent curing accelerators and the like. As said latent hardening accelerator etc., a high melting | dispersion type latent hardening accelerator (for example, an amine addition type accelerator), a microcapsule type latent hardening accelerator, an amine salt type latent hardening accelerator, a high temperature dissociation type | formula Polymeric latent hardening accelerators etc. are mentioned.

As a specific example of such a catalyst, ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole etc. are mentioned as said primary or secondary organic amine.

Examples of the tertiary organic amine include triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene and the like.

As said quaternary organic amine salt, tetramethylammonium hydroxide etc. are mentioned, for example.

Examples of the tertiary amines (excluding tertiary organic amines as the organic base) include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine, and the like. have.

Examples of the imidazole derivatives include 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimida. Sol, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-sia Noethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) Imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n Undecyl imidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n -Undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2 Isocyanuric acid adduct of methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] Isocyanuric acid adducts of ethyl-s-triazine and the like.

Moreover, a diphenyl phosphine, a triphenyl phosphine, a triphenyl phosphite etc. are mentioned as said organophosphorus compound, for example.

Examples of the quaternary phosphonium salts include benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetra Phenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazole Tetra, n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate and the like;

As said diazabicycloalkene, 1,8- diazabicyclo [5.4.0] undecene-7, its organic acid salt, etc. are mentioned, for example.

As said organometallic compound, zinc octylate, tin octylate, an aluminum acetylacetone complex, etc. are mentioned, for example.

As said quaternary ammonium halide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc. are mentioned, for example.

As said metal halogen compound, For example, boron compounds, such as boron trifluoride and a triphenyl borate; Zinc chloride, a 2nd tin chloride, etc. are mentioned.

As said high melting-point dispersion type latent hardening accelerator, the adduct of dicyandiamide or an amine, and an epoxy resin etc. are mentioned, for example.

As said microcapsule-type latent hardening accelerator, the latent hardening accelerator etc. which coat | covered the surface of hardening accelerators, such as the said imidazole derivative, an organophosphorus compound, a quaternary phosphonium salt, with a polymer etc. are mentioned.

As said high temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, a Lewis acid salt, Bronsted acid salt, etc. are mentioned, respectively.

Of these, it is preferable to use quaternary organic amine salts or quaternary ammonium halides.

The use ratio of a catalyst becomes like this. Preferably it is 0.01 mass part-100 mass parts, More preferably, it is 0.1 mass part-20 mass parts with respect to 100 mass parts of precursor polyorganosiloxane (A ').

Examples of the organic solvent used in the reaction between the precursor polyorganosiloxane (A ') and the carbonic acid include ketones, ethers, esters, amides and alcohols. Specific examples of such organic solvents include the ketones. For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc. are mentioned,

Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, and the like.

As said ester, ethyl acetate, n-butyl acetate, iso-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc. are mentioned,

Examples of the amide include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N -Dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-form Milpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. are mentioned,

Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like.

The use ratio of an organic solvent is a ratio which the total mass of components other than the organic solvent in a reaction solution occupies for the total amount of reaction solution, It is preferable to set it as the ratio used as 0.1 mass%-50 mass%, and 5 mass%-50 It is more preferable to set it as the ratio used as mass%.

The reaction between the precursor polyorganosiloxane (A ') and the carbonic acid is preferably 0 ° C to 200 ° C, more preferably at a temperature of 50 ° C to 150 ° C, preferably 0.1 hour to 50 hours, more preferably Is done for 0.5 hours to 20 hours

[Reaction of Light Bulb Polyorganosiloxane (A ") with Carbonic Acid]

The specific carboxylic acid 1 used in the production method (4) is a compound having a group containing a polymerizable carbon-carbon double bond and a carboxyl group. About the group containing the polymerizable carbon-carbon double bond which specific carbonic acid 1 has, it is the same as what was demonstrated above about the group containing the polymerizable carbon-carbon double bond which the polyorganosiloxane compound (A) has.

As specific carbonic acid 1 used in the manufacturing method 4, it is (meth) acrylic acid, a crotonic acid, (alpha)-ethyl acrylic acid, the (alpha)-n-propyl acrylic acid, the (alpha)-n-butylacrylic acid, maleic acid, fumaric acid, a citraconic acid, for example. And mesaconic acid, itaconic acid, and the like, and one or more kinds selected from these can be used.

In the manufacturing method 4, only specific carbonic acid 1 may be used as carbonic acid, or only the said specific carbonic acid 2 may be used with specific carbonic acid 1, or may be used together.

In this invention, you may replace and use a part of specific carbonic acid by the compound represented by said formula (4) in the range which does not impair the effect of this invention. In this case, synthesis | combination of a polyorganosiloxane compound (A) is performed by making the polyorganosiloxane which has an epoxy group, and the mixture of the specific carbonic acid and the compound represented by said formula (4) react. The compound represented by the said Formula (4) is the same as that shown by the manufacturing method 3.

In the present invention, when the other pretilt-angle expressing compound is used together with the specific carbon acid, the ratio of the sum of the specific carbon acid and the other pretilt-expressing compound is 1 mole of the epoxy group of the polyorganosiloxane. Preferably it is 0.001 mol-1.5 mol, More preferably, it is 0.01 mol-1 mol, More preferably, it is 0.05 mol-0.9 mol. In this case, the other pretilt-angle expressing compound is preferably used in a range of 75 mol% or less, more preferably 50 mol% or less, based on the total amount with the specific carbonic acid. When the use ratio of the other pretilt-angle expressing compound exceeds 75 mol%, adverse effects may appear on the high-speed response of the liquid crystal.

The suitable use ratio of each carbonic acid in the manufacturing method 4 is as follows, respectively.

As a usage ratio of the sum total of a carbonic acid, 0.1 mol-0.9 mol, More preferably, 0.2 mol-0.7 mol, More preferably, with respect to 1 mol of the epoxy group which precursor polyorganosiloxane (A ") has. 0.3 mol-0.5 mol.

As use ratio of specific carbonic acid 1, Preferably it is 50 mol% or more, More preferably, it is 70 mol% or more, More preferably, it is 90 mol% or more with respect to all carbonic acids.

As a usage ratio of specific carbonic acid 2, Preferably it is 50 mol% or less with respect to all carbonic acids, More preferably, it is 1 mol%-30 mol%, More preferably, it is 5 mol%-10 mol%.

Reaction of the precursor polyorganosiloxane (A ") and the carbonic acid in the manufacturing method 4 is the precursor polyorganosiloxane in the manufacturing method 3 except using the precursor polyorganosiloxane (A") and the said carbon acid. It can carry out similarly to the above-mentioned as reaction of (A ') and carboxylic acid.

As described above, the polyorganosiloxane compound (A) in the present invention can be obtained.

As the [A] polymer component, a liquid crystal aligning agent (A) may be called polymer other than a polyorganosiloxane compound (A) other than the said polyorganosiloxane compound (A) (henceforth "other polymer"). ) May be contained.

[Other polymers]

Other polymer can be used in order to improve the solution characteristic of a liquid crystal aligning agent (A), and the electrical characteristic of the obtained liquid crystal display element further. As other polymers, for example

At least one polymer (polymer (B)) selected from the group consisting of polyamic acid and polyimide;

At least one selected from the group consisting of a polyorganosiloxane represented by the following formula (a1), a hydrolyzate thereof and a condensate of the hydrolyzate thereof (hereinafter, may be referred to as "other polyorganosiloxane");

Polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrenephenylmaleimide) derivative, poly (meth) acrylate and the like.

In said formula (a1), X ^<A> is a hydroxyl group, a halogen atom, a C1-C20 alkyl group, a C1-C6 alkoxy group, or a C6-C20 aryl group. Y ^A is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

[Polymer (B)]

The polymer (B) is at least one polymer selected from the group consisting of polyamic acid and polyimide. Hereinafter, polyamic acid and polyimide are explained in full detail.

[Polyamic acid]

Polyamic acid can be obtained by making tetracarboxylic dianhydride and a diamine compound react.

As tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. These tetracarboxylic dianhydrides can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, butane tetracarboxylic dianhydride etc. are mentioned, for example.

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 -Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornan-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3 , 5,8,10-tetraon and the like.

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. are mentioned, for example, The tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 is mentioned.

Among these tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides are preferred, and 2,3,5-tricarboxycyclopentyl acetic dianhydride or 1,2,3,4-cyclobutanetetracarboxylic dianhydride is more preferred. Preferred, 2,3,5-tricarboxycyclopentylacetic acid dianhydride is particularly preferred.

