KR20130025808A - Manufacturing method for liquid crystal display device, polymer composition, and the liquid crystal display device - Google Patents

Abstract

PURPOSE: A manufacturing method of a liquid crystal display device, a polymer composition thereof, and the liquid crystal display device thereof are provided to widen a view angle and to improve the response speed of a liquid crystal molecule. CONSTITUTION: A coating layer is formed on a pair of substrates by applying and heating a polymer composition. A liquid crystal molecule layer is placed on the substrates. A liquid crystal cell is formed by the facing placement of the coating layer. A voltage is supplied to a conductive layer included in the substrates. Light is emitted to the liquid crystal cell. [Reference numerals] (AA) ITO line(35μm width, 200 in number); (BB) ITO line(35μm width, 199 in number)

Description

MANUFACTURING METHOD FOR LIQUID CRYSTAL DISPLAY DEVICE, POLYMER COMPOSITION, AND THE LIQUID CRYSTAL DISPLAY DEVICE

This invention relates to the manufacturing method of a liquid crystal display element. More specifically, the present invention relates to a novel method for producing a liquid crystal display device having a wide viewing angle, a fast response speed, and high long-term reliability.

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

 Recently, in order to solve the above problems of the MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed. PSA mode is a polymerizable compound in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film not having a pattern, or a gap of a pair of substrates formed of two substrates with a patterned conductive film. It is a technique which tries to control the orientation direction of a liquid crystal by sandwiching the liquid crystal composition containing and polymerizing a polymeric compound by irradiating an ultraviolet-ray in the state which applied the voltage between electrically conductive films, thereby expressing a pretilt angle characteristic. According to this technique, by setting the conductive film to a specific structure, the viewing angle can be expanded and the liquid crystal molecular response can be increased, and the problems of the transmittance and the lack of contrast which are inevitable in the MVA panel are also solved. However, for the polymerization of the polymerizable compound, irradiation of a large amount of ultraviolet light, for example, 100,000 J / m 2, is required, and thus, the problem of decomposing liquid crystal molecules occurs, and thus, the polymer that has not been polymerized by ultraviolet light irradiation also occurs. Reaction compounds remain in the liquid crystal layer, and these interact with each other to cause display unevenness, adversely affect voltage preservation characteristics, or problems with long-term reliability of the panel.

About these, Nonpatent literature 1 has proposed the method of using the liquid crystal aligning film formed from the polyimide-type liquid crystal aligning agent containing a reactive mesogen. According to the nonpatent literature 1, the liquid crystal display element provided with the liquid crystal aligning film formed by such a method says that the response of a liquid crystal molecule is high speed. However, Non-Patent Document 1 does not describe any reactive mesogen in what amount, and there is still a large amount of ultraviolet irradiation required, and concerns about display characteristics, in particular, voltage integrity characteristics, are not dismissed. .

Moreover, patent document 3 has proposed the manufacturing method of the liquid crystal display element using the organic film obtained by apply | coating the polymer composition containing the polyimide containing a reactive mesogen which has a specific structure, and a solvent on a board | substrate, and heating this. . Patent Document 3 describes that according to the method described in this document, a liquid crystal display device having a wide viewing angle, a fast response speed of liquid crystal molecules, and excellent display characteristics can be produced. And patent document 3 describes that arbitrary temperature in the extremely wide range of 120-300 degreeC can be employ | adopted as heating temperature (post baking temperature) at the time of forming an organic film. However, according to the examination of the present inventors, in the method of patent document 3, it turned out that the effect which this document expects is not expressed, unless the postbaking temperature at the time of forming an organic film is made into low temperature of about 150 degreeC or less. When the post-baking temperature is set at such a low temperature, the solvent of the composition remains in the organic film to be formed, and as a result, the display performance is impaired (long-term reliability is low) in the liquid crystal display device after a long time has elapsed after production. It turned out that there was a case.

