KR102008788B1 - Liquid crystal aligning agent for psa mode liquid crystal display device, liquid crystal alignment film for psa mode liquid crystal display device, and the psa mode liquid crystal display device and manufacturing method thereof - Google Patents

Abstract

(Problem) The PSA mode liquid crystal display element which shows the appropriate pretilt angle with a small light irradiation amount, can maintain a high voltage holding ratio after light irradiation, and has a quick response speed.
(Solution means) In the liquid crystal aligning agent used for forming the liquid crystal aligning film in the liquid crystal display element of PSA mode, in the radical generating function which generate | occur | produces a radical by light irradiation, and the photosensitivity function which shows the sensitization effect by light irradiation. The compound (A) which has the structure (a) which can express at least any function is contained.

Description

Liquid crystal aligning agent for PSA mode liquid crystal display elements, liquid crystal aligning film for PSA mode liquid crystal display elements, and PSA mode liquid crystal display element and its manufacturing method {LIQUID CRYSTAL ALIGNING AGENT FOR PSA MODE LIQUID CRYSTAL DISPLAY DEVICE, CRYSTAL DISPLAY DEVICE, AND THE PSA MODE LIQUID CRYSTAL DISPLAY DEVICE AND MANUFACTURING METHOD THEREOF}

This invention relates to the liquid crystal aligning agent and liquid crystal aligning film for PSA mode liquid crystal display elements, a PSA mode liquid crystal display element, and its manufacturing method. Specifically, It is related with the technique for reducing the amount of light irradiation at the time of PSA treatment. .

Conventionally, as a liquid crystal display element, the various drive system from which an electrode structure, the physical property of the liquid crystal molecule to be used, etc. differ is developed. For example, the MVA (Multi-Domain Vertical Alignment) panel conventionally known as the vertical alignment mode is intended to enlarge the viewing angle by regulating the inclination direction of liquid crystal molecules by projections formed in the liquid crystal panel. However, according to this system, the lack of transmittance and contrast derived from the projections is inevitable, and the response speed of the liquid crystal molecules tends to be slow.

Recently, in order to solve the problem of the MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed as a new driving mode for controlling the alignment of liquid crystal molecules. In the PSA mode, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling the liquid crystal cell, the photopolymerizable monomer is irradiated by irradiating the liquid crystal cell with a voltage applied between a pair of electrodes sandwiching the liquid crystal layer. It is a technique which superposes | polymerizes and controls the molecular orientation of a liquid crystal molecule. According to this technique, there is an advantage that the viewing angle can be increased and the response speed can be increased. Moreover, in recent years, further high-speed response of the PSA type liquid crystal panel is examined, and as such a technique, the monofunctional liquid crystalline compound which has either an alkenyl group and a fluoro alkenyl group (henceforth "alkenyl-type liquid crystal" is also called. Attempts are introduced (see, for example, Patent Documents 1 to 3).

Japanese Laid-Open Patent Publication No. 2010-285499 Japanese Patent Laid-Open No. 9-104644 Japanese Patent Application Laid-open No. Hei 6-108053

According to the PSA mode, the viewing angle can be increased and the response speed can be increased. However, a large amount of ultraviolet irradiation is required for the polymerization reaction of the photopolymerizable monomer, and the display quality of the panel is degraded due to the ultraviolet irradiation. . When the amount of light irradiation is insufficient, an unreacted photopolymerizable monomer remains in the liquid crystal layer, and burn-in of an image easily occurs due to the unreacted monomer. In this regard, in the PSA mode, it is possible to polymerize the photopolymerizable monomer with as little light irradiation as possible, and furthermore, it is necessary to make as few unreacted monomers as possible.

In addition, in the liquid crystal display element using an alkenyl-based liquid crystal, it is possible to speed up the response speed, but by light irradiation for the polymerization of the photopolymerizable monomer, a voltage is higher than that of the liquid crystal cell which does not contain the alkenyl-based liquid crystal in the liquid crystal layer. It is clear that the decrease in the retention rate is increased. From the viewpoint of further improving the display quality of the liquid crystal display device, it is necessary to maintain a high voltage holding ratio after light irradiation for polymerization of the photopolymerizable monomer.

This invention is made | formed in view of the said subject, PSA which can show the appropriate pretilt angle with a small amount of light irradiation, can maintain a high voltage holding ratio after light irradiation, and can provide the PSA mode liquid crystal display element with a quick response speed. It is a main object to provide a liquid crystal aligning agent for mode liquid crystal display elements.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject can be solved by forming a liquid crystal aligning film using the liquid crystal aligning agent containing a specific compound, as a result of earnestly examining in order to achieve the subject of the said prior art. It was completed. Specifically, this invention provides the following liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element for PSA mode liquid crystal display elements, and its manufacturing method.

In one aspect, the present invention provides a compound having a structure (a) capable of expressing at least any one of a radical generating function for generating radicals by light irradiation and a photosensitizing function having a sensitizing effect by light irradiation. The liquid crystal aligning agent for PSA mode liquid crystal display elements containing (A) is provided.

This invention is another one side WHEREIN: The 1st process of apply | coating the liquid crystal aligning agent of this invention on the said electrically conductive film of a pair of board | substrates which have an electrically conductive film, respectively, and then heating this to form a coating film, and the said coating film The second process of forming a liquid crystal cell by arranging a pair of board | substrates which formed the said film so that the said coating film may oppose through the liquid crystal layer containing a liquid crystalline compound, and applying the voltage between the electrically conductive film which a pair of board | substrates has The manufacturing method of the liquid crystal display element containing the 3rd process of irradiating light to a liquid crystal cell in a state is provided.

This invention provides the liquid crystal aligning film for PSA mode liquid crystal display elements formed using the liquid crystal aligning agent of this invention in another aspect, and the PSA mode liquid crystal display element provided with this liquid crystal aligning film.

The liquid crystal display element of the PSA mode type manufactured using the liquid crystal aligning agent of this invention can exhibit a suitable pretilt angle with a small amount of light irradiation by including a compound (A) in a liquid crystal aligning film. In addition, a liquid crystal display device having a high voltage holding ratio and a fast response speed can be obtained.

In particular, by forming the liquid crystal aligning film of the liquid crystal display element provided with the liquid crystal layer containing an alkenyl-type liquid crystal using the liquid crystal aligning agent of this invention, while trying to speed up a response speed in a liquid crystal display element, The fall of the voltage holding ratio with light irradiation resulting from addition can be suppressed suitably.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the electrode pattern of the transparent electrode film used by the Example and the comparative example.
It is a figure which shows the electrode pattern of the transparent electrode film used by the Example and the comparative example.
It is a figure which shows the electrode pattern of the transparent electrode film used by the Example and the comparative example.

(Form to carry out invention)

Below, each component contained in the liquid crystal aligning agent for PSA mode liquid crystal display elements (henceforth simply a liquid crystal aligning agent) of this invention, and the other component arbitrarily mix | blended as needed are demonstrated.

<Compound (A)>

The liquid crystal aligning agent of this invention is a compound (A), The structure (a) which can express at least any function among the radical generating function which generate | occur | produces a radical by light irradiation, and the photosensitization function which shows a sensitization effect by light irradiation (following) , "Also referred to as" specific structure "). Here, a "photosensitization function" means the function which, after becoming a singlet excited state by irradiation of light, quickly makes a crossover between ports and transitions to a triplet excited state. Colliding with another molecule in this triplet excited state changes the opponent to the excited state and returns itself to the ground state. This photosensitization function may coexist with the radical generation function which generate | occur | produces a radical by light irradiation.

As said specific structure which a compound (A) has, it is preferable that it is a structure which can express a photosensitive function at least, ie, a structure which can express only a photosensitive function, or a structure which can express a photosensitive function and a radical generating function.

The said compound (A) may be a comparatively low molecular weight compound which does not have a repeating unit, or a polymer may be sufficient as it. In addition, a compound (A) can be used individually by 1 type or in combination of 2 or more types.

It is preferable that it is molecular weight 1,000 or less, and, as for the compound (A) as a low molecular weight compound, it is more preferable that it is 800 or less. As a specific example when a compound (A) is a low molecular compound, it has acetophenone structure, such as acetophenone, acetophenone benzyl ketal, 2, 2- dimethoxy- 2-phenylacetophenone, and 3-methyl acetophenone, for example. compound;

Benzophenone, 4-diethylamino-2-hydroxybenzophenone, 2-hydroxybenzophenone, 4-methylbenzophenone, 3,4-dimethylbenzophenone, 3- (4-benzoyl-phenoxy) propyl, 4 Compounds having a benzophenone structure such as -chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone (Mihiler ketone) ;

Nitroaryl structures such as 3,5-dinitrobenzene, 4-methyl-3,5-dinitrobenzene, 3- (3,5-dinitrophenoxy) propyl, and 2-methyl-3,5-dinitrobenzene A compound having; In addition to,

9,10-dioxodihydroanthracene, 3- (9,10-dioxo-9,10-dihydroanthracen-2-yl) propyl, 3- (4,5-dimethoxy-3,6-dioxo Cyclohexa-1,4-dienyl) propyl, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, xanthone, fluorenone , Benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, benzoin propylether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2, 4, 4- trimethyl pentyl phosphine oxide etc. are mentioned.