As a usage-amount of 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 10 mol% or more is preferable with respect to the total tetracarboxylic dianhydride, 20 mol% or more is more preferable, It is especially preferable to consist only of 2,3,5- tricarboxy cyclopentyl acetic acid dianhydride or 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

As a diamine compound, aliphatic diamine, alicyclic diamine, diamino organosiloxane, aromatic diamine, etc. are mentioned, for example. These diamine compounds can be used individually or in combination of 2 or more types.

Examples of the aliphatic diamines include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like.

As alicyclic diamine, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc. are mentioned, for example.

As diamino organosiloxane, 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc. are mentioned, for example, Diamine of Unexamined-Japanese-Patent No. 2010-97188 is mentioned.

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4- Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy-2, 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2,5- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-dia Minobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid chole Stanyl, 3,5-diaminobenzoic acid cholesterol, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6- S (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclo Hexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) Phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl ) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine and represented by the following formula (A-1) And diamine compounds.

In said formula (A-1), X ^B is a methylene group, a C2 or C3 alkylene group, -O-, -COO-, or -OCO-. r is 0 or 1; s is an integer of 0-2. t is an integer of 1-20.

As an use ratio of the tetracarboxylic dianhydride and a diamine compound provided for the synthesis reaction of polyamic acid, 0.2 equivalent-2 equivalent of the acid anhydride group of tetracarboxylic dianhydride is preferable with respect to 1 equivalent of the amino group contained in a diamine compound, 0.3 equivalent-1.2 equivalent are more preferable.

It is preferable to perform a synthesis reaction in an organic solvent. As reaction temperature, -20 degreeC-150 degreeC is preferable, and 0 degreeC-100 degreeC is more preferable. As reaction time, 0.5 hour-24 hours are preferable, and 2 hours-12 hours are more preferable.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide Aprotic polar solvents such as N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned.

As the usage-amount (a) of an organic solvent, 0.1 mass%-50 mass% are preferable with respect to the total amount (b) of the total amount (b) of tetracarboxylic dianhydride and a diamine compound, and the usage-amount (a) of an organic solvent. 5 mass%-30 mass% are more preferable.

The polyamic acid solution obtained after reaction may be used as it is for preparation of a liquid crystal aligning agent (A), and may be used for preparation of a liquid crystal aligning agent (A) after isolating the polyamic acid contained in a reaction solution, and isolated polyamic acid After refine | purifying, you may provide for preparation of a liquid crystal aligning agent (A). As a method for isolating polyamic acid, for example, a method of drying the precipitate obtained by pouring the reaction solution in a large amount of poor solvents under reduced pressure, a method of distilling the reaction solution under reduced pressure with an evaporator, and the like can be given. As a purification method of a polyamic acid, the method of dissolving isolated polyamic acid again in an organic solvent, precipitating with a poor solvent, the method of carrying out the process of distilling a vacuum solvent and the like off under reduced pressure in an evaporator once or several times is mentioned. have.

[Polyimide]

Polyimide can be manufactured by dehydrating and ring-closing the acid-acid structure which the said polyamic acid has, and imidizing it. The polyimide may be a complete imide obtained by dehydrating and ring-closing all of the dark acid structures possessed by the polyamic acid as its precursor, or by partially dehydrating and ring-closing a part of the dark acid structure, and the partial imide compound in which the dark acid structure and the imide ring structure coexist. It may be.

As a method for synthesizing the polyimide, for example, (i) a method of heating polyamic acid (hereinafter may be referred to as "method (iii)"), (ii) polyamic acid is dissolved in an organic solvent, and in this solution. The method by the dehydration ring closure reaction of polyamic acid, such as the method of adding a dehydrating agent and a dehydration ring closure catalyst, and heating as needed (henceforth a "method (ii)") is mentioned.

As reaction temperature in a method (i), 50 degreeC-200 degreeC is preferable, and 60 degreeC-170 degreeC is more preferable. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance and when the reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide obtained may fall. As reaction time, 0.5 hour-48 hours are preferable, and 2 hours-20 hours are more preferable.

The polyimide obtained in the method (iii) may be provided as it is to the preparation of the liquid crystal aligning agent (A), and after isolation of the polyimide, may be provided to the preparation of the liquid crystal aligning agent (A) or the purified polyimide is purified. You may provide for preparation of a liquid crystal aligning agent (A) after or after refine | purifying the polyimide obtained.

Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride.

As a usage-amount of a dehydrating agent, although it selects suitably according to a desired imidation ratio, 0.01 mol-20 mol are preferable with respect to 1 mol of dark acid structures of polyamic acid.

Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine and the like.

As a usage-amount of a dehydration ring-closure catalyst, 0.01 mol-10 mol are preferable with respect to 1 mol of dehydrating agents that contain. The imidation ratio can be made higher as the content of the dehydrating agent and the dehydrating ring closure catalyst increases.

As an organic solvent used by method (ii), the organic solvent similar to the organic solvent illustrated as what is used for synthesis | combination of polyamic acid, etc. are mentioned, for example.

As reaction temperature in a method (ii), 0 degreeC-180 degreeC is preferable, and 10 degreeC-150 degreeC is more preferable. As reaction time, 0.5 hour-20 hours are preferable, and 1 hour-8 hours are more preferable. By making reaction conditions into the said range, dehydration ring-closure reaction fully advances and the molecular weight of the polyimide obtained can be made into the appropriate thing.

In method (ii), the reaction solution containing a polyimide is obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent (A), may be provided to preparation of a liquid crystal aligning agent (A) after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and liquid crystal aligning after isolating a polyimide You may use for preparation of the agent (A), or may provide for preparation of a liquid crystal aligning agent (A) after refine | purifying an isolated polyimide. As a method of removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, the method of solvent substitution etc. are mentioned, for example. As an isolation method and a purification method of a polyimide, the method similar to what was illustrated as an isolation method and a purification method of polyamic acid, etc. are mentioned, for example.

[Other Polyorganosiloxanes]

The liquid crystal aligning agent (A) may contain other polyorganosiloxane in addition to the polyorganosiloxane compound (A). It is preferable that the other polyorganosiloxane is at least 1 sort (s) chosen from the group which consists of a polyorganosiloxane represented by said formula (a1), its hydrolyzate, and the condensate of this hydrolyzate. In addition, when a liquid crystal aligning agent (A) contains other polyorganosiloxane, the majority of other polyorganosiloxane exists independently of a polyorganosiloxane compound (A), and part thereof is polyorgano. It may exist as a condensate with a siloxane compound (A).

In X ^A and Y ^A in the formula (a1),

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octade Practical groups, n-nonadecyl groups, n-eicosyl groups and the like;

As a C1-C16 alkoxy group, For example, a methoxy group, an ethoxy group, etc .;

As a C6-C20 aryl group, a phenyl group etc. are mentioned, for example.

The other polyorganosiloxane is preferably at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as "raw material silane compound"). In a solvent, it can synthesize | combine by hydrolysis or hydrolysis-condensation in presence of water and a catalyst.

As a raw silane compound which can be used here, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec Tetraalkoxysilanes, such as -butoxysilane and tetra-tert-butoxysilane; Tetrachlorosilane; Methyltrialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane; Methyltriaryloxysilanes such as methyltriphenoxysilane; Methyltrichlorosilane; Ethyltrialkoxysilanes such as ethyltrimethoxysilane; Phenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; Phenyltrichlorosilane; Dimethyl dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; Dimethyldichlorosilane; Trimethylalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; Trimethylchlorosilane, etc. are mentioned. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and trimethylmethoxy Silane and trimethylethoxysilane are preferable.

When synthesize | combining other polyorganosiloxane, as an organic solvent which can be arbitrarily used, an alcohol compound, a ketone compound, an amide compound, or an ester compound, or other aprotic compound is mentioned, for example. These compounds and each solvent compound may be used alone or in combination of two or more thereof.

As an alcohol compound, for example

Monoalcohol compounds such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol and t-butanol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, Polyhydric alcohol compounds such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene And partial ethers of polyhydric alcohol compounds such as glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

As a ketone compound, for example

Monoketone compounds such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, and methyl-n-butyl ketone;

(Beta) -diketone compounds, such as acetyl acetone, 2, 4- hexanedione, 2, 4- heptanedione, 3, 5- heptanedione, and 2, 4- octanedione, etc. are mentioned.

Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. are mentioned.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate and acetic acid. n-butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, diethylene glycol mono-n-butyl ether, acetic acid propylene glycol monome Butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, Ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl lactate, dimethyl phthalate, diphthalate Ethyl and the like.