Japanese Patent Application Laid-Open No. 5-107544 Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Laid-Open Patent Publication No. 2011-76065

 Y.-J.Lee et al., SID 09 DIGEST, p.666 (2009)  T. J. Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)  F. Nakano, et al., JPN. J. Appl. Phys. Vol. 19, p. 2013 (1980)

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

According to this invention, the said subject of this invention is

It is achieved by a method for producing a liquid crystal display device, characterized by the following process:

On the said conductive film of a pair of board | substrates which have a conductive film, respectively,

(A) 100 parts by weight of at least one polymer selected from the group consisting of polyamic acid and polyimide,

(B) 10 to 100 parts by weight of a compound having two or more polymerizable unsaturated bonds, and

(C) 1 to 50 parts by weight of radical scavenger

Applying a polymer composition containing, and then heating it to form a coating film,

Forming a liquid crystal cell by 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 layer of liquid crystal molecules;

Irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

The liquid crystal display device produced by the method of the present invention has a wide viewing angle, a fast response speed of liquid crystal molecules, a sufficient transmittance and contrast, excellent display characteristics, and no deterioration of display characteristics even when continuously driven for a long time. .

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

Therefore, the liquid crystal display element manufactured by the method of this invention is superior to the liquid crystal display element conventionally known in both performance and cost, and can be applied suitably for various uses.

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

(Mode for carrying out the invention)

<Polymer composition>

The polymer composition used in the method of the present invention,

(A) 100 parts by weight of at least one polymer selected from the group consisting of polyamic acid and polyimide,

(B) 10 to 100 parts by weight of a compound having two or more polymerizable unsaturated bonds, and

(C) 1 to 50 parts by weight of radical scavenger

It contains.

[(A) Polymer]

The polymer (A) contained in the polymer composition used in the present invention is at least one selected from the group consisting of polyamic acid and polyimide.

The said polyamic acid can be synthesize | combined, for example by making tetracarboxylic dianhydride and diamine react, and the said polyimide can be synthesize | combined by dehydrating and ring-closing the said polyamic acid.

{Tetracarboxylic dianhydride}

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic 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, 4 , 9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride etc. can be mentioned, respectively, In addition, you may use tetracarboxylic dianhydride of patent document 2 (Unexamined-Japanese-Patent No. 2010-97188). .

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, among these, using only alicyclic tetracarboxylic dianhydride or using a mixture of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride is used. desirable. In the latter case, the ratio of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 20 mol% or more, more preferably 40 mol% or more.

{Diamine}

As a diamine used for synthesize | combining the said polyamic acid, following formula (D '):

In formula (D '), R <^I> is a C4-C40 alkyl group or a C4-C40 fluoroalkyl group, or a C17-51 hydrocarbon group which has a steroid skeleton;

Z ^I is a single bond, ^* -O-, ^* -COO- or ^* -OCO- (wherein the bond to which "*" is attached is the R ^I side),

R ^II is a cyclohexylene group or a phenylene group,

n1 is 1 or 2,

Provided that when n 1 is 2, two R ^IIs may be the same as or different from each other, and n 2 is 0 or 1;

Z ^II is ^* -O-, ^* -COO- or ^* -OCO- (wherein the bond to which "*" is attached is R ^I side),

n3 is an integer of 0 to 2,

n4 is 0 or 1)

It is preferable to use the diamine containing the diamine (henceforth "specific diamine") which has group represented by.

As a C4-C40 alkyl group of R <^I> in said Formula (D '), a C6-C40 alkyl group is preferable, Specifically, for example, hexyl group, octyl group, decyl group, dodecyl group, hexade Real groups, stearyl groups and the like;

As a C4-C40 fluoroalkyl group, a C4-C20 fluoroalkyl group is preferable, For example, a trifluoromethylpropyl group, a trifluoromethylbutyl group, a trifluoromethylhexyl group, and a tri Fluoromethyldecyl group, pentafluoroethylpropyl group, pentafluoroethylbutyl group, pentafluoroethyloctyl group, etc .;

As a 17-51 hydrocarbon group which has a steroid skeleton, a cholestanyl group, a cholesteryl group, a lanostanyl group, etc. are mentioned, for example.

It is preferable that the cyclohexylene group and phenylene group of R <^II> in said Formula (D ') are 1, 4- cyclohexylene group and 1, 4- phenylene group, respectively. As a divalent group represented _by- ( ^RII ) _n1- in the said Formula (D '), when n1 is 1, For example, a 1, 4- phenylene group, a 1, 2- cyclohexylene group, etc .;

As n1 is 2, for example, a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group, and a following formula:

(In the above formula, the bonding hand with "*" is the R ^I side.)

The group etc. which are represented by each of are mentioned as a preferable thing, respectively.

It is preferable that n3 in said Formula (D ') is two.