Although the compound (A) as a polymer may have the above-described specific structure in either of the main chain and the side chain of the polymer, it is easy to control the amount introduced, and the point of improving the pretilt angle characteristic, voltage holding ratio and response speed more. WHEREIN: It is preferable to have in the side chain of a polymer.

As a main skeleton of the polymer which has the said specific structure (henceforth a "polymer (A)"), for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, And skeletons made of cellulose derivatives, polyacetal derivatives, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylate derivatives and the like. As said polymer (A), 1 or more types of polymer which has a skeleton chosen from these can be suitably selected and used according to the use of a liquid crystal display element, etc. In addition, (meth) acrylate means containing an acrylate and a methacrylate.

Among the polymers (A), those having a skeleton selected from polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane and poly (meth) acrylate are preferred among the above, and polyamic acid, polyimide, polyamic acid ester and It is more preferable to have a skeleton selected from polyorganosiloxanes.

As said specific structure in the said polymer (A), when it has this specific structure in a principal chain, it is preferable that it is a benzophenone structure.

In the case where the specific structure is present in the side chain, specific examples of the specific structure include acetophenone structure, benzophenone structure, xanthone structure, fluorenone structure and benzaldehyde structure as a structure capable of expressing a radical generating function. Fluorene structure, anthraquinone structure, triphenylamine structure, carbazole structure, alkylphenone structure, benzoin structure, thioxanthone structure, acylphosphine oxide structure and the like;

As a structure capable of expressing a photosensitizing function, for example, acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure (nitrobenzene structure, 1,3-dinitrobenzene structure, etc.) And naphthalene structure, fluorene structure, anthracene structure, acridine structure, indole structure, 1,4-dioxocyclohexa-2,5-diene structure and the like. In addition, each of these structures is acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, alkylphenone, benzoin, thioxanthone, acylphosphine oxide, biphenyl , A structure consisting of a group obtained by removing 1 to 4 hydrogen atoms from nitrobenzene, 1,3-dinitrobenzene, naphthalene, anthracene, acridine, indole, 1,4-dioxocyclohexa-2,5-diene to be.

In the case of having the specific structure in the side chain, the specific structure is selected from among the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure and a naphthalene structure, among others. It is preferable that it is at least 1 sort (s), and it is more preferable that it is at least 1 sort (s) chosen from the group which consists of an acetophenone structure, a benzophenone structure, and a nitroaryl structure.

[Polymer (A): Polyamic Acid]

In this invention, the polyamic acid (henceforth "polyamic acid (A)") as a polymer (A) can be obtained by making tetracarboxylic dianhydride and the diamine which has the said specific structure, for example.

[Tetracarboxylic dianhydride]

As tetracarboxylic dianhydride used for synthesize | combining the polyamic acid (A) in this invention, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. Can be mentioned. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, 1,2,3,4-butane tetracarboxylic dianhydride etc .;

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-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, 2 , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxotricyclo [5.3.1.0 ^2,6 ] undecane-3, 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride, and the like;

As aromatic tetracarboxylic dianhydride, For example, pyromellitic dianhydride etc .;

In addition to each of them, tetracarboxylic dianhydride and the like described in JP 2010-97188 A can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

As tetracarboxylic dianhydride used for synthesize | combining a polyamic acid (A), it is preferable to contain an alicyclic tetracarboxylic dianhydride, It is 2,3,5- tricarboxy cyclopentyl acetic dianhydride and 1,2,3. It is more preferable to include at least any one of the 4-cyclobutanetetracarboxylic dianhydride, and it is particularly preferable to include 2,3,5-tricarboxycyclopentyl acetic dianhydride. Moreover, as tetracarboxylic dianhydride used for synthesize | combining a polyamic acid (A), content of 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride is content. It is preferable that it is 60 mol% or more, and, as for (total amount) with respect to the total amount of tetracarboxylic dianhydride used for synthesis, it is more preferable that it is 80 mol% or more.

[Diamine]

As the diamine used for synthesizing the polyamic acid in the present invention, a diamine capable of imparting at least any one of a radical generating function and a photosensitizing function to the polymer by having the specific structure (hereinafter also referred to as "specific diamine"). Can be mentioned. As a specific example of such specific diamine, it is 4,4'- diamino benzophenone, 3,3'- diamino benzophenone, {4- [2- (3, 5- diamino phenoxy) -ethoxy], for example. -Phenyl} -ethanone, 3,4-diaminobenzophenone, {4- [2- (3,5-diaminophenoxy) -ethoxy] -phenyl} -phenyl-methanone, {4- [2 -(2,4-Diaminophenoxy) -ethoxy] -phenyl} -phenyl-methanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -p- Toluyl-methanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -o-toluyl-methanone, 9,9-bis (4-aminophenyl) flu Orene, etc. are mentioned. The said specific diamine can be used individually by 1 type selected from these, or in combination of 2 or more type.

As the diamine for synthesizing the polyamic acid (A) in the present invention, the specific diamine may be used alone, but together with the specific diamine, diamines other than the specific diamine (hereinafter also referred to as "other diamines") You can also use

Here, as said other diamine, aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example. As these specific examples, As aliphatic diamine, For example, metaxylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .; As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

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, 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, tetradecane Oxy-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-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy- 2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bi (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-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, 1- (4-aminophenyl) -2,3-dihydro-1,3,3- Trimethyl-1H-inden-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3- (3,5-dia Minobenzoyloxy) choletan and the following formula (D-1):

(In formula (D-1), ^XI and ^XII are each independently a single bond, -O-, -COO-, or -OCO-, R <^I> is a C1-C3 alkanediyl group, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, n is 0 or 1, provided that a and b do not become 0 at the same time)

Compounds represented by these;

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be cited, and the diamine described in JP 2010-97188 A can be used. Can be.

The formula (D-1) from the ^{"-X Ⅰ - (R Ⅰ -X Ⅱ} ) n - " As the divalent group represented by, alkanediyl group having a carbon number of 1~3, * -O-, * -COO- Or * -OC ₂ H ₄ -O-, provided that the bond to which "*" is attached is combined with a diaminophenyl group.

Specific examples of the group "-C _c H _{2c +1",} for example, methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl group , n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octade A practical group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. It is preferable that two amino groups in a diaminophenyl group exist in 2, 4-position or 3, 5-position with respect to another group.

As a specific example of a compound represented by said formula (D-1), the compound etc. which are represented by each of following formula (D-1-1) (D-1-4) are mentioned, for example.

In addition, as other diamine, 1 type of these compounds can be used individually or in combination of 2 or more types.

In the synthesis of the polyamic acid (A), the amount of the specific diamine used is preferably 0.1 to 80 mol%, more preferably 1 to 60 mol% with respect to the total amount of the diamine used for the synthesis. It is preferable and it is more preferable to set it as 5-50 mol%.

Synthesis of Polyamic Acid

The use ratio of tetracarboxylic dianhydride and diamine provided for the polyamic acid synthesis reaction in the present invention is such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents to the amino equivalent of the diamine. It is preferable that the ratio of 0.3 to 1.2 equivalents is more preferable. In addition, the synthesis reaction of polyamic acid is preferably performed in an organic solvent. -20 degreeC-150 degreeC is preferable, and, as for reaction temperature at this time, 0-100 degreeC is more preferable. In addition, the reaction time is preferably 0.5 to 24 hours, more preferably 2 to 10 hours.

Here, as an organic solvent used for reaction, what is necessary is just to melt | dissolve the polyamic acid synthesize | combined, For example, N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, N, Ratios such as N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide (Non) protic polar solvents; phenol solvents such as m-cresol, xylenol, phenol and halogenated phenol; Etc. can be mentioned. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.

Moreover, as an organic solvent used for reaction, you may use together the poor solvent of the said polyamic acid in the range which does not precipitate the polyamic acid synthesize | combined. As such a poor solvent, For example, Alcohol, such as methanol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methylmethoxypropionate, diethyl oxalate, and isoamylpropionate; Ethers such as diethyl ether, ethylene glycol methyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran and diisopentyl ether; Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane and trichloroethane; Hydrocarbons, such as hexane, heptane, octane, benzene, toluene, and xylene, etc. are mentioned. In addition, these poor solvents can be used individually by 1 type or in mixture of 2 or more types.