As other aprotic compounds, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholine, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-pi Peridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone Etc. can be mentioned. Among these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, or ester compounds are particularly preferred.

The amount of water to be used in the synthesis of other polyorganosiloxanes is preferably 0.01 mol to 100 mol, more preferably 0.1 mol to 1 mol of the total amount of the alkoxy group and the halogen atom of the raw silane compound. 30 mol, Furthermore, it is preferable that they are 1 mol-1.5 mol.

As a catalyst which can be used at the time of the synthesis | combination of other polyorganosiloxane, a metal chelate compound, an organic acid, an inorganic acid, an organic base, ammonia, an alkali metal compound, etc. are mentioned, for example.

As said metal chelate compound, For example, Trialkoxy mono (acetylacetonate) titanium, such as triethoxy mono (acetylacetonate) titanium; Dialkoxy bis (acetylacetonate) titanium, such as diethoxy bis (acetylacetonate) titanium; Monoalkoxy tris (acetylacetonate) titanium such as monoethoxy tris (acetylacetonate) titanium; Tetrakis (acetylacetonate) titanium; Trialkoxy mono (ethyl acetate acetate) titanium, such as triethoxy mono (ethyl acetate acetate) titanium; Dialkoxy bis (ethylacetate acetate) titanium, such as diethoxy bis (ethylacetate acetate) titanium; Monoalkoxy tris (ethyl acetate acetate) titanium such as monoethoxy tris (ethyl acetate acetate) titanium; Tetrakis (ethylacetate acetate) titanium; Two or more chelating ligands such as mono (acetylacetonate) tris (ethylacetate acetate) titanium, bis (acetylacetonate) bis (ethylacetate acetate) titanium, tris (acetylacetonate) mono (ethylacetate acetate) titanium Titanium chelate compounds such as titanium compounds to be used;

Trialkoxy mono (acetylacetonate) zirconium such as triethoxy mono (acetylacetonate) zirconium; Dialkoxy bis (acetylacetonate) zirconium such as diethoxy bis (acetylacetonate) zirconium; Monoalkoxy tolyl (acetylacetonate) zirconium such as monoethoxy tris (acetylacetonate) zirconium; Tetrakis (acetylacetonate) zirconium; Trialkoxy mono (ethyl acetate acetate) zirconium, such as triethoxy mono (ethyl acetate acetate) zirconium; Dialkoxy bis (ethylacetate acetate) zirconium such as diethoxy bis (ethylacetate acetate) zirconium; Monoalkoxy tris (ethyl acetate acetate) zirconium, such as monoethoxy tris (ethyl acetate acetate) zirconium; Tetrakis (ethylacetate acetate) zirconium; Two or more chelating ligands such as mono (acetylacetonate) tris (ethylacetate acetate) zirconium, bis (acetylacetonate) bis (ethylacetate acetate) zirconium, tris (acetylacetonate) mono (ethylacetate acetate) zirconium Zirconium chelate compounds such as zirconium compounds;

And aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetate acetate) aluminum.

As said organic acid, For example, aliphatic saturated carboxylic acids, such as formic acid, an acetic acid, a propionic acid; Aliphatic unsaturated carboxylic acids such as malonic acid and fumaric acid; Aromatic carboxylic acids such as salicylic acid, benzoic acid and phthalic acid; aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Halogen-containing carboxylic acids such as monochloroacetic acid, trichloroacetic acid and trifluoroacetic acid; Citric acid, tartaric acid, and the like.

As said inorganic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc. are mentioned, for example.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine and monomethyl diethanol. Amine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydrooxide, etc. are mentioned.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide etc. are mentioned, for example. These catalysts may be used alone or in combination of two or more.

Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred. As a metal chelate compound, a titanium chelate compound is more preferable.

The usage-amount of a catalyst becomes like this. Preferably it is 0.001 mass part-10 mass parts with respect to 100 mass parts of raw material silane compounds, More preferably, it is 0.001 mass part-1 mass part.

The catalyst may be added in advance in a silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

Water added during the synthesis of other polyorganosiloxanes can be added intermittently or continuously in a silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent.

As reaction temperature at the time of the synthesis | combination of other polyorganosiloxane, Preferably it is 0 degreeC-100 degreeC, More preferably, it is 15 degreeC-80 degreeC. The reaction time is preferably 0.5 hour to 24 hours, more preferably 1 hour to 8 hours.

When a liquid crystal aligning agent (A) contains another polymer with a polyorganosiloxane compound (A), as content of another polymer, it is 10,000 mass parts or less with respect to 100 mass parts of polyorganosiloxane compound (A). It is preferable. More preferable content of another polymer changes with kinds of other polymers.

As a preferable use ratio of both in a case where a liquid crystal aligning agent (A) contains a polyorganosiloxane compound (A) and a polymer (B), a polymer (with respect to 100 mass parts of polyorganosiloxane compounds (A) As a total amount of B), 100 mass parts-5,000 mass parts are preferable, and 200 mass parts-3,000 mass parts are more preferable.

On the other hand, when the liquid crystal aligning agent (A) contains a polyorganosiloxane compound (A) and other polyorganosiloxane, the preferable use ratio of both is 100 mass of polyorganosiloxane compounds (A). The amount of other polyorganosiloxane relative to the part is usually 5 parts by mass to 2,000 parts by mass, and preferably 100 parts by mass to 2,000 parts by mass.

When a liquid crystal aligning agent (A) contains another polymer with a polyorganosiloxane compound (A), as another polymer, a polymer (B) or other polyorganosiloxane is preferable.

<Other ingredients>

As long as the liquid crystal aligning agent (A) does not impair the effect of this invention, the compound which has a hardening | curing agent, a hardening catalyst, a hardening accelerator, and at least 1 epoxy group in a molecule | numerator (henceforth an "epoxy compound"), functional property You may contain other components, such as a silane compound and surfactant.

[Curing Agents, Curing Catalysts, and Curing Accelerators]

A hardening | curing agent and a hardening catalyst can be contained in a liquid crystal aligning agent (A) for the purpose of strengthening the crosslinking reaction of a polyorganosiloxane compound (A). A hardening accelerator can be included in a liquid crystal aligning agent (A) for the purpose of promoting the hardening reaction which a hardening agent plays.

As a hardening | curing agent, the hardening | curing agent generally used for hardening of the curable compound containing an epoxy group or the compound which has an epoxy group can be used. As such a hardening | curing agent, polyhydric amine, polyhydric carboxylic acid anhydride, polyhydric carboxylic acid is mentioned, for example.

As polyhydric carboxylic anhydride, the anhydride of cyclohexane tricarboxylic acid and other polyhydric carboxylic acid anhydride are mentioned, for example.

As cyclohexane tricarboxylic acid anhydride, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4- anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5- anhydride, cyclo Hexane-1,2,3-tricarboxylic acid-2,3- anhydride etc. are mentioned. As other polyhydric carboxylic acid anhydride, for example, 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, following formula (6) Diels-Alder reaction products of alicyclic compounds having conjugated double bonds, such as α-terpinene and allocymen, and maleic anhydride, in addition to tetracarboxylic acid dianhydrides generally used for the synthesis of the compounds and polyamic acids, and their Hydrogenated substance etc. are mentioned.

In said formula (6), x is an integer of 1-20.

As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, an aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze cationic polymerization of an epoxy group by heating.

As said hardening accelerator, it is an imidazole compound, for example; Quaternary phosphorus compounds; Quaternary amine compounds; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, octylate tin and aluminum acetylacetone complex; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and second tin chloride; High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type accelerator, such as a dicyandiamide and an adduct of an amine and an epoxy resin; Microcapsule-type latent curing accelerators in which a surface such as a quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing accelerators; High temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

[Epoxy Compound]

The said epoxy compound can be contained in a liquid crystal aligning agent (A) from a viewpoint of improving the adhesiveness with respect to the board | substrate surface of the liquid crystal aligning film formed.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol di. Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6- tetraglycol Cydyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, N-diglycidyl-aminomethylcyclo Hexane is preferred.

When the liquid crystal aligning agent (A) contains an epoxy compound, as the content ratio, it is preferably 0.01 mass with respect to 100 mass parts in total of the said polyorganosiloxane compound (A) and the other polymer used arbitrarily. 40 parts by mass, more preferably 0.1 part by mass to 30 parts by mass.

Moreover, when a liquid crystal aligning agent (A) contains an epoxy compound, you may use together base catalysts, such as 1-benzyl- 2-methylimidazole, in order to raise the crosslinking reaction efficiently.