As specific diamine in this invention, it is preferable that it is aromatic diamine which has group represented by said formula (D '), As a specific example, dodecaneoxy-2, 4- diamino benzene, pentadecaneoxy- 2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2, 5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, and the like. It is preferable to use species or more. Specific diamines in the present invention are, in particular, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene and cholesteryl It is preferable to use at least 1 sort (s) chosen from the group which consists of oxy-3, 5- diamino benzene.

As a diamine used for synthesize | combining the said polyamic acid, only the specific diamine mentioned above may be used, and a specific diamine and other diamine may be used together.

The other diamine which can be used here is a diamine which does not have group represented by said formula (D '), For example, it does not correspond to the said specific diamine as aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. It is not. As these specific examples, As an aliphatic diamine, For example, 1,1-methyylenediamine, 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, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl -3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine and the like;

Examples of the diaminoorganosiloxanes include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and are described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188). You may use the diamine described.

As diamine used in order to synthesize | combine the said polyamic acid, it is preferable to contain 2 mol% or more of said specific diamine with respect to all diamine, It is more preferable to contain 2-60 mol%, It is more preferable that it is 5-40 mol It is more preferable to contain%, and it is preferable to contain 10-30 mol% especially.

{Molecular weight regulator}

When synthesize | combining the said polyamic acid, you may make it synthesize | combine the terminal-modified polymer using the appropriate molecular weight modifier with tetracarboxylic dianhydride and diamine as mentioned above. By setting it as such a terminal modified polymer, the coating property (printability) of a polymer composition can be improved, without impairing the effect of this invention.

As said molecular weight modifier, an acid anhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as an acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. of;

As a monoamine compound, For example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc .;

As a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, respectively.

It is preferable to make the use ratio of a molecular weight modifier into 10 weight part or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine to be used.

{Synthesis of Polyamic Acid}

The use ratio of the tetracarboxylic dianhydride and diamine provided in the polyamic acid synthesis reaction is preferably such that the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine. Preferably it is the ratio which becomes 0.3-1.2 equivalent.

Synthesis reaction of polyamic acid, Preferably in an organic solvent, Preferably it is -20 degreeC-150 degreeC, More preferably, it is 0-100 degreeC, Preferably it is 0.1-24 hours, More preferably, it is 0.5-12 Time is done.

Here, as an organic solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Aprotic polar solvents such as hexamethylphosphortriamide; Phenolic solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned. It is preferable that the usage-amount (a) of an organic solvent is an amount so that the total amount (b) of tetracarboxylic dianhydride and diamine may be 0.1-30 weight% with respect to the total amount (a + b) of a reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid can be obtained.

This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, may be provided to preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in a reaction solution, or after refine | purifying the isolated polyamic acid, preparation of a liquid crystal aligning agent You may provide to. When polyamic acid is dehydrated and closed, and it is set as polyimide, the said reaction solution may be used for a dehydration ring-closure reaction as it is, may be used for dehydration ring-closure reaction after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid After purification, the dehydration ring-closure reaction may be used. Isolation and purification of polyamic acid can be performed according to a well-known method.

{Synthesis of Polyimide}

The said polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesize | combined as mentioned above and imidating.

The polyimide in the present invention may be a complete imide obtained by dehydrating and ring-closing all of the dark acid structures possessed by the polyamic acid as its precursor. A partial imide may be sufficient. It is preferable that the imidation ratio is 40% or more, and, as for the polyimide in this invention, it is more preferable that it is 45 to 80%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. . Among these, it is preferable by the latter method.

In the method of adding the dehydrating agent and the dehydrating ring-closure catalyst to the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. 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 organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid 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 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing a polyimide can be obtained. This reaction solution may be provided as it is to preparation of a liquid crystal aligning agent as it is, may be provided to preparation of a liquid crystal aligning agent after removing a dehydrating agent and a dehydration ring-closure catalyst from a reaction solution, and after isolation of a polyimide to preparation of a liquid crystal aligning agent You may provide, or after refine | purifying an isolated polyimide, you may provide for preparation of a liquid crystal aligning agent. These purification operations can be performed by a well-known method.

The polystyrene reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid and polyimide is preferably 1,000 to 500,000, particularly preferably 2,000 to 300,000, and Mw and The ratio (Mw / Mn) to polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 15 or less, and particularly preferably 10 or less. By being in such a molecular weight range, the favorable orientation and stability of a liquid crystal display element can be ensured.