When using the said poor solvent of polyamic acid as an organic solvent used for reaction, the use ratio is preferably 50 weight% or less with respect to the total amount of the organic solvent used for synthesis | combination, More preferably, it is 40 weight It is% or less, More preferably, it is 30 weight% or less.

The amount (x) of the organic solvent is preferably set to an amount such that the total amount (y) of the tetracarboxylic dianhydride and the diamine is 0.1 to 50% by weight relative to the total amount (x + y) of the reaction solution. It is more preferable to set it as the quantity made to be 30 weight%.

As described above, a reaction solution obtained by dissolving the polyamic acid (A) is obtained. This reaction solution may be used for preparation of a liquid crystal aligning agent as it is, may be used for preparation of a liquid crystal aligning agent after isolating the polyamic acid (A) contained in a reaction solution, or refine | purifies the isolated polyamic acid (A). After making it, you may provide for preparation of a liquid crystal aligning agent. When the polyamic acid (A) is dehydrated and closed to form a polyimide, the reaction solution may be used as it is for the dehydration ring closure reaction, or the polyamic acid (A) contained in the reaction solution is isolated and then subjected to the dehydration ring closure reaction. After purification of the isolated polyamic acid (A), it may be used for a dehydration ring closure reaction. Isolation and purification of the polyamic acid (A) can be performed according to a well-known method.

<Polymer (A): Polyimide>

In the present invention, the polyimide (hereinafter also referred to as "polyimide (A)") as the polymer (A) can be obtained by, for example, dehydrating and ring-closing the polyamic acid (A) synthesized as described above. have.

The polyimide (A) may be a complete imide obtained by dehydrating and ring-closing all of the dark acid structures possessed by the polyamic acid (A) as a precursor thereof, and dehydrating and ring-closing only a part of the dark acid structure to form a dark acid structure and an imide ring structure. The partial imide which coexists may be sufficient. It is preferable that the imidation ratio is 40% or more, and, as for the polyimide (A) in this invention, it is more preferable that it is 50 to 99%. This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. In addition, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid (A) may be carried out by (i) heating the polyamic acid (A), or (ii) dissolving the polyamic acid (A) in an organic solvent, and dehydrating the dehydrating ring closure catalyst in this solution. It can carry out by the method of adding and heating as needed.

In the method of said (i), reaction temperature becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide (A) obtained may fall. The reaction time is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

In addition, in the method of said (ii), acid anhydrides, such as acetic anhydride, a propionic anhydride, a trifluoro acetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of dark acid structural units. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, triethylamine, and N-methylpiperidine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the solvent illustrated as an organic solvent used for the synthesis | combination of a polyamic acid (A) is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide (A) obtained by the said method (i) may be provided as it is to preparation of a liquid crystal aligning agent, or may be provided to preparation of a liquid crystal aligning agent after refine | purifying the obtained polyimide (A). On the other hand, in the said method (ii), the reaction solution containing a polyimide (A) is obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent as it is, for example, after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution by methods, such as a solvent substitution, you may provide for preparation of a liquid crystal aligning agent, and a polyimide After (A) is isolated, you may provide for preparation of a liquid crystal aligning agent, or after refine | purifying an isolated polyimide (A), you may provide for preparation of a liquid crystal aligning agent. Isolation and purification of the polyimide (A) can be carried out according to a known method.

<Polymer (A): Polyamic Acid Ester>

The polyamic acid ester (henceforth "polyamic acid ester (A)") as a polymer (A) in this invention is the tetracarbon illustrated as a compound used for the synthesis | combination of the said polyamic acid (A), for example. After reacting an acid dianhydride and other diamine to obtain polyamic acid, it can synthesize | combine by making the obtained polyamic acid and the compound which has the said specific structure and an epoxy group react. In addition, the polyamic acid ester (A) may have only a dark acid ester structure, and may be the partial ester compound in which a dark acid structure and a female acid ester structure coexist.

When polyamic acid (A), polyamic acid ester (A), and polyimide (A) obtained as mentioned above are made into the solution of 10 weight% of concentration, it is preferable to have the solution viscosity of 10-800 mPa * s, It is more preferable to have a solution viscosity of 15-500 mPa * s. In addition, the solution viscosity (mPa * s) of the said polymer is the density | concentration 10weight prepared using the quantity solvent of these polymers (for example, (gamma) -butyrolactone, N-methyl- 2-pyrrolidone, etc.). It is the value measured at 25 degreeC using the E-type rotational viscometer about% polymer solution. Moreover, it is preferable that the said polyamic acid (A), a polyamic acid ester (A), and a polyimide (A) have a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) of 500-300,000, It is more preferable that it is 1,000-200,000.

[Polymer (A): Polyorganosiloxane]

The polyorganosiloxane (henceforth "polyorganosiloxane (A)") as said polymer (A) can be synthesize | combined by combining suitably the method of organic chemistry. As an example, a polymer (henceforth "epoxy group containing polyorgano" is obtained by hydrolytically condensing the hydrolyzable silane compound (s1) which has an epoxy group, or the mixture of the said silane compound (s1) and another silane compound, for example. After the synthesis | combination "is also carried out, the obtained epoxy group containing polyorganosiloxane, the carbonic acid (c1) which has the said specific structure, etc. are mentioned.

The silane compound (s1) is not particularly limited as long as it is a hydrolyzable silane compound having an epoxy group. Specific examples thereof include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyl. Methyl diethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrie Methoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane , 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4 Glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxycycle Hexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxy Cyclohexyl) propyl triethoxysilane etc. are mentioned. As the silane compound (s1), one of these may be used alone or in combination of two or more thereof.

In the synthesis | combination of an epoxy-group containing polyorganosiloxane, as another silane compound which can be used as needed, for example, methyl trichlorosilane, methyl trimethoxysilane, methyl triethoxysilane, phenyl trichlorosilane, and phenyl Trimethoxysilane, phenyltriethoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane, tetra Ethoxysilane, Octadecyltrichlorosilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, 3- (meth) acryloxy A ropil trichlorosilane, 3- (meth) acryloxy propyl trimethoxy silane, 3- (meth) acryloxy-propyltriethoxysilane, and the like silane. As other silane compounds, 1 type of these can be used individually or in mixture of 2 or more types. In addition, in this specification, "(meth) acryloxy" is meant to contain acryloxy and methacryloxy.

The silane compound used in the synthesis of the polyorganosiloxane (A) preferably contains 10 to 100 mol% of the silane compound (s1) with respect to the total amount of the silane compound, and contains 20 to 100 mol%. It is more preferable. When using the said other silane compound, it is preferable that it is 30 mol% or less with respect to the total amount of the silane compound used for synthesis | combination, and, as for the content rate, it is more preferable that it is 10 mol% or less.

The hydrolysis-condensation reaction of the silane compound in the above can be carried out by reacting one or two or more kinds of the above silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. At the time of a hydrolysis-condensation reaction, the use ratio of water becomes like this. Preferably it is 0.5-100 mol with respect to 1 mol of silane compounds (total amount), More preferably, it is 1-30 mol.

As a catalyst which can be used at the time of a hydrolysis-condensation reaction, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. As specific examples of these catalysts, for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid and the like; As an alkali metal compound, For example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc .; As the organic base, for example, primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, pyrrole: triethylamine, tri-n-propylamine, tri-n- Tertiary organic amines such as butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene: quaternary organic amines such as tetramethylammonium hydroxide and the like; Each can be mentioned.

Examples of the catalyst include alkali metal compounds or organic bases in terms of suppressing side reactions such as ring opening of epoxy groups, increasing hydrolytic condensation speed, and excellent storage stability. Preferred, especially organic bases. As the organic base, tertiary organic amines or quaternary organic amines are preferable.

Although the usage-amount of an organic base differs according to reaction conditions, such as a kind of organic base, temperature, etc., it should be set suitably, For example, Preferably it is 0.01-3 times mole with respect to all the silane compounds, More preferably, it is 0.05 It is -1 time molar.

As an organic solvent which can be used at the time of said hydrolysis-condensation reaction, a hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example. As those specific examples, As a hydrocarbon, For example, toluene, xylene, etc .; As a ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone etc .; As ester, For example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; 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; Each can be mentioned. It is preferable to use a water-insoluble organic solvent among these. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.