[Functional silane compound]

A functional silane compound can be used for the purpose of improving the adhesiveness with the board | substrate of the liquid crystal aligning film obtained. As a functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminoprop Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N- Bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Examples thereof include a reaction product of tetracarboxylic dianhydride and a silane compound having an amino group described in JP-A-63-291922.

When a liquid crystal aligning agent (A) contains a functional silane compound, as the content ratio, it is 50 mass parts with respect to a total of 100 mass parts of said polyorganosiloxane compound (A) and the other polymer arbitrarily used. The following is preferable and 20 mass parts or less are more preferable.

[Surfactants]

As surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a silicone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant etc. are mentioned, for example.

When the liquid crystal aligning agent (A) contains a surfactant, it is 10 mass parts or less with respect to 100 mass parts of all of liquid crystal aligning agents (A) as the content rate, More preferably, it is 1 mass part or less to be.

<Preparation method of liquid crystal aligning agent (A)>

As above-mentioned, a liquid crystal aligning agent (A) contains a polymer component [A] as an essential component, and may contain other arbitrary components as needed, Preferably, the solution which each component melt | dissolved in the organic solvent is preferable. It is prepared as a composition of the phase.

As an organic solvent which can be used in order to prepare a liquid crystal aligning agent (A), it is preferable that the [A] polymer component and the other components used arbitrarily are melt | dissolved and do not react with these. The organic solvent which can be used preferably for a liquid crystal aligning agent (A) changes with kinds of other polymer added arbitrarily.

As a preferable organic solvent in the case where a liquid crystal aligning agent (A) contains a [A] polymer component and a polymer (B), the organic solvent illustrated above is mentioned as what is used for synthesis | combination of a polyamic acid. Under the present circumstances, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents may be used alone or in combination of two or more thereof.

On the other hand, when a liquid crystal aligning agent (A) contains only a polyorganosiloxane compound (A) as a [A] polymer component, or when it contains a polyorganosiloxane compound (A) and other polyorganosiloxanes, As a preferable organic solvent of 1-ethoxy-2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol, for example Ethyl ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl ether , Ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve Acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, n-propyl acetate, i-propyl acetate, n-acetic acid Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n acetate -Hexyl, cyclohexyl acetate, octyl acetate, amyl acetate, isoamyl acetate, etc. are mentioned. Among these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate and sec-pentyl acetate are preferable.

The preferable solvent used for preparation of a liquid crystal aligning agent (A) can be obtained combining the 1 or more types of said organic solvent according to the presence or absence of use of another polymer, and its kind. In such a solvent, each component contained in a liquid crystal aligning agent (A) does not precipitate in the following preferable solid content concentration, and the surface tension of a liquid crystal aligning agent (A) becomes the range of 25-40 mN / m.

Although the solid content concentration of a liquid crystal aligning agent (A), ie, the ratio which the mass of all components other than the solvent in a liquid crystal aligning agent (A), occupies for the total mass of a liquid crystal aligning agent (A), although it considers viscosity, volatility, etc., Preferably it is the range of 1 mass%-10 mass%. Although a liquid crystal aligning agent (A) is apply | coated to the surface of a board | substrate, and forms the coating film used as a liquid crystal aligning film, when solid content concentration is 1 mass% or more, the film thickness of this coating film becomes hard to become small and a favorable liquid crystal aligning film can be obtained. have. On the other hand, when solid content concentration is 10 mass% or less, it can suppress that the film thickness of a coating film becomes excessive and can obtain a favorable liquid crystal aligning film, and also prevents the viscosity of a liquid crystal aligning agent (A) from increasing, and coating characteristics. Can be made favorable. The range of especially preferable solid content concentration changes with the method employ | adopted when apply | coating a liquid crystal aligning agent (A) to a board | substrate. For example, when using the spinner method, the range of 1.5 mass%-4.5 mass% is especially preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3% by mass to 9% by mass, and the solution viscosity is in the range of 12 mPa · s to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 mass%-5 mass%, and to make solution viscosity into the range of 3 mPa * s-15 mPa * s. The temperature at the time of preparing a liquid crystal aligning agent (A) becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 0 degreeC-40 degreeC.

(Example)

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

The weight average molecular weight (Mw) of the polyorganosiloxane and polyorganosiloxane compound (A) which have an epoxy group obtained in the following examples is the polystyrene conversion value measured by GPC of the following specification.

Column: Tosoh Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

In addition, the required amount of the raw material compound and the polymer used in the following Examples was ensured by repeating synthesis | combination of the raw material compound and a polymer in the synthesis scale shown to the following synthesis example as needed.

<Synthesis of Specific Carbonic Acid>

[Synthesis of Specific Carbonic Acid 1]

Specific carboxylic acid 1 was synthesized according to the following scheme.

Synthesis Example 1

In a 500 mL three-necked flask equipped with a cooling tube, 6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of 11-bromodecanoate, 14.2 g of potassium carbonate, and 200 mL of N, N-dimethylformamide were added. Furthermore, it stirred at 160 degreeC for 5 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was thrown into 500 mL of water, and the mixture was stirred. The precipitated white solid was filtered off and further washed with water. 11 g of compounds 1 were obtained by vacuum-drying the obtained solid at 80 degreeC.

[Synthesis Example 2]

Next, 10 g of compound 1, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed in the order of water and ethanol. 8g of specific carbonic acid 1 was obtained by vacuum-drying the obtained solid at 80 degreeC.

[Synthesis of Specific Carbonic Acid 2]

Specific carboxylic acid 2 was synthesized according to the following scheme.

[Synthesis Example 3]

To a 500 mL three-necked flask equipped with a cooling tube, 15 g of 4-cyano-4'-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB), and 300 mL of N, N-dimethylformamide were added. It heated and stirred at 150 degreeC for 9 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was separated and washed with a mixed solution of 300 mL of ethyl acetate and 100 mL of an aqueous 1N-sodium hydroxide solution. After extracting the organic layer, liquid separation washing was carried out in order of 100 mL of 1N-sodium hydroxide aqueous solution and 100 mL of water. The organic layer was dried over magnesium sulfate, and then the organic solvent was distilled off. 13.1g of compounds 2 were obtained by vacuum-drying the obtained solid and recrystallizing with 100 mL of ethanol / 250 mL of hexane.

[Synthesis Example 4]

To a 200 mL three-necked flask equipped with a cooling tube and a dropping funnel, 12 g of Compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated methylene chloride were added and mixed. In the state which cooled the reaction solution by the ice bath, the 10 mL solution of dehydration methylene chloride of 6.6g of triethylamine was dripped over 10 minutes. It stirred for 30 minutes, being in the ice bath state, returned to room temperature, and stirred for further 6 hours. 150 mL of chloroform was added to the reaction solution, and the liquid was washed four times with 100 mL of water. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was distilled off. 16.1g of compound 3 was obtained by wash | cleaning the obtained solid with ethanol.

Synthesis Example 5

15 g of compound 3, 11 g of 4-hydroxybenzoate, 12.5 g of potassium carbonate, and 180 mL of N, N-dimethylformamide were added to a 300 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 9 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The application liquid was poured into 500 mL of water, and mixed and stirred. The precipitated white solid was filtered off and further washed with ethanol. 10g of compounds 4 were obtained by vacuum drying the obtained solid at 80 degreeC.

[Synthesis Example 6]

To a 100 mL three-necked flask equipped with a cooling tube, 9.5 g of Compound 4, 1.6 g of lithium hydroxide-1 hydrate, 30 mL of methanol, 15 mL of tetrahydrofuran, and 15 mL of water were added, and the mixture was heated and stirred at 80 ° C for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed in the order of water and ethanol. 9g of specific carbonic acid 2 was obtained by vacuum-drying the obtained solid at 80 degreeC.

[Synthesis of Specific Carbonic Acid 3]

Specific carboxylic acid 3 was synthesized according to the following scheme.

[Synthesis Example 7]

In Synthesis Example 1, compound 5 was 13.7 by using 10.7 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4'-hydroxybiphenyl. g was obtained.

[Synthesis Example 8]

In Synthesis Example 2, 11.2 g of specific carboxylic acid 3 was obtained by using 13.5 g of Compound 5 instead of Compound 1.

[Synthesis of Specific Carbonic Acid 4]

Specific carboxylic acid 4 was synthesized according to the following scheme.

Synthesis Example 9

Compound 6 was prepared in Synthesis Example 3 by using 25.5 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4'-hydroxybiphenyl. 23.1 g was obtained.