[(B) COMPOUND]

The compound (B) used in the present invention is a compound having two or more polymerizable unsaturated bonds in the molecule.

As said polymerizable unsaturated bond, it is a following formula (B-I), for example:

(In formula (BI), R is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.)

The group represented by is mentioned. It is preferable that Y <^1> and Y <^2> in said Formula (BI) are oxygen atoms, respectively. It is preferable that the compound (B) has two or more groups represented by the above formula (BI) in the molecule.

It is preferable that the compound (B) has only two polymerizable unsaturated bonds in a molecule.

The compound (B) has the following formula (B-II) in addition to two or more polymerizable unsaturated bonds in its molecule:

-X ¹ -Y ³ -X ^2- (B-II)

(In formula (B-II), X <^1> and X <^2> are respectively independently a 1, 4- phenylene group or a 1, 4- cyclohexylene group, Y <^3> is a single bond, C1-C4 bivalent A hydrocarbon group, an oxygen atom, a sulfur atom or -COO-, provided that X ¹ and X ² are substituted with one or more alkyl groups of 1 to 4 carbon atoms, alkoxyl groups of 1 to 4 carbon atoms, fluorine atoms or cyano groups May be)

It is preferable to further have group represented by. When Y <^3> in the said Formula (B-II) is a hydrocarbon group, it is preferable that the carbon number is 1-3.

As a C1-C4 bivalent hydrocarbon group in said Formula (B-II), a methylene group, a dimethyl methylene group, etc. are mentioned, for example. As a specific example of the bivalent group represented by said formula (B-II), the following formula (B-II-1)-(B-II-6):

And the like. The benzene ring and the cyclohexane ring in the formulas (B-II-1) to (B-II-6) are each an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a fluorine atom or a cyano group, respectively. It may be substituted.

As the compound (B) used in the present invention,

Di (meth) acrylate which has a biphenyl structure (Y <^1> and Y <^2> in said Formula (B-II) are oxygen atoms, respectively, and the divalent group represented by said Formula (B-II) is a said formula ( B-II-1)),

Di (meth) acrylate which has a phenyl-cyclohexyl structure (Y <^1> and Y <^2> in said Formula (BI) are oxygen atoms, respectively, and the divalent group represented by said Formula (B-II) is a said formula ( B-II-2)),

Di (meth) acrylate which has a 2, 2- diphenyl propane structure (Y <^1> and Y <^2> in said Formula (BI) are oxygen atoms, respectively, and divalent group represented by said Formula (B-II) Group represented by the formula (B-II-3)),

Di (meth) acrylate which has a diphenylmethane structure (Y <^1> and Y <^2> in said Formula (BI) are oxygen atoms, respectively. The bivalent group represented by said formula (B-II) is a said formula (B -Ⅱ-4)),

Di-thio (meth) acrylate having a diphenylthioether structure (Y ¹ in the formula (BI) is an oxygen atom, Y ² is a sulfur atom; a divalent group represented by the formula (B-II). Group represented by the formula (B-II-5)) and

Other (B) compounds are mentioned.

As these specific examples, it is di (meth) acrylate which has a biphenyl structure, for example, 4'-acryloyloxy biphenyl-4-yl-acrylate,

4'-methacryloyloxy-biphenyl-4-yl-methacrylate,

2- [4 '-(2-acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl acrylate,

2- [4 '-(2-methacryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl methacrylate,

Bishydroxyethoxybiphenyl diacrylate,

Bishydroxyethoxybiphenyl dimethacrylate,

2- (2- {4 '-[2- (2-acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethylacrylate,

2- (2- {4 '-[2- (2-methacryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl methacrylate,

Diacrylates of ethylene oxide adducts of biphenyls,

Dimethacrylate of an ethylene oxide adduct of biphenyl,

Diacrylates of propylene oxide adducts of biphenyls,

Dimethacrylate of propylene oxide adducts of biphenyl,

2- (4'-acryloyloxy-biphenyl-4-yloxy) -ethylacrylate,

2- (4'-methacryloyloxy-biphenyl-4-yloxy) -ethyl methacrylate and the like;

As the di (meth) acrylate having a phenyl-cyclohexyl structure, for example, 4- (4-acryloyloxy-phenyl) -cyclohexyl acrylate,