The use ratio of the organic solvent in a hydrolysis condensation reaction becomes like this. Preferably it is 10-10,000 weight part with respect to 100 weight part of all the silane compounds used for reaction, More preferably, it is 50-1,000 weight part.

It is preferable to perform said hydrolysis and condensation reaction, melt | dissolving the above-mentioned silane compound in an organic solvent, mixing this solution with an organic base and water, for example, heating by oil bath etc., and performing it. At the time of a hydrolysis-condensation reaction, it is preferable to make heating temperature 130 degrees C or less, and it is more preferable to set it as 40-100 degreeC. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixed liquid may be stirred or placed under reflux. Moreover, after completion | finish of reaction, it is preferable to wash the organic solvent layer fractionated from the reaction liquid with water. At the time of this washing | cleaning, washing | cleaning using water containing a small amount of salts (for example, about 0.2 weight% of ammonium nitrate aqueous solution etc.) is preferable at the point which a washing operation becomes easy. Washing is performed until the water layer after washing | cleaning becomes neutral, and after drying an organic solvent layer with drying agents, such as anhydrous calcium sulfate and molecular sieves as needed, and then removing a solvent, the target polyorganosiloxane is carried out. (Epoxy-containing polyorganosiloxane) can be obtained.

Next, the epoxy group containing polyorganosiloxane obtained by the said hydrolysis and condensation reaction is made to react with the carboxylic acid (c1) which has the said specific structure. Thereby, the polyorganosiloxane (A) which has the said specific structure in a side chain can be obtained. Carbonic acid used at the time of this reaction may be carbonic acid (c1) alone, and carbon which has group (henceforth "liquid crystal aligning group") which has a function which orientates liquid crystal molecule with carbonic acid (c1). At least one of an acid (c2) and other carbonic acid (c3) may be used.

Here, as long as the carboxylic acid (c1) has the said specific structure and a carboxyl group, the remainder of structure is not specifically limited. Specifically, 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 4- (2-hydroxybenzoyl) benzoic acid, 3- (2-hydroxybenzoyl ) Benzoic acid, 2- (2-hydroxybenzoyl) benzoic acid, 4- (4-methylbenzoyl) benzoic acid, 4- (3,4-dimethylbenzoyl) benzoic acid, 3- (4-benzoyl-phenoxy) propionic acid, 9, 10-dioxodihydroanthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3- (9,10-dioxo-9,10-dihydroanthracen-2-yl) propionic acid, [3- ( 4,5-dimethoxy-3,6-dioxocyclohexa-1,4-dienyl) propoxy] acetyl acid, 3,5-dinitrobenzoic acid, 4-methyl-3,5-dinitrobenzoic acid, 3 -(3,5-Dinitrophenoxy) propionic acid, 2-methyl-3,5-dinitrobenzoic acid, 4-phenylbenzoic acid, 11-((4'-nitro- [1,1'-biphenyl] -4 -Yl) oxy) undecanoic acid, etc. are mentioned.

As long as the said carbonic acid (c2) has a liquid crystal aligning group and a carboxyl group, the remainder of structure is not specifically limited. As a liquid crystal aligning group, group which has a C4-C20 alkyl group, an alkoxy group, or a fluoroalkyl group, a C17-51 steroid skeleton, a polycyclic structure, etc. are mentioned, for example.

As a specific example of such a carbonic acid (c2), for example, 4-butyloxybenzoic acid, 4-pentyloxybenzoic acid, 4-hexyloxybenzoic acid, 4-heptyloxybenzoic acid, 4-octyloxybenzoic acid, 4-nonyloxybenzoic acid, 4 -Decyloxybenzoic acid, 4-undecyloxybenzoic acid, 4-dodecyloxybenzoic acid, 4-tridecyloxybenzoic acid, 4-tetradecyloxybenzoic acid, 4-pentadecyloxybenzoic acid, 4-hexadecyloxybenzoic acid, 4-hepta Decyloxybenzoic acid, 4-octadecyloxybenzoic acid, 4-nonadecyloxybenzoic acid, 4-eicosyloxybenzoic acid, 4- (4-propylcyclohexyl) benzoic acid, 4- (4-butylcyclohexyl) benzoic acid, 4- ( 4-pentylcyclohexyl) benzoic acid, 4- (4-hexylcyclohexyl) benzoic acid, 4- (4-heptylcyclohexyl) benzoic acid, 4- (4-octylcyclohexyl) benzoic acid, 4- (4'-propylbicyclo Hexyl-4-yl) benzoic acid, 4- (4'-butylbicyclohexyl-4-yl) benzoic acid, 4- (4'-pentylbicyclohexyl-4-yl) benzoic acid, 4- (4'-hexylbi Cyclohexyl-4-yl ) Benzoic acid, 4- (4'-heptylbicyclohexyl-4-yl) benzoic acid, 4- (4'-octylbicyclohexyl-4-yl) benzoic acid, succinic acid = 5ξ-cholestan-3-yl, 11- (4- (4-pentylcyclohexyl) phenoxy) undecanoic acid, etc. are mentioned.

The said carbonic acid (c3) is carbonic acid other than the said carbonic acid (c1) and (c2). As the specific example, formic acid, acetic acid, propionic acid, benzoic acid, methyl benzoic acid, etc. are mentioned, for example.

It is preferable to set it as 0.02-0.5 mol with respect to 1 mol of epoxy groups of the epoxy group containing polyorganosiloxane used for reaction, and, as for the usage ratio of carbonic acid (c1), it is more preferable to set it as 0.05-0.4 mol, and it is 0.05-0.3 mol More preferably. Moreover, it is preferable to set it as 0.7 mol or less with respect to 1 mol of epoxy groups of the epoxy group containing polyorganosiloxane used for reaction, and, as for the usage ratio of carbonic acid (c2), it is more preferable to set it as 0.2-0.6 mol. It is preferable to set it as 0.3 mol or less with respect to 1 mol of epoxy groups of the epoxy group containing polyorganosiloxane used for reaction, and, as for the usage ratio of carbonic acid (c3), it is more preferable to set it as 0.2 mol or less.

It is preferable that the epoxy equivalent of the polyorganosiloxane (A) in this invention is 5,000 g / mol or less, and it is more preferable that it is 500-3,000 g / mol. Therefore, it is preferable to adjust suitably so that the epoxy equivalent of a polyorganosiloxane (A) may become the said range about the use ratio of the sum total of the said carbonic acid (c1), (c2), and (c3).

Reaction of the epoxy group and carbonic acid which an epoxy group containing polyorganosiloxane has, Preferably it can carry out in presence of a catalyst and an organic solvent. Here, as a catalyst used for reaction, a well-known compound etc. can be used as a so-called hardening accelerator which accelerates | stimulates the reaction of an organic base and an epoxy compound, for example.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; Quaternary organic amines such as tetramethylammonium hydroxide; Etc. can be mentioned. As an organic base, tertiary organic amine or quaternary organic amine is preferable among these.

Examples of the curing accelerator include tertiary amines, imidazole compounds, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, metal halide compounds, and the like. In addition to those that can be used, known ones can be used as the latent curing accelerator.

The catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of polyorganosiloxane to react with carbonic acid. .

Examples of the organic solvent that can be used in the reaction between the polyorganosiloxane and the carbonic acid include hydrocarbons, ethers, esters, ketones, amides, alcohols, and the like. Of these, ethers, esters and ketones are preferred in view of solubility of raw materials and products and ease of purification of the products. Solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies with respect to the total weight of a solution) of the said organic solvent becomes like this. Preferably it is 0.1 weight% or more, More preferably, it becomes 5-50 weight% Used as a ratio.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. In addition, after completion | finish of reaction, it is preferable to wash the organic solvent layer fractionated from the reaction liquid with water. After washing with water, the organic solvent layer is dried with a suitable desiccant, if necessary, and then the solvent is removed to obtain the target polyorganosiloxane. In addition, you may provide the polyorganosiloxane (A) of the state melt | dissolved in the reaction solution as it is for preparation of the next liquid crystal aligning agent, without performing the isolation operation of a polyorganosiloxane (A).

As for the polyorganosiloxane (A) to be contained in the liquid crystal aligning agent of this invention, it is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) is 500-100,000, and it is 1,000-30,000. More preferred.

Moreover, when the polymer (A) in this invention uses a poly (meth) acrylate derivative as a main skeleton, it can synthesize | combine as follows, for example. First, the monomer raw material containing the monomer which has an epoxy group is polymerized, the poly (meth) acrylate derivative which has an epoxy group is synthesize | combined, and then the said derivative and the compound which has the said specific structure and carboxyl group (for example, the said carboxylic acid ( c1)). Thereby, the poly (meth) acrylate derivative which has the said specific structure in a side chain can be obtained.