Synthesis Example 10

24.1g of compounds 7 were obtained by using 18.9g of compounds 6 instead of compound 2 in the synthesis example 4.

Synthesis Example 11

In the synthesis example 5, 15.4g of compound 8 was obtained by using 20g of compound 7 instead of compound 3.

[Synthesis Example 12]

By using 13 g of compound 8 instead of compound 4 in the synthesis example 6, 11.4 g of specific carboxylic acid 4 was obtained.

[Synthesis of Specific Carbonic Acid 5]

Specific carboxylic acid 5 was synthesized according to the following scheme.

[Synthesis Example 13]

15g of specific carbonic acid 5 which changed the number of methylene groups from 10 to 5 similarly to the synthesis of specific carbonic acid 1 was synthesize | combined.

[Synthesis of Specific Carbonic Acid 6]

Specific carboxylic acid 6 was synthesized according to the following scheme.

[Synthesis Example 14]

10.1 g of 2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl, 10 g of methyl 11-bromodecanoate and potassium carbonate in a 500 mL three-necked flask equipped with a cooling tube 14.2 g and 200 mL of N, N-dimethylformamide were added, and it stirred with heat at 160 degreeC for 5 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was thrown into 500 mL of water, and the mixture was stirred. The precipitated white solid was filtered off and further washed with water. 10.8g of compounds 9 were obtained by vacuum drying the obtained solid at 80 degreeC.

Synthesis Example 15

Next, 10 g of compound 9, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed in the order of water and ethanol. By vacuum drying the obtained solid at 80 degreeC, 6g of specific carbonic acid 6 was obtained.

[Synthesis of Specific Carbonic Acid 7]

According to the following scheme, specific carboxylic acid 7 was synthesized.

Synthesis Example 16

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- (4) described in the above scheme. 5.9 g of specific carboxylic acid 7 was obtained in the same manner as in the synthesis of the specific carboxylic acid 6, except that 9.1 g of propyl-cyclohexyl) phenol) was changed.

[Synthesis of Specific Carbonic Acid 8]

According to the following scheme, specific carboxylic acid 8 was synthesized.

Synthesis Example 17

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,2', 3,3'-tetrafluoro) described in the above scheme. 7.1 g of specific carbon acids 8 was obtained in the same manner as the synthesis of the specific carbon acids 6, except that 12.9 g of r-4--4- (4-hydroxy-phenyl)) was obtained.

[Synthesis of Specific Carbonic Acid 9]

According to the following scheme, specific carboxylic acid 9 was synthesized.

Synthesis Example 18

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4- (4) described in the above scheme. 6.5g of specific carbonic acids 9 were obtained in the same manner as in the synthesis of the specific carbonic acid 6, except that 10.2 g of -propylcyclohexylmethoxy) phenol) was changed.

[Synthesis of Specific Carbonic Acid 10]

According to the following scheme, specific carboxylic acid 10 was synthesized.

Synthesis Example 19

10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) was added to the compound (2,3-difluoro-4'-( 7.2 g of specific carbon acids 10 was obtained in the same manner as in the synthesis of the specific carbon acids 6, except that 12.6 g of 4-propylphenylethyl) biphenyl) was changed.

[Synthesis of Specific Carbonic Acid 11]

According to the following scheme, specific carboxylic acid 11 was synthesized.

Synthesis Example 20

Except for replacing 10.1 g of the starting compound (2,2 ', 3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl) with 14.2 g of the compound described in the above scheme, In the same manner as in the synthesis, 7.6 g of specific carbonic acid 11 was obtained.

[Synthesis of Specific Carbonic Acid 12]

According to the following scheme, specific carboxylic acid 12 was synthesized.

Synthesis Example 21

In a 500 mL three-necked flask equipped with a cooling tube, 12.5 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 10 g of 11-bromodecanoate, carbonic acid 14.2 g of potassium and 200 mL of N, N-dimethylformamide were added, and the mixture was heated and stirred at 160 ° C. for 5 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was thrown into 500 mL of water, and the mixture was stirred. The precipitated white solid was filtered off and further washed with water. 14.8g of compounds 10 were obtained by vacuum drying the obtained solid at 80 degreeC.

Synthesis Example 22

Next, 10 g of compound 10, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming completion | finish of reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered and washed in the order of water and ethanol. By vacuum drying the obtained solid at 80 degreeC, 6g of specific carbonic acid 12 was obtained.

<Synthesis of Polyorganosiloxanes (Electrode Polyorganosiloxanes) Having Epoxy Groups>

Hydrolytic Condensation Reaction

Synthesis Example S-1

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine Was added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and it reacted at 80 degreeC for 6 hours, mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, thereby obtaining polyorganosiloxane S-1. Was obtained as a viscous transparent liquid.

Is obtained with respect to the polyorganosiloxane having the epoxy group, ^l H-NMR performing the analysis results, the chemical shifts (δ) = a peak based on the epoxy group in the vicinity of 3.2ppm as theoretical strength, a side reaction of the epoxy group is not up in the reaction Was confirmed. The weight average molecular weight (Mw) of the polyorganosiloxane S-1 which has the epoxy group obtained here was Mw = 2,200, and the epoxy equivalent was 186g / mol.

Synthesis Example S-2

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 73.9 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) and γ-methacryloxypropyl as hydrolyzable silane compounds 24.8 g of trimethoxysilane (GMPTS) (ECETS: GMPTS = 75: 25 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, stirring under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain viscous transparent liquid having an epoxy group. Liquid S-2 was obtained.

As a result of ^l- H-NMR analysis of the hydrolyzed condensate, a peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no side reaction of the epoxy group occurred during the reaction. . The weight average molecular weight (Mw) of the polyorganosiloxane S-2 which has the epoxy group obtained here was Mw = 2,900.

Synthesis Example S-3

123.2 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) and γ-methacryloxypropyl as a hydrolyzable silane compound in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling tube 124.2 g of trimethoxysilane (GMPTS) (ECETS: GMPTS = 50: 50 (molar ratio)), 1250 g of methyl isobutyl ketone as a solvent, and 25.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 250 g of deionized water was dripped over 45 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, stirring under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain viscous transparent liquid having an epoxy group. Liquid S-3 was obtained.

As a result of ^l- H-NMR analysis of the hydrolyzed condensate, a peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no side reaction of the epoxy group occurred during the reaction. . The weight average molecular weight (Mw) of the polyorganosiloxane S-3 which has the epoxy group obtained here was Mw = 3,200.

Synthesis Example S-4

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, as a hydrolyzable silane compound, 88.7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) and γ-methacryloxypropyl 9.93 g of trimethoxysilane (GMPTS) (ECETS: GMPTS = 90: 10 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, stirring under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain viscous transparent liquid having an epoxy group. Liquid S-4 was obtained.

As a result of ^l- H-NMR analysis of the hydrolyzed condensate, a peak based on the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no side reaction of the epoxy group occurred during the reaction. . The weight average molecular weight (Mw) of the polyorganosiloxane S-4 which has the epoxy group obtained here was Mw = 2,700.

<Synthesis of Polyorganosiloxane Compound (A)>

[Synthesis Example A-1]

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane S-1 having an epoxy group obtained in Synthesis Example S-1, 28 g of methyl isobutyl ketone, 5.0 g of specific carbonic acid 1 obtained in Synthesis Example 2, and 3.3 g of 4-octyloxybenzoic acid (pretilt component 1) represented by Formula (5-5) exemplified as one of the compounds represented by Formula (4) and UCAT 18X (a quaternary amine salt manufactured by San Afro Corporation) 0.20 g was added and it stirred at 80 degreeC for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to prepare polyorganosiloxane compound A-1 as a white powder. 14.5 g was obtained. Mw of the polyorganosiloxane compound A-1 was 6,500.

Synthesis Example A-2

Except for using 3.6 g of 4- (4-pentylcyclohexyl) benzoic acid (pretilt component 2) represented by Formula (5-7) as one of the compounds represented by the formula (4) instead of 4-octyloxybenzoic acid. In the same manner as in Synthesis Example A-1, 13.4 g of a white powder of the polyorganosiloxane compound A-2 was obtained. Mw of A-2 was 7,900.

Synthesis Example A-3

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane S-1 having an epoxy group obtained in Synthesis Example S-1, 28 g of methyl isobutyl ketone, 8.0 g of specific carbonic acid 1 obtained in Synthesis Example 2, and 1.4 g of 4- (4-pentylcyclohexyl) benzoic acid (pretilt component 2) represented by the formula (5-7) and 0.20 g of UCAT 18X (a quaternary amine salt manufactured by San Afro Co., Ltd.) were added thereto at 80 ° C. It stirred for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and then the solvent was distilled off to obtain 13.9 g of polyorganosiloxane compound A-3 as a white powder. . The Mw of the A-3 was 8,900.