4- (4-methacryloyloxy-phenyl) -cyclohexyl methacrylate,

2- {4- [4- (2-acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl acrylate,

2- {4- [4- (2-methacryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl methacrylate,

2- [2- (4- {4- [2- (2-Acryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl acrylate,

2- [2- (4- {4- [2- (2-methacryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl methacrylate, etc. ;

As di (meth) acrylate which has a 2, 2- diphenyl propane structure, it is 4- [1- (4-acryloyloxy-phenyl) -1-methyl-ethyl] -phenylacrylate,

4- [1- (4-methacryloyloxy-phenyl) -1-methyl-ethyl] -phenyl methacrylate,

2- (4- {1- [4- (2-acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethylacrylate,

2- (4- {1- [4- (2-Methacryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl methacrylate, bishydroxyethoxy-bisphenol A diacrylate,

Bishydroxyethoxy-bisphenol A dimethacrylate,

2- {2- [4- (1- {4- [2- (2-Acryloyloxy-ethoxy) -ethoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -ethoxy} Ethyl acrylate,

2- {2- [4- (1- {4- [2- (2-Methacryloyloxy-ethoxy) -ethoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -ethoxy } -Ethyl methacrylate,

Diacrylate of ethylene oxide adduct of bisphenol A,

Dimethacrylate of ethylene oxide adducts of bisphenol A,

Diacrylate of propylene oxide adduct of bisphenol A,

Dimethacrylate of propylene oxide adducts of bisphenol A,

2- (4- {1- [4- (2-acryloyloxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethylacrylate,

2- (4- {1- [4- (2-Methacryloyloxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethyl methacrylate,

2- {2- [4- (1- {4- [2- (2-Acryloyloxy-propoxy) -propoxy] -phenyl} -1-methyl-1-ethyl) -phenoxy] -1 -Methyl-ethoxy} -1-methyl-ethylacrylate,

2- {2- [4- (1- {4- [2- (2-Methacryloyloxy-propoxy) -propoxy] -phenyl} -1-methyl-1-ethyl) -phenoxy]- 1-methyl-ethoxy} -1-methyl-ethyl methacrylate,

3- {4- [1- (3- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenyl) -1-methyl Ethylphenoxy-2-hydroxy-propylacrylate,

3- {4- [1- (3- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenyl) -1- Methyl-ethylphenoxy-2-hydroxy-propylmethacrylate,

3- (4- {1- [4- (3-Acryloyloxy-2-hydroxy-propoxy) -3-cyclohexyl-phenyl] -1-methyl-ethyl} -2-cyclohexyl-phenoxy ) -2-hydroxy-2-propyl acrylate,

3- (4- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -3-cyclohexyl-phenyl] -1-methyl-ethyl} -2-cyclohexyl-phenoxy C) -2-hydroxy-2-propyl methacrylate,

3- (5- {1- [6- (3-acryloyloxy-2-hydroxy-propoxy) -biphenyl-3-yl] -1-methyl-ethyl} -biphenyl-2-yloxy ) -2-hydroxy-propyl acrylate,

3- (5- {1- [6- (3-Methacryloyloxy-2-hydroxy-propoxy) -biphenyl-3-yl] -1-methyl-ethyl} -biphenyl-2-yl jade C) -2-hydroxy-propyl methacrylate,

3- {4- [1- (4- {1- [4- (3-Acryloyloxy-2-hydroxy-propoxy) -3-methyl-phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethyl] -2-methyl-phenoxy} -2-hydroxy-propyl acrylate,

3- {4- [1- (4- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -3-methyl-phenyl] -1-methyl-ethyl} -phenyl ) -1-methyl-ethyl] -2-methyl-phenoxy} -2-hydroxy-propylmethacrylate,

3- (4- {1- [4- (3-Acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propylacrylate ,

3- (4- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propylmetha Acrylate,

3- [4- (1- {4- [3- (4- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl}- Phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propylacrylate,

3- [4- (1- {4- [3- (4- {1- [4- (3-methacryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -Phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propylmethacrylate,

3- {4- [1- (4- {3- [4- (1- {4- [3- (4- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) ) -Phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy} -2-hydroxy-propyl acrylate,