The said compound (A) contained in the liquid crystal aligning agent of this invention can be used individually by 1 type or in combination of 2 or more types chosen from the group which consists of the said low molecular weight compound and a polymer (A). In the point which can control suitably the liquid crystal aligning on the film surface of a liquid crystal aligning film, and can reduce the voltage retention by light irradiation at the time of PSA treatment, the liquid crystal aligning agent of this invention is said compound (A). It is preferable to contain at least a polymer (A), It is more preferable that the said compound (A) is a polymer (A), It is especially preferable that it is a polymer (A) which has the said specific structure in a side chain.

<Polymer (B)>

When the liquid crystal aligning agent of this invention contains only a low molecular weight compound as said compound (A), the said liquid crystal aligning agent contains the polymer (B) which does not have the said specific structure as a polymer component with the said compound (A). . As the polymer (B), for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (styrene-phenylmalee) The polymer which has frame | skeleton consisting of a mid) derivative | guide_body, a poly (meth) acrylate derivative, etc. are mentioned. Polymer (B) can select and use suitably one or more types of polymers which have a skeleton chosen from these.

The polymer (B) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, and from the group consisting of polyamic acid, polyimide and polyorganosiloxane. It is more preferable that it is at least 1 sort (s) selected.

The said polymer (B) can be synthesize | combined by combining suitably the method of organic chemistry. For example, the polyamic acid as a polymer (B) can be obtained by making tetracarboxylic dianhydride illustrated as a compound used for the synthesis | combination of the said polyamic acid (A), and other diamine react. The polyimide as the polymer (B) can be obtained by dehydrating and closing the polyamic acid as the polymer (B), and the polyamic acid ester can be obtained by esterifying the polyamic acid. In addition, polyorganosiloxane can be obtained by hydrolytically condensing at least 1 sort (s) chosen from the group which consists of the said silane compound (s1) and the said other silane compound. In addition, the description of the said polymer (A) is applicable about the reaction conditions of each polymer.

When the said compound (A) contained in the liquid crystal aligning agent of this invention is a low molecular weight compound, the content rate of the said compound (A) is 100 weight part of polymers contained in a liquid crystal aligning agent from a viewpoint of fully obtaining the effect of this invention. It is preferable that it is 0.1-20 weight part with respect to, and it is more preferable that it is 0.5-15 weight part.

In addition, when the liquid crystal aligning agent of this invention contains a polymer (A) as said compound (A), in order to improve a solution characteristic and an electrical property, it is the said with a polymer (A) as a polymer component of a liquid crystal aligning agent. You may use a polymer (B). In this case, it is preferable to set it as 1 weight% or more with respect to the total amount of the polymer contained in a liquid crystal aligning agent, and, as for the content rate of a polymer (A), it is more preferable to set it as 5-50 weight%.

As a preferable aspect in the liquid crystal aligning agent of this invention, As a polymer component, (I) The aspect which consists only of polyorganosiloxane (A); (II) an aspect composed of at least one selected from the group consisting of polyamic acid (A) and polyimide (A); (III) an aspect consisting of at least one member selected from the group consisting of polyorganosiloxane (A), polyamic acid (A) and polyimide (A); (IV) It consists of a polyorganosiloxane (A) and another polymer (B), and another polymer (B) is at least 1 sort (s) chosen from the group which consists of polyamic acid and polyimide which do not have the said specific structure. Sun; (V) It consists of at least 1 sort (s) chosen from the group which consists of a polyamic acid (A) and a polyimide (A), another polymer (B), and the other polymer (B) does not have the said specific structure. At least one embodiment selected from the group consisting of polyorganosiloxane, polyamic acid and polyimide; Etc. can be mentioned. In addition, the compounding ratio of the polyorganosiloxane, polyamic acid, and polyimide in each aspect can be arbitrarily set according to the use etc. of the liquid crystal display element to apply.

Among these, the aspect containing at least any one of polyamic acid and a polyimide is preferable at the point of mechanical strength, electrical property, affinity with a liquid crystal, etc., and the aspect of said (II) and (IV) is more preferable. In addition, the aspect of the above (IV) is particularly preferable.

The use ratio of the polyorganosiloxane (A), the polyamic acid, and the polyimide (total) in the aspect of the above (IV) is 100 parts by weight of the total amount of the polyorganosiloxane (A), the polyamic acid, and the polyimide. It is preferable to contain 1-50 weight part of polyorganosiloxanes (A), It is more preferable to contain 2-40 weight part, It is still more preferable to contain 3-30 weight part.

It is preferable to contain 0.5-5 mmol / g of said specific structure with respect to the whole polymer component in a liquid crystal aligning agent, and, as for a polymer (A), it is more preferable to contain 1-4 mmol / g.

Moreover, in this invention, by forming a liquid crystal aligning film using the liquid crystal aligning agent containing a compound (A), reaction of the photopolymerizable compound (photopolymerizable monomer) contained in a liquid crystal layer at the time of light irradiation at the time of PSA treatment is carried out. It is inferred that it may be able to help from the liquid crystal aligning film side. Accordingly, it is inferred that a sufficient pretilt angle can be provided even with a small amount of light irradiation, and a reduction in voltage holding ratio and a decrease in response speed due to light irradiation can be suppressed.

<Other ingredients>

The liquid crystal aligning agent of this invention may contain other components as needed. As such other components, the compound (henceforth "epoxy group containing compound"), functional silane compound, etc. which have at least 1 epoxy group in a molecule | numerator are mentioned, for example.

Epoxy Compound

An epoxy compound can be used in order to improve adhesiveness and electrical characteristics with the board | substrate surface in a liquid crystal aligning film. Here, as an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol digly Cydylether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N -Diglycidyl-cyclohexylamine, etc. are mentioned as a preferable thing. When adding these epoxy compounds to a liquid crystal aligning agent, 40 weight part or less is preferable with respect to a total of 100 weight part of polymers contained in a liquid crystal aligning agent, and 0.1-30 weight part is more preferable.

[Functional silane compound]

A functional silane compound can be used for the purpose of improving the printability of a liquid crystal aligning agent. As such a functional silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 9-tri Methoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. Can.

When adding these functional silane compounds to a liquid crystal aligning agent, 2 weight part or less is preferable with respect to a total of 100 weight part of polymers, and 0.02-0.2 weight part is more preferable.

Moreover, as said other component, the compound, antioxidant, etc. which have at least 1 oxetanyl group in a molecule | numerator can be used other than the compound illustrated above.

<Solvent>

The liquid crystal aligning agent of this invention is a polymer component, and the other component arbitrarily mix | blended as needed, Preferably melt | dissolves in an organic solvent, and is comprised.

Here, as a solvent used for preparation of the liquid crystal aligning agent of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, di Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether There may be mentioned the lactate, dipropylene glycol monomethyl ether (DPM), di-isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These can be used individually or in mixture of 2 or more types.

Solid content concentration (the ratio which the total weight of components other than the solvent of a liquid crystal aligning agent occupies for the total weight of a liquid crystal aligning agent) in the liquid crystal aligning agent of this invention is chosen suitably in consideration of viscosity, volatility, etc., Preferably Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate as mentioned later, Preferably it heats, and the coating film which becomes a coating film which is a liquid crystal aligning film, or a liquid crystal aligning film is formed. At this time, when solid content concentration is less than 1 weight%, the film thickness of this coating film becomes small and it is difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 weight%, the film thickness of a coating film becomes excessive and it is difficult to obtain a favorable liquid crystal aligning film, and also the viscosity of a liquid crystal aligning agent increases and it is inferior to coating characteristic.

The range of especially preferable solid content concentration changes with the method of apply | coating a liquid crystal aligning agent to a board | substrate. For example, when using the spinner method, it is especially preferable to make solid content concentration into the range of 1.5 to 4.5 weight%. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is in the range of 12 to 50 mPa · s. When using the inkjet method, it is especially preferable to make solid content concentration into the range of 1 to 5 weight%, and to make solution viscosity into the range of 3-15 mPa * s. The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

<Liquid crystal aligning film and liquid crystal display element>

The liquid crystal aligning film of this invention is formed of the liquid crystal aligning agent prepared as mentioned above, and is used as a liquid crystal aligning film of a PSA mode liquid crystal display element. Moreover, the PSA mode liquid crystal display element of this invention is equipped with the said liquid crystal aligning film. The manufacturing method of the said liquid crystal display element is following (i)-(i);

(i) The 1st process of apply | coating the liquid crystal aligning agent of this invention on the said electrically conductive film of a pair of board | substrates which have a electrically conductive film, respectively, and then heating this to form a coating film,

(Ii) a second step of arranging a pair of substrates on which the coating film is formed so as to face the coating film so as to face each other via a liquid crystal layer containing a liquid crystal compound;

(Iii) A third 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. Hereinafter, each of these processes is explained in full detail.