Synthesis Example A-4

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane S-1 having an epoxy group obtained in Synthesis Example S-1, 28 g of methyl isobutyl ketone, 2.0 g of specific carbonic acid 1 obtained in Synthesis Example 2, 5.8 g of 4- (4-pentylcyclohexyl) benzoic acid (pretilt component 2) represented by the formula (5-7) and 0.20 g of UCAT 18X (a quaternary amine salt manufactured by San Afro Co., Ltd.) were added thereto at 80 ° C. It stirred for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to prepare polyorganosiloxane compound A-4 as a white powder. 13.4 g was obtained. Mw of A-4 was 7,600.

Synthesis Example A-5

Except having used 6.8 g of specific carboxylic acids 3 obtained by the synthesis example 8 instead of the specific carboxylic acids 1, it operated like a synthesis example A-1 and obtained 14.7g of white powders of the polyorganosiloxane compound A-5. Mw of A-5 was 8,100.

It shows below about the silsesquioxane which has an acryloyl group.

(Silsesquioxane having acryloyl group)

AC-SQ: `` AC-SQ TA-100 '', Toagose Co., Ltd.

Synthesis Example A-6

[Reaction of silsesquioxane having acryloyl group with nucleophilic compound (thiol)]

165.0 g of AC-SQ TA-100 (manufactured by Toagosei Co., Ltd.), a silsesquioxane having acryloyl group, in a 500 mL three-necked flask equipped with a stirrer and a thermometer, n-dodecyl-1 as a nucleophilic compound 40.5 g of -thiol (DT) (ac-yl group of AC-SQ, 160 mL of acetonitrile as a solvent, and 22.3 g of triethylamine as a catalyst) were added, and the reaction mixture was heated to 50 ° C and stirred for 90 minutes. The organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and the catalyst were distilled off under reduced pressure to obtain a polyorganosiloxane A-6 as a transparent liquid. 205.0 g were obtained About the polyorganosiloxane A-6, the weight average molecular weight Mw of polystyrene conversion measured by GPC was 5,900.

Synthesis Example A-7

[Reaction of Hydrolyzed Condensate Having Epoxy Group with Carbonic Acid]

Into a 200 mL three-necked flask, 80 g of a hydrolysis-condensation product S-2 having an epoxy group obtained in Synthesis Example S-2 was placed, and 25.0 g of methyl isobutyl ketone as a solvent and 4 represented by the formula (5-5) as carboxylic acid -33.8 g of octyloxybenzoic acid (pretilt component 1) and 1.0 g of UCAT 18X (the hardening accelerator of the epoxy compound manufactured by San Afro Inc.) were added as a catalyst, and reaction was performed at 100 degreeC for 48 hours with stirring. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to obtain 100.2 g of polyorganosiloxane A-7. About this polyorganosiloxane A-7, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 7,100.

Synthesis Example A-8

In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane S-1 having an epoxy group obtained in Synthesis Example S-1, 28 g of methyl isobutyl ketone, 8.0 g of specific carbonic acid 1 obtained in Synthesis Example 2, and 2.6 g of succinic acid 5ξ-cholestan-3-yl (pretilt component 3) represented by the formula (5-6) and 0.20 g of UCAT 18X (a quaternary amine salt manufactured by San Afro Co., Ltd.) were added thereto. It stirred for hours. After the completion of the reaction, the precipitate was reprecipitated with methanol, the precipitate was dissolved in ethyl acetate, the solution was washed three times with water, and then the solvent was distilled off to obtain 15.5 g of polyorganosiloxane compound A-8 as a white powder. . Mw of A-10 was 9,200.

Synthesis Example A-9

Into a 200 mL three-necked flask, 80 g of a hydrolysis-condensed product S-2 having an epoxy group obtained in Synthesis Example S-2 was placed, 25.0 g of methyl isobutyl ketone, 42.7 g of specific carboxylic acid 1 as a solvent, and UCAT 18X (as a catalyst). 0.8 g of hardening accelerators of the epoxy compound manufactured by San Afro Co., Ltd. were added, and reaction was performed at 100 degreeC under stirring for 48 hours. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to obtain 98.2 g of polyorganosiloxane A-9. About this polyorganosiloxane A-9, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 8,100.

Synthesis Example A-10

Into a 200 mL three-necked flask, 80 g of a hydrolysis-condensation product S-2 having an epoxy group obtained in Synthesis Example S-2 was placed, as a solvent, 25.0 g of methyl isobutyl ketone and 42.7 g of specific carboxylic acid 1, the formula (5- 28.2 g of 4-octyloxybenzoic acid (pretilt component 1) represented by 5) and 1.7 g of UCAT 18X (an epoxy accelerator produced by San Afro Inc.) were added as a catalyst, and the reaction was stirred at 100 ° C. for 48 hours. Done. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to obtain 125.7 g of polyorganosiloxane A-10. About this polyorganosiloxane A-10, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 10,200.

Synthesis Example A-11

Synthesis Example A- except that 30.9 g of 4- (4-pentylcyclohexyl) benzoic acid (pretilt component 2) represented by Formula (5-7) was used instead of 28.2 g of 4-octyloxybenzoic acid (pretilt component 1). In the same manner as in 10, 128.5 g of polyorganosiloxane A-11 was obtained. About this polyorganosiloxane A-11, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 11,500.

Synthesis Example A-12

Into a 200 mL three-necked flask, 60 g of a hydrolysis condensate S-3 having an epoxy group obtained in Synthesis Example S-3 was placed, 20.0 g of methyl isobutyl ketone, 20.1 g of specific carbonic acid 2 as a solvent, and UCAT 18X (as a catalyst). 0.5 g of hardening accelerators of the epoxy compound manufactured by San Afro Inc. were put, and reaction was performed at 100 degreeC under stirring for 48 hours. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to give 56.8 g of polyorganosiloxane A-12. About this polyorganosiloxane A-12, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 8,600.

Synthesis Example A-13

Into a 200 mL three-necked flask, 60 g of a hydrolysis-condensed product S-3 having an epoxy group obtained in Synthesis Example S-3 was added, as a solvent, 20.0 g of methyl isobutyl ketone and 11.1 g of specific carboxylic acid 4, the formula (5- 12.3 g of 4- (4-pentylcyclohexyl) benzoic acid (the pretilt component 2) represented by 7) and 0.6 g of UCAT 18X (the curing accelerator of an epoxy compound manufactured by San Afro Inc.) were added as a catalyst, and 48 at 100 ° C. The reaction was carried out under time stirring. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to give 55.9 g of polyorganosiloxane A-13. About this polyorganosiloxane A-13, the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 8,300.

Synthesis Example A-14

In a 100 mL three-necked flask, 10 g of polyorganosiloxane S-4 having an epoxy group obtained in Synthesis Example S-4, 20 g of methyl isobutyl ketone, 4.35 g of specific carboxylic acid 5 obtained in Synthesis Example 13 and UCAT 18X 0.10 g (the quaternary amine salt manufactured by San Afro Co., Ltd.) was added thereto, followed by stirring at 80 ° C for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to obtain polyorganosiloxane compound A-14 as a white powder. 10.9 g was obtained. Mw of the polyorganosiloxane compound A-14 was 6,400.

Synthesis Example A-15

In a 100 mL three-necked flask, 10 g of polyorganosiloxane S-4 having an epoxy group obtained in Synthesis Example S-4, 20 g of methyl isobutyl ketone, 6.95 g of the specific carboxylic acid 5 obtained in Synthesis Example 13, 1.54 g of 4- (4-pentylcyclohexyl) benzoic acid (pretilt component 2) represented by (5-7) and 0.20 g of UCAT 18X (a quaternary amine salt manufactured by San Afro Co., Ltd.) were added thereto. It stirred for hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to prepare polyorganosiloxane compound A-15 as a white powder. 13.7 g was obtained. Mw of the polyorganosiloxane compound A-15 was 7,700.

Synthesis Example A-16

Instead of 1.54 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the formula (5-7), 2.75 g of succinic acid 5ξ-cholestan-3-yl (pretilt component 3) represented by the formula (5-6) was substituted. Except what was used, it carried out similarly to the synthesis example A-15, and obtained 15.1g of polyorganosiloxane compound A-16 as a white powder. Mw of the polyorganosiloxane compound A-16 was 8,200.