3- {4- [1- (4- {3- [4- (1- {4- [3- (4- {1- [4- (3-methacryloyloxy-2-hydroxy-pro Foxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propoxy] -phenyl } -1-methyl-ethyl) -phenoxy} -2-hydroxy-propylmethacrylate,

1- (2- {4- [1- (4- {2- [2-hydroxy-3- (1-methylene-aryloxy) -propoxy] -propoxy} -phenyl) -1-methyl-ethyl ] -Propoxy} -1-methyl-ethoxy) -3- (1-methylene-aryloxy) -propan-2-ol and the like;

As di (meth) acrylate which has a diphenylmethane structure, it is 4- (4-acryloyloxy-benzyl) -phenylacrylate,

4- (4-methacryloyloxy-benzyl) -phenylmethacrylate,

2- {4- [4- (2-acryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl acrylate,

2- {4- [4- (2-methacryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl methacrylate,

Diacrylates of ethylene oxide adducts of bisphenol F,

Dimethacrylate of ethylene oxide adducts of bisphenol F,

Diacrylates of propylene oxide adducts of bisphenol F,

Dimethacrylate of propylene oxide adducts of bisphenol F,

2- [2- (4- {4- [2- (2-Acryloyloxy-ethoxy) -ethoxy] -benzyl} -phenoxy) -ethoxy] -ethyl acrylate,

2- [2- (4- {4- [2- (2-Methacryloyloxy-ethoxy) -ethoxy] -benzyl} -phenoxy) -ethoxy] -ethyl methacrylate,

2- {4- [4- (2-acryloyloxy-propoxy) -benzyl-phenoxy} -1-methyl-ethylacrylate,

2- {4- [4- (2-methacryloyloxy-propoxy) -benzyl-phenoxy} -1-methyl-ethylmethacrylate,

2- [2- (4- {4- [2- (2-Acryloyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl-ethyl Ethyl acrylate,

2- [2- (4- {4- [2- (2-Methacryloyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl- Ethyl ethyl methacrylate and the like;

As di-thio (meth) acrylate which has a diphenylthio ether structure, it is 4- (4-thioacryloylsulfanyl- phenylsulfanyl) -phenyldithioacrylate,

4- (4-thiomethacryloylsulfanyl-phenylsulfanyl) -phenyldithiomethacrylate,

Bis (4-methacryloylthiophenyl) sulfide and the like;

As another (B) compound, 2, 5-bis {4- (3-acryloyloxy-propoxy)-benzoic acid} toluene etc. are mentioned, for example.

Such (B) compound can be synthesize | combined by combining suitably the method of organic chemistry, and can obtain it as a commercial item. As a commercial item of the (B) compound, for example, bishydroxyethoxy BP diacrylate and bishydroxyethoxy Bis-A diacrylate (manufactured by Honshu Chemical Co., Ltd.);

Aronix M-208 and Aronix M-210 (manufactured by Toagosei Co., Ltd.);

SR-349, SR-601, SR-602 (Sartomer Co., Ltd.);

KAYARAD R-712, KAYARAD R-551 (manufactured by Nippon Kayaku Co., Ltd.);

NK ester BPE-100, NK ester BPE-200, NK ester BPE-500, NK ester BPE-1300, NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Actilane 420 (Nihon Shiberhe Gner's Co., Ltd.);

LIGHT ESTER BP-2EM, LIGHT ACRYLATE BP-4EA, light acrylate BP-4PA, epoxy ester 3000M, epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.);

V # 540, V # 700 (manufactured by Osaka Yuki Chemical Co., Ltd.);

FA-321M (manufactured by Hitachi Chemical Co., Ltd.);

MPSMA (manufactured by Sumitomo Seka Co., Ltd.);

Ripoxy VR-77 (made by Showa Co., Ltd.) is mentioned.

As (B) compound used in this invention, it is preferable to use at least 1 sort (s) chosen from the group which consists of the compound illustrated above.

The use ratio of the (B) compound in the polymer composition used in this invention is 1-100 weight part with respect to 100 weight part of (A) polymer, and it is preferable to set it as 5-50 weight part.

[(C) radical scavengers]

The (C) radical scavenger in this invention is used in order to prevent the said (B) compound from causing undesirable crosslinking reaction in a coating film formation process.

As the (C) radical scavenger in the present invention, for example, a compound having at least one structure selected from the group consisting of a hindered phenol structure, a hindered amine structure, and a diphenylamine structure; Hydroquinone