[First Step: Formation of Coating Film]

As said board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the conductive film, a transparent conductive film is preferably used. For example, a NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ) and indium tin oxide (In ₂ O ₃ —SnO ₂ ) are formed. ITO membrane etc. can be used. It is preferable that this conductive film is a patterned conductive film partitioned in a plurality of regions. With such a conductive film, when a voltage is applied between the conductive films, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage in each region, thereby making the viewing angle characteristic wider. .

As a method of apply | coating the liquid crystal aligning agent of this invention on the formation surface of the transparent conductive film in a pair of board | substrate, Preferably, it can carry out by an offset printing method, a spin coating method, a roll coating method, or the inkjet printing method. At the time of coating of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, a functional titanium compound, etc. The pretreatment to be applied in advance may be performed.

After apply | coating a liquid crystal aligning agent to a board | substrate, Preferably, preheating (prebaking) is performed for the purpose of liquid flow prevention of the apply | coated liquid crystal aligning agent. Prebaking temperature becomes like this. Preferably it is 30-200 degreeC, More preferably, it is 40-150 degreeC, Especially preferably, it is 40-100 degreeC. Prebaking time becomes like this. Preferably it is 0.25-10 minutes, More preferably, it is 0.5-5 minutes. Thereafter, the solvent is completely removed and a firing (postbaking) step is performed for the purpose of thermally imidizing the dark acid structure present in the polymer as necessary. Post-baking temperature becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes. Thus, the film thickness of the film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The coating film used as an oriented film is formed by removing an organic solvent by the heating after apply | coating a liquid crystal aligning agent. At this time, when the polymer contained in the liquid crystal aligning agent of this invention is a polyamic acid, a polyamic acid ester, or the imidized polymer which has an imide ring structure and a dark acid structure, dehydration ring-closure reaction is advanced by further heating after coating film formation. It is good also as a coating film which was imidated more.

The coating film formed in this way may be provided as it is to the following 2nd process as it is, and may be provided to a 2nd process after performing the rubbing process with respect to a coating film surface as needed. This rubbing process can be performed by rubbing in a fixed direction with the roll which wound the cloth which consists of fibers, such as nylon, a rayon, and cotton, with respect to a coating film surface, for example.

Second Process: Construction of Liquid Crystal Cell

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning the liquid crystal layer containing a liquid crystalline compound and a photopolymerizable compound between two board | substrates which oppose. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method (vacuum injection 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 compound and a photopolymerizable compound in a cell gap, a liquid crystal cell is manufactured by sealing an injection hole. The second method is a method called an ODF (One Drop Fill) method. An ultraviolet-ray curable sealing compound is apply | coated to predetermined | prescribed place on one of the two board | substrates with which the liquid crystal aligning film was formed, for example, and a liquid crystal compound and light are carried out to predetermined several places on the liquid crystal aligning film surface further. After dropping the mixture with the synthetic compound, the other substrate was bonded to face the liquid crystal alignment film, the liquid crystal compound was spread on the entire surface of the substrate, and then the ultraviolet light was irradiated onto the entire surface of the substrate to seal the sealing agent. By hardening, a liquid crystal cell is manufactured.

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

As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

As a liquid crystalline compound, the nematic liquid crystal which has negative dielectric anisotropy can be used preferably, For example, a dicyano benzene system liquid crystal, a pyridazine system liquid crystal, a siphonbase liquid crystal, a cyanide liquid crystal, a biphenyl system A liquid crystal, a phenyl cyclohexane type liquid crystal, a terphenyl type liquid crystal, etc. can be used. Moreover, as a liquid crystalline compound, since the response speed of a PSA mode liquid crystal display element can be made faster, it uses together the alkenyl-type liquid crystal which is a monofunctional liquid crystalline compound which has either an alkenyl group and a fluoro alkenyl group. It is preferable. As such an alkenyl liquid crystal, a conventionally well-known thing can be used, For example, the compound etc. which are represented by each of following formula (L1-1)-formula (L1-9) are mentioned.

As the photopolymerizable compound, a compound having a functional group capable of radical polymerization such as acryloyl group, methacryloyl group, vinyl group or the like can be used. It is preferable to use the polyfunctional compound which has at least any two or more of acryloyl group and a methacryloyl group especially from a reactive viewpoint. In addition, from the viewpoint of stably maintaining the orientation of the liquid crystal molecules, as the photopolymerizable compound, it is preferable to use, as the liquid crystal skeleton, a compound having at least any one ring of at least one of a cyclohexane ring and a benzene ring in total. Moreover, a conventionally well-known thing can be used as such a photopolymerizable compound. It is preferable that the compounding ratio of a photopolymerizable compound shall be 0.1 to 0.5 weight% with respect to the total amount of the liquid crystalline compound to be used. It is preferable that the thickness of a liquid crystal layer shall be 1-5 micrometers.

[3rd process: light irradiation process]

After construction of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V DC or alternating current. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 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. In addition, the ultraviolet-ray of the said preferable wavelength range can be obtained by a means which uses a light source together with a filter diffraction grating etc., for example. As irradiation amount of light, Preferably it is 1,000 J / m <2> or less than 200,000 J / m <2>, More preferably, it is 1,000-100,000 J / m <2>.

In addition, although it was necessary to irradiate about 100,000 J / m <2> light at the time of manufacture of the conventionally known PSA mode liquid crystal display element, according to the method of this invention, the light irradiation amount is 50,000 J / m <2> or less and 10,000J / Even when it is set to m2 or less, a desired liquid crystal display element can be obtained. Therefore, in addition to reducing manufacturing cost of a liquid crystal display element, the fall of the voltage holding ratio resulting from strong light irradiation, and the fall of the response speed of a liquid crystal can be avoided.

And a PSA mode liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after light irradiation. As a polarizing plate used here, the polarizing plate which interposed the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol by the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The PSA mode liquid crystal display element of the present invention can be effectively applied to various apparatuses, for example, a clock, a portable game, a word processor, a notebook PC, a car navigation system, a camcorder, a PDA, a digital camera, a portable It can be used for various display devices, such as a telephone, a smart phone, various monitors, a liquid crystal television, and an information display.

EXAMPLE

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

The weight average molecular weight, epoxy equivalent, solution viscosity of each polymer solution, and the imidation ratio of the polyimide of each polymer in each synthesis example were measured by the following method.

[Weight Average Molecular Weight of Polymer]

The weight average molecular weight Mw of a polymer is a polystyrene conversion value measured by the gel permeation chromatography on the following conditions.

Column: Toso Corporation, TSKgelGRCXLⅡ

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

[Epoxy equivalent]

Epoxy equivalent is the value measured according to the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

[Solution Viscosity of Polymer Solution]

The solution viscosity [mPa * s] of a polymer solution was measured at 25 degreeC using the E-type rotational viscometer about the solution prepared at 10 weight% of polymer concentration using the predetermined solvent.

[Imidation Rate of Polyimide]

The solution of polyimide was put into pure water, the obtained precipitate was dried under reduced pressure sufficiently at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the formula represented by the following formula (1):

Imidation ratio [%] = {(1-A ¹ ) / (A ² × α)} × 100. (One)

(In Formula (1), A <^1> is the peak area derived from the proton of the NH group represented by 10 ppm of chemical shifts, A <^2> is the peak area derived from other protons, and (alpha) is a precursor (polyamic acid) of a polymer. Number ratio of other protons to one proton of NH group).

Synthesis of Polymer

Synthesis Example P1 Synthesis of Polyimide (A) (Side Chain Introduction)

112 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA) as tetracarboxylic dianhydride, and 49 g (0.10 mol) of cholestanyloxy-2,4-diaminobenzene as diamine, 9 52 g (0.15 mole), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 67 g, 9-bis (4-aminophenyl) fluorene (0.25 mol) was dissolved in 750 g of N-methyl-2-pyrrolidone (NMP), and reaction was performed at 60 degreeC for 6 hours, and the solution containing polyamic acid was obtained. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 900 mPa · s.

Subsequently, 63 g of NMP were added to the obtained polyamic acid solution, 3.8 g of N-methyl piperidine and 10.6 g of acetic anhydride were added, and dehydration ring-closing reaction was performed at 80 degreeC for 8 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, it dried at 40 degreeC under reduced pressure for 15 hours, and obtained polyimide (P-1) of about 50% of imidation ratio as a polymer (A). The obtained polyimide (P-1) was prepared so that it might become 10 weight% in NMP. It was 330 mPa * s when the viscosity of this solution was measured.