Synthesis Example A-17

In a 100 mL three-necked flask, 10 g of polyorganosiloxane S-4 having an epoxy group obtained in Synthesis Example S-4, 20 g of methyl isobutyl ketone, 7.26 g of specific carbonic acid 3 obtained in Synthesis Example 8, 4- 3.52 g of octyloxybenzoic acid (pretilt component 1) and 0.20 g of UCAT 18X (the quaternary amine salt manufactured by San Apro Co., Ltd.) were put, and it stirred at 80 degreeC for 12 hours. After the completion of the reaction, the precipitate was reprecipitated with methanol to dissolve the precipitate in ethyl acetate to obtain a solution. The solution was washed three times with water, and then the solvent was distilled off to prepare polyorganosiloxane compound A-17 as a white powder. 15.8 g were obtained. Mw of the polyorganosiloxane compound A-17 was 9,100.

Synthesis Example A-18

Synthesis Example A except that 3.86 g of 4- (4-pentylcyclohexyl) benzoic acid (pritil component 2) represented by the formula (5-7) was used instead of 3.52 g of 4-octyloxybenzoic acid (pretilt component 1). In the same manner as for -17, 15.4 g of a polyorganosiloxane compound A-18 was obtained as a white powder. Mw of the polyorganosiloxane compound A-18 was 8,900.

Synthesis Example A-19

15.5 g of polyorganosiloxane compound A-19 was obtained in the same manner as in Synthesis Example A-17 except that 6.17 g of the specific carbon acid 6 obtained in Synthesis Example 15 was used instead of 7.26 g of the specific carbon acid 3. . Mw of the polyorganosiloxane compound A-19 was 9,100.

Synthesis Example A-20

15.3 g of polyorganosiloxane compound A-20 was obtained as white powder in the same manner as in Synthesis Example A-17 except that instead of 7.26 g of specific carbonic acid 3, 5.78 g of specific carbonic acid 7 obtained in Synthesis Example 16 was used. . Mw of the polyorganosiloxane compound A-20 was 9,000.

Synthesis Example A-21

15.6 g of polyorganosiloxane compound A-21 was obtained as a white powder in the same manner as in Synthesis Example A-17 except that 7.18 g of the specific carbon acid 8 obtained in Synthesis Example 17 was used instead of 7.26 g of the specific carbon acid 3. . Mw of the polyorganosiloxane compound A-21 was 9,300.

Synthesis Example A-22

15.2 g of polyorganosiloxane compound A-22 was obtained as a white powder in the same manner as in Synthesis Example A-17, except that 6.18 g of the specific carbon acid 9 obtained in Synthesis Example 18 was used instead of 7.26 g of the specific carbon acid 3. . Mw of the polyorganosiloxane compound A-22 was 8,900.

Synthesis Example A-23

Instead of using 7.26 g of specific carboxylic acid 3, except for using 7.07 g of specific carboxylic acid 10 obtained in Synthesis Example 19, 15.8 g of polyorganosiloxane compound A-23 was obtained as a white powder in the same manner as in Synthesis Example A-17. . Mw of the polyorganosiloxane compound A-23 was 9,500.

Synthesis Example A-24

15.6 g of polyorganosiloxane compound A-24 was obtained as a white powder in the same manner as in Synthesis Example A-17, except that 8.39 g of the specific carbon acid 11 obtained in Synthesis Example 20 was used instead of 7.26 g of the specific carbon acid 3. . Mw of the polyorganosiloxane compound A-24 was 9,200.

Synthesis Example A-25

15.5 g of polyorganosiloxane compound A-25 was obtained as a white powder in the same manner as in Synthesis Example A-17 except that 7.02 g of the specific carbon acid 12 obtained in Synthesis Example 22 was used instead of 7.26 g of the specific carbon acid 3. . Mw of the polyorganosiloxane compound A-19 was 9,100.

The synthesis result of the above polyorganosiloxane compound (A) was put together in the following Table 1. "?" In Table 1 shows that the corresponding compound was not used.

In the said Table 1, the other pretilt-angle expressing compound shows the following compounds. In addition, usage-amount (mol%) shows mol% with respect to Si atom in precursor polyorganosiloxane.

Pretilt component 1: 4-octyloxybenzoic acid

Pretilt component 2: 4- (4-pentylcyclohexyl) benzoic acid

Pretilt component 3: Succinic acid 5ξ-cholestan-3-yl

<Synthesis of Polymer (B)>

Synthesis Example P-1

19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2,2'-dimethylbiphenyl It dissolved in 367.6 g of pyrrolidone and reacted for 6 hours at room temperature. The reaction mixture was then poured into excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. for 15 hours under reduced pressure to obtain 35 g of polyamic acid PA-1.

Synthesis Example P-2

18.85 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 8.84 g of diamine represented by the following formula (G-4) as a diamine compound, and 7.31 g of p-phenyleneamine were substituted with N-methyl- It melt | dissolved in 140 g of 2-pyrrolidone, and made it react at 60 degreeC for 4 hours. As a result of measuring the viscosity of this polymerization liquid, it was 2,150 mPa * s. The reaction solution was poured into a large amount of methyl alcohol to precipitate the reaction product. Then, the polyamic acid was obtained by wash | cleaning with methyl alcohol and drying for 24 hours at 40 degreeC under reduced pressure. All the obtained polyamic acid was re-dissolved in 465 g of N-methyl-2-pyrrolidone, and 6.65 g of pyridine and 8.59 g of acetic anhydride were added and dehydrated and closed for 4 hours at 110 ° C. It dried and obtained 23.1g of polyimide PI-1 of 50% of imidation ratio.

Synthesis Example P-3

24.94 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 11.24 g of diamine represented by the following formula (G-5) as a diamine compound, and 13.82 g of 3,5-diaminobenzoic acid were N- It dissolved in 200 g of methyl-2-pyrrolidone and reacted at 60 degreeC for 4 hours. It was 1,400 mPa * s when the viscosity of this polymerization liquid was measured. The reaction solution was poured into a large amount of methyl alcohol to precipitate the reaction product. Then, the polyamic acid was obtained by wash | cleaning with methyl alcohol and drying for 24 hours at 40 degreeC under reduced pressure. All of the obtained polyamic acid was re-dissolved in 450 g of N-methyl-2-pyrrolidone, and 13.20 g of pyridine and 17.04 g of acetic anhydride were added and dehydrated and closed for 4 hours at 110 ° C. It dried and obtained 27.8g of polyimides PI-2 of 69% of imidation ratios.

Synthesis Example P-4

23.06 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 11.01 g of 3,5-diaminobenzoic acid as a diamine compound, 10.81 g of diamine represented by the formula (G-4) and the above formula 5.12 g of diamines represented by (G-5) were dissolved in 200 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 4 hours. It was 1,300 mPa * s when the viscosity of this polymerization liquid was measured. The reaction solution was poured into a large amount of methyl alcohol to precipitate the reaction product. Then, the polyamic acid was obtained by wash | cleaning with methyl alcohol and drying for 24 hours at 40 degreeC under reduced pressure. All of the obtained polyamic acid was re-dissolved in 450 g of N-methyl-2-pyrrolidone, and 8.14 g of pyridine and 10.50 g of acetic anhydride were added to dehydrate and ring-close at 110 ° C. for 4 hours. It dried and obtained 30.5g of polyimides PI-3 of 55% of imidation ratios.

<Preparation of liquid crystal aligning agent>

Example 1

As another polymer, the solution containing the polyamic acid PA-1 obtained by the said synthesis example P-1 is taken as 100 mass parts by conversion into the polyamic acid PA-1 contained in it, and the said polyorgano is 5 parts by mass of siloxane compound A-1 and 5 parts by mass of the polyorganosiloxane compound A-6 were added, and N-methyl-2-pyrrolidone and butyl cellosolve were further added, and the solvent composition was N-methyl. 2-pyrrolidone: butyl cellosolve = 50:50 (mass ratio), solid content concentration was made into the solution of 3.5 mass%. Liquid crystal aligning agent E-1 was prepared by filtering this solution with the filter of 0.2 micrometer of pore diameters.

<Production and Evaluation of Liquid Crystal Cells>

Using the liquid crystal aligning agent prepared above, the pattern (two types) and ultraviolet irradiation amount (three levels) of a transparent electrode were changed as follows, and six liquid crystal display elements in total were manufactured and evaluated.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

After apply | coating the liquid crystal aligning agent E-1 prepared in the said Example 1 using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, and prebaking for 1 minute on 80 degreeC hotplate, In the oven substituted by nitrogen, it heated at 200 degreeC for 1 hour, and formed the coating film (liquid crystal aligning film) of 0.08 micrometer in film thickness. This operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film were created.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon cloth at roll rotation speed 400rpm, stage movement speed of 3 cm / sec, and hair pressing indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge which has one liquid crystal aligning film of the said pair of board | substrates, it overlaps and crimps | bonds so that a liquid crystal aligning film surface may face, and an adhesive agent Hardened. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it was. The remaining two liquid crystal cells were subjected to light irradiation in the state where a voltage was applied between the ITO electrodes by the following method, respectively, and then used for evaluation of the pretilt angle and the voltage holding ratio.

Two of the liquid crystal cells obtained above were applied with an ultraviolet irradiation device using a metal halide lamp as a light source, with an alternating current of 1 Hz having a frequency of 60 Hz between the ITO electrodes and driving the liquid crystal, respectively. Irradiation was carried out at a dose of J / m 2 or 100,000 J / m 2. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference.

[Evaluation of Pretilt Angle]

For each liquid crystal cell produced above, Non-Patent Document 2 (TJ Schffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977) and Non-Patent Document 3 (F. Nakano et al., JPN.J). Pretilt angle of the value of the inclination angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using He-Ne laser light in accordance with the method described in Appl. Phys.vol. 19, p.2013 (1980)). I did.

Table 2 shows each pretilt angle of the liquid crystal cell of tailings irradiation, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2>.

[Evaluation of Voltage Integrity]

About each liquid crystal cell produced above, after applying the voltage of 5V at 23 degreeC in 60 microseconds application time and the span of 167 milliseconds, the voltage preservation rate after 167 milliseconds after application | release cancellation was measured. As a measuring apparatus, VHR-1 manufactured by Toyo Technica Co., Ltd. was used.

Table 2 shows the voltage holding ratios of the liquid crystal cell having an irradiation amount of 10,000 J / m 2 and the liquid crystal cell having an irradiation amount of 10,000 J / m 2.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (1)]

The liquid crystal aligning agent E-1 prepared in the said Example 1 is patterned in the slit shape shown in FIG. 1, and is spin-coated on each electrode surface of the glass substrates A and B which respectively have the ITO electrode divided into the some area | region. After the coating was carried out, the solvent was removed by heating (prebaking) for 1 minute on an 80 ° C hot plate, and then heated at 200 ° C for 1 hour in an oven substituted with nitrogen to form a coating film (liquid crystal aligning film) having a film thickness of 0.08 μm. did. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Subsequently, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of 5.5 micrometers in diameter to the outer edge which has one liquid crystal aligning film of the said pair of board | substrates, it overlapped and crimped | bonded so that a liquid crystal aligning film surface could face and hardened the adhesive agent. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it is. For the remaining two liquid crystal cells, the irradiation amount of 10,000 J / m 2 or 100, OOOJ / m 2 in the state in which a voltage was applied between the conductive films by the same method as in the manufacture of the liquid crystal cell having the transparent electrode without the above pattern. After light irradiation, it provided for evaluation of response speed.

In addition, the pattern of the electrode used here is a pattern similar to the electrode pattern in PSA mode.

[Evaluation of response speed]

About each liquid crystal cell manufactured above, the brightness of the light which permeate | transmitted the liquid crystal cell by irradiating a visible light lamp first without applying a voltage was measured with the photomultimeter, and this value was made into 0% of the relative transmittance. Next, the transmittance | permeability when AC 60V was applied for 5 second between electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability.

At this time, when AC 60V was applied to each liquid crystal cell, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated.

Table 2 shows the response speed of the liquid crystal cell of tailings irradiation, the liquid crystal cell of irradiation amount 10,000 J / m <2>, and the liquid crystal cell of irradiation amount 100,000 J / m <2>, respectively.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (2)]

Using the prepared liquid crystal aligning agent, except having used glass substrates A and B which respectively have the ITO electrode patterned in the fishbone shape shown in FIG. 2, it is the same as that of manufacture (1) of the liquid crystal cell which has the said patterned transparent electrode. The liquid crystal cell of tailings irradiation, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2> were manufactured, and it carried out similarly to the above, and used for evaluation of response speed. The evaluation results are shown in Table 2.

[Examples 2 to 34 and Comparative Examples 1 and 2]

In the said Example 1, it is the same as Example 1 except having set the kind and compounding quantity of a polymer (B) and a polyorganosiloxane compound (A) (component 1 and component 2 as needed) as respectively shown in Table 2. The liquid crystal aligning agent was prepared, the various liquid crystal cells were manufactured and evaluated using this liquid crystal aligning agent. The evaluation results are shown in Table 2.

From the results in Table 2, in the method of the present invention, when the amount of ultraviolet irradiation is set to 100,000 J / m 2 (the value conventionally employed in the PSA mode), the degree of pretilt angle obtained is excessive, and 10,000 J / m 2 or the It turns out that it becomes an appropriate pretilt angle in the following irradiation amounts. Moreover, even if the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage holding ratio is also excellent.

Therefore, according to the method of this invention, it is possible to realize the merit of PSA mode with a small amount of light irradiation, and can manufacture the liquid crystal display element with a quick liquid crystal response speed compared with the conventional PSA mode liquid crystal display element.

According to this invention, the manufacturing method of the liquid crystal display element which has a wide viewing angle, quick response speed of a liquid crystal molecule, and excellent display property and long-term reliability is provided.

1: ITO electrode
2: slit part
3: shading film

Claims (8)

(1) [A] A pair having a conductive film using a liquid crystal aligning agent containing a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymers: Forming a coating film on the conductive film of the substrate of
(2) forming a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so that the pair of coating films face each other and through the liquid crystal layer;
(3) A method of manufacturing a liquid crystal display device having the step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

(In formula (A1), R <^1> is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group; some or all of the hydrogen atoms which these groups have may be substituted; R <^2> is a double bond. , A linking group comprising any of a triple bond, an ether bond, an ester bond and an oxygen atom, R ³ is a group having at least two monocyclic structures; a is 0 or 1). The method of claim 1,
[A] A method for producing a liquid crystal display device, wherein the polymer component contains a polymer having a group containing the [A-1] polymerizable carbon-carbon double bond and a group represented by the formula (A1). The method of claim 1,
Preparation of the liquid crystal display element in which a polymer component [A] contains the polymer which has a group containing the [A-2] polymerizable carbon-carbon double bond, and the polymer which has a group represented by [A-3] said Formula (A1). Way. 4. The method according to any one of claims 1 to 3,
The manufacturing method of the liquid crystal display element in which R <^3> in said Formula (A1) is represented by following formula (A2):

(In formula (A2), R ⁴ is a phenylene group, a biphenylene group, a naphthylene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a bivalent heterocyclic group; Some or all of them may be substituted; R ⁵ is a linking group including at least one of a methylene group which may have a substituent, an alkylene group having 2 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond, and a heterocyclic group; R ⁶ is a (c + 1) valent group excluding (c + 1) hydrogen atoms from benzene, biphenyl, naphthalene, cyclohexane, bicyclohexane, cyclohexylbenzene, or a heterocyclic compound; some or all of the hydrogen atoms of the group May be substituted; R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group; b is 0 or 1 C is an integer of 1 to 9, d is 1 or 2, and when R ⁴ , R ⁵ and R ⁷ each are plural, a plurality of R ⁴ , R ⁵ and R ⁷ may be the same or different, respectively) . 4. The method according to any one of claims 1 to 3,
The manufacturing method of the liquid crystal display element in which a polymer component (A) has a polyorganosiloxane structure. 4. The method according to any one of claims 1 to 3,
[A] The method for producing a liquid crystal display device, in which the polymer component further comprises at least one polymer selected from the group consisting of polyamic acid and polyimide. The liquid crystal display element manufactured by the manufacturing method of the liquid crystal display element in any one of Claims 1-3. [A] A liquid crystal aligning agent containing a polymer component having a group containing a polymerizable carbon-carbon double bond and a group represented by the following formula (A1) in the same or different polymer:

(In formula (A1), R <^1> is a methylene group, a C2-C30 alkylene group, a phenylene group, or a cyclohexylene group; some or all of the hydrogen atoms which these groups have may be substituted; R <^2> is a double bond. , A linking group comprising any of a triple bond, an ether bond, an ester bond and an oxygen atom, R ³ is a group having at least two monocyclic structures; a is 0 or 1).

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