Synthesis Example P2 Synthesis of Polyimide (A) (Main Chain Introduction Type)

A solution containing polyamic acid was carried out in the same manner as in Synthesis Example P1, except that 32 g (0.15 mol) of 4,4'-diaminobenzophenone was used in place of 9,9-bis (4-aminophenyl) fluorene. Got it. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 1,050 mPa · s. Moreover, the polyimide (P-2) of about 50% of imidation ratio was obtained as a polymer (A) by performing operation similar to the synthesis example P1 using the obtained polyamic acid solution. The obtained polyimide (P-2) was prepared so that it might become 10 weight% in NMP. It was 420 mPa * s when the viscosity of this solution was measured.

Synthesis Example P3 Synthesis of Polymer (B) (Synthesis of Polyimide)

A solution containing polyamic acid was obtained in the same manner as Synthesis Example P1 except that 23 g (0.15 mol) of 3,5-diaminobenzoic acid was used in place of 9,9-bis (4-aminophenyl) fluorene. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 2,400 mPa · s.

Next, 330 g of NMP were added to the obtained polyamic acid solution, 25 g of N-methyl piperidine and 25.5 g of acetic anhydride were added, and dehydration ring-closure reaction was performed at 80 degreeC for 8 hours. The reaction mixture was then poured into excess methanol to precipitate the reaction product. After wash | cleaning the collect | recovered precipitate with methanol, it dried at 40 degreeC under reduced pressure for 15 hours, and obtained polyimide (P-3) of about 50% of imidation ratio as a polymer (B). The obtained polyimide (P-3) was prepared so that it might become 10 weight% in NMP. It was 340 mPa * s when the viscosity of this solution was measured.

Synthesis Example S1 Synthesis of Polyorganosiloxane (A)

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 246 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) as a hydrolyzable silane compound and 500 g of methyl isobutyl ketone as a solvent And 10.0 g of triethylamine was put as a catalyst, and it mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and it stirred at 80 degreeC under reflux for 6 hours, stirring. After completion of the reaction, the organic layer was taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to thereby obtain a hydrolysis condensate having an epoxy group (PECETS). Was obtained as a viscous transparent liquid. As a result of ¹ H-NMR analysis of this hydrolysis-condensation product, it was confirmed that a peak attributed to the epoxy group was obtained according to the theoretical strength near the chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. .

Subsequently, in a 200 mL three-necked flask, a hydrolysis-condensation product (PECETS) having an epoxy group obtained above, 30.0 g of methyl isobutyl ketone as a solvent, and 25.0 g of 4-octyloxybenzoic acid as a carboxylic acid (hydrolysable silane compound used as a raw material) Equivalent to 20 mol%) and 11-((4'-nitro- [1,1'-biphenyl] -4-yl) oxy) undecanoic acid 19.9 g (10 for hydrolyzable silane compound used as raw material) Equivalent to mol%), and 0.10 g of tetrabutylammonium bromide (TBAB, which is a curing accelerator of an epoxy compound) was added as a catalyst, and the reaction was performed at 100 ° C under stirring for 2 hours. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water five times, dried using magnesium sulfate, and then the solvent was distilled off to obtain 251.2 g of polyorganosiloxane (S-1) as the polymer (A). Got it. About this polyorganosiloxane (S-1), the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography (GPC) was 7,200.

Synthesis Example S2: Synthesis of Polyorganosiloxane (A)

The carbonic acid to be used is 11- (4- (4-pentylcyclohexyl) phenoxy) undecanoic acid (equivalent to 20 mol% relative to the hydrolyzable silane compound used as a raw material) and 4-phenylbenzoic acid (a hydrolyzate used as a raw material) Polyorganosiloxane (S-2) which is a polymer (A) was obtained by performing the same operation as Synthesis Example S1 except having changed to 10 mol% with respect to a decomposable silane compound. The weight average molecular weight Mw of polystyrene conversion measured by GPC about this polyorganosiloxane (S-2) was 7,500.

The compounding quantity (molar ratio) of the compound used for the synthesis | combination of a polymer is shown in following Table 1. In addition, about polyimide, the ratio of each compound with respect to the number-of-moles of the sum total of tetracarboxylic dianhydride and diamine used for synthesis is shown. About polyorganosiloxane, the use ratio (molar ratio) of each compound with respect to the sum total of the hydrolyzable silane compound used for the synthesis | combination of an epoxy-group containing polyorganosiloxane is shown.

The abbreviation of each compound in the said Table 1 has the following meanings, respectively.

(Diamine)

d-1; 9,9-bis (4-aminophenyl) fluorene

d-2; 4,4'-diaminobenzophenone

d-3; Cholestanyloxy-2,4-diaminobenzene

d-4; 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine

d-5; 3,5-diaminobenzoic acid

(Carbonic acid)

CA-1; 4-octyloxybenzoic acid

CA-2; 11-((4'-nitro- [1,1'-biphenyl] -4-yl) oxy) undecanoic acid

CA-3; 11- (4- (4-pentylcyclohexyl) phenoxy) undecanoic acid

CA-4; 4-phenylbenzoic acid

<Preparation of liquid crystal composition>

[Preparation of liquid crystal composition LC1]

0.3 weight% of 5 weight% of liquid crystalline compounds represented by said formula (L1-1), and the photopolymerizable compound represented by following formula (L2-1) with respect to 10 g of nematic liquid crystals (MLC-6608 by Merck Co., Ltd.). Liquid crystal composition LC1 was obtained by adding and mixing.

Example 1

<Preparation of liquid crystal aligning agent>

To the solution containing polyimide (P-1) obtained in Synthesis Example P1 as compound (A), NMP and butyl cellosolve (BC) were added as an organic solvent, and the solvent composition was NMP: BC = 50: 50 ( Weight ratio) and a solid content concentration of 6.0 wt%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

<Evaluation of Printability>

The printability of the liquid crystal aligning agent prepared above was evaluated. First, about the said liquid crystal aligning agent, it apply | coats to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film using the offset type liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.), The solvent was removed by heating (prebaking) on a hot plate for 1 minute, and then heated (postbaking) on a hot plate at 200 ° C. for 10 minutes, and the average film thickness measured by a tactile film thickness meter (KLA Tencor Co., Ltd.) was 600 kPa. A coating film was formed. This coating film was observed under the microscope of 20 times magnification, and the presence or absence of the printing stain and the pinhole was examined. The evaluation performed the case where printing unevenness | corrugation and a pinhole were not observed at least any one of printability "goodness", printing unevenness, and pinhole as printability "badness." As a result, neither printing unevenness nor pinhole was observed in the coating film formed using the liquid crystal aligning agent prepared above, and printability was "good."

<Evaluation of Film Thickness Uniformity>

About the coating film formed above, the film thickness in the center part of a board | substrate and the film thickness in the position which deviated to the center 15 mm from the outer end of a board | substrate were used, respectively, using a stylus type film thickness gauge (made by KLA Tencor) Measured. The film thickness uniformity "good" and the case where the film thickness difference exceeded 20 microseconds were evaluated as film thickness uniformity "poor" when both film thickness difference is 20 kPa or less. As a result, in the coating film formed using the said liquid crystal aligning agent, the film thickness difference between the center part and the edge part was small, and film thickness uniformity was "good."

<Production and Evaluation of Liquid Crystal Cells>

The pattern (two types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed using the liquid crystal aligning agent prepared above, and six liquid crystal display elements were produced in total. Moreover, various evaluation was performed about the liquid crystal cell which manufactured them.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

The said liquid crystal aligning agent is apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.), and it heats on a 80 degreeC hotplate for 1 minute. (Prebaking) After removing a solvent, it heated on 10 degreeC hotplates (postbaking) for 10 minutes, and formed the coating film of average film thickness of 600 Pa. About this coating film, the rubbing process was performed by the rubbing machine which has the roll which wound the rayon spring at roll rotation speed 400rpm, stage movement speed | rate 3cm / sec, and hair pressing indentation length 0.1mm. 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. Moreover, the said rubbing process is a weak rubbing process performed in order to control the inclination of a liquid crystal, and to perform orientation division by a simple and easy method.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film with respect to one of the said pair of board | substrates, a pair of board | substrates are a liquid crystal aligning film surface It overlapped and crimped | matched so that it might correspond, and the adhesive agent was hardened. Subsequently, after filling the liquid crystal composition LC1 prepared above 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. For the remaining two liquid crystal cells, an alternating current of 10 V at a frequency of 60 Hz is applied between the electrodes, respectively, and 10,000 J / m 2 or 100,000 J using an ultraviolet irradiation device using a metal halide lamp as the light source while the liquid crystal is driven. Ultraviolet rays were irradiated at an irradiation amount of / m 2, and then used for evaluation of the pretilt angle and voltage holding ratio. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference.

[Evaluation of Pretilt Angle]

Using the liquid crystal cell manufactured above, document "T. J. Scheffer et al., J. Appl. Phys. vo. 19, p. 2013 (1980) ", the value of the inclination-angle from the board | substrate surface of the liquid crystal molecule measured by the crystal rotation method using a He-Ne laser beam was made into the pretilt angle. 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> is shown in following Table 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, Toyo Technica Corporation make and VHR-1 were used.

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 100,000 J / m 2 are shown in Table 2 below.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode]

The liquid crystal aligning agent prepared above is patterned in the slit shape as shown in FIG. 1, and is a liquid crystal aligning film printer (Nippon Shashin Inc. (Nippon Shasin Ins. Co., Ltd.) on each electrode surface of two glass substrates each having the ITO electrode partitioned in several area | region. (Manufacture), and the solvent was removed by heating (prebaking) for 1 minute on an 80 ° C hot plate. Subsequently, it heated on the 150 degreeC hotplate for 10 minutes (post-baking), and formed the coating film of 600 kPa of average film thicknesses. After performing ultrasonic cleaning for 1 minute in ultrapure water about this coating film, the board | substrate which has a liquid crystal aligning film was obtained by drying for 10 minutes in 100 degreeC clean oven. 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 diameter 5.5micrometer to the outer edge of the surface which has a liquid crystal aligning film, one board | substrate of the said pair of board | substrates is made so that a liquid crystal aligning film surface may face a pair of board | substrates. They were overlaid and pressed to harden the adhesive. Subsequently, after filling the liquid crystal composition LC1 prepared above 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 directly for evaluation of the response speed mentioned later. For the remaining two liquid crystal cells, light is emitted at a dose of 10,000 J / m 2 or 100,000 J / m 2 in a state where a voltage is applied between the conductive films by the same method as in the production of the liquid crystal cell having the transparent electrode without the pattern. After the investigation, the response speed was evaluated. In addition, the pattern of the electrode used here is a pattern similar to the electrode pattern in PSA mode.

[Evaluation of response speed]

After each liquid crystal cell prepared above was sandwiched with two polarizing plates arranged in a cross nicol state, first, a visible light lamp was irradiated without applying a voltage, and the luminance of light transmitted through the liquid crystal cell was measured by a photo multimeter. This value was made into 0% of a relative transmittance. Next, the transmittance | permeability when the alternating current 10V was applied for 5 second between the electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability. When alternating current 10V 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. The response speeds 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> are shown in the said Table 2.

Example 2

A liquid crystal aligning agent was prepared by performing the same operation as in Example 1 except that the polyimide (P-2) obtained in Synthesis Example P2 was used as the compound (A). Moreover, it evaluated similarly to Example 1 using this liquid crystal aligning agent. The evaluation results are shown in Table 2 above.

Example 3

To the solution containing polyimide (P-3) obtained in Synthesis Example P3, NMP and BC were added as an organic solvent, and benzophenone was further added as a compound (A) to 80 parts by weight of polyimide (P-3). It added 5 weight part (6.25 weight part with respect to 100 weight part of polyimide (P-3)), and the solvent composition was made into the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 6.0weight%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters. In addition, various evaluation was performed similarly to Example 1 using this liquid crystal aligning agent. The evaluation results are shown in Table 2 above.

Example 4

To the solution containing polyimide (P-3) obtained in Synthesis Example P3, NMP and BC were added as an organic solvent, and further, polyorganosiloxane (S-1) obtained in Synthesis Example S1 as Compound (A). 5 weight part was added with respect to 95 weight part of polyimides (P-3), and the solvent composition was made into the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 6.0weight%. The liquid crystal aligning agent was prepared by filtering this solution using the filter of 1 micrometer of pore diameters. In addition, various evaluation was performed similarly to Example 1 using this liquid crystal aligning agent. The evaluation results are shown in Table 2 above.

Example 5

In the said Example 4, the liquid crystal aligning agent was prepared by performing the same operation as Example 4 except having used the polyorganosiloxane (S-2) instead of the polyorganosiloxane (S-1). In addition, various evaluation was performed similarly to Example 1 using this liquid crystal aligning agent. The evaluation results are shown in Table 2 above.

Comparative Example 1

In Example 1, the same operation as in Example 1 was carried out except that the solution containing polyimide (P-3) obtained in Synthesis Example P3 was used instead of the solution containing polyimide (P-1). The liquid crystal aligning agent was prepared. In addition, various evaluation was performed similarly to Example 1 using this liquid crystal aligning agent. The evaluation results are shown in Table 2 above.

As shown in Table 2, in Examples 1-5, the high voltage holding ratio was maintained after ultraviolet irradiation to the liquid crystal cell, and the response speed was also favorable. Moreover, in Examples 1-5, the appropriate pretilt angle was shown by the light irradiation amount of 10,000 J / m <2>. Moreover, even a small amount of light irradiation had a sufficiently fast response speed, and the voltage holding ratio was also good. In particular, when an alkenyl-based liquid crystal is used as the liquid crystal, a decrease in the voltage holding ratio due to ultraviolet irradiation tends to increase. However, in Examples 1 to 5, a high voltage holding ratio was shown even after ultraviolet irradiation. Moreover, the printability and film uniformity of the liquid crystal aligning agent were also favorable. From these results, it can be said that according to the liquid crystal aligning agent of this invention, the merit of PSA mode can be expressed with a small amount of light irradiation. In contrast, in Comparative Example 1, an appropriate pretilt angle was not shown with a light irradiation amount of 10,000 J / m 2. Moreover, the fall of the voltage holding ratio by ultraviolet irradiation was remarkable.

For each of the liquid crystal aligning agents used in Examples 1 to 5, a liquid crystal cell was prepared in the same manner as in Example 1 except that the pattern of the ITO electrode on the glass substrate was changed to the electrode patterns of FIGS. 2 and 3, respectively. And various evaluations were made. Also in this case, the same effects as in Examples 1 to 5 were exhibited.

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

Claims (9)

Liquid crystal for PSA mode liquid crystal display element containing the compound (A) which has a structure (a) which can express at least any function among the radical generation function which generate | occur | produces a radical by light irradiation, and the photosensitization function which exhibit a sensitization effect by light irradiation. Aligning agent,
It is for manufacture of PSA mode liquid crystal display element containing the monofunctional liquid crystalline compound which has either an alkenyl group and a fluoro alkenyl group in a liquid crystal layer, The liquid crystal aligning agent for PSA mode liquid crystal display elements characterized by the above-mentioned. The method of claim 1,
The liquid crystal aligning agent for PSA mode liquid crystal display elements whose said compound (A) is a polymer which has the said structure (a) in a side chain. The method of claim 1,
Liquid crystal aligning agent for PSA mode liquid crystal display elements whose said compound (A) is at least 1 sort (s) of polymer chosen from the group which consists of a polyamic acid, a polyimide, a polyamic acid ester, and a polyorganosiloxane. The method of claim 1,
The liquid crystal aligning agent for PSA mode liquid crystal display elements in which the said compound (A) has a structure which can express the said photosensitive function at least as said structure (a). delete The agent which apply | coats the liquid crystal aligning agent for PSA mode liquid crystal display elements in any one of Claims 1-4 on the said conductive film of a pair of board | substrate which has a conductive film, respectively, and then heats this and forms a coating film. 1 process,
A pair of substrates on which the coating film is formed is disposed to face each other such that the coating films face each other via a liquid crystal layer containing a monofunctional liquid crystalline compound having any one of an alkenyl group and a fluoroalkenyl group. 2 processes,
A third step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates
Method for producing a PSA mode liquid crystal display device comprising a. delete It is a liquid crystal aligning film for PSA mode liquid crystal display elements formed using the liquid crystal aligning agent for PSA mode liquid crystal display elements in any one of Claims 1-4,
It is for manufacture of PSA mode liquid crystal display element containing the monofunctional liquid crystalline compound which has either an alkenyl group and a fluoro alkenyl group in a liquid crystal layer, The liquid crystal aligning film for PSA mode liquid crystal display elements characterized by the above-mentioned. The liquid crystal aligning film for PSA mode liquid crystal display elements of Claim 8 is provided,
A monofunctional liquid crystalline compound having any one of an alkenyl group and a fluoro alkenyl group is included in the liquid crystal layer, PSA mode liquid crystal display device.

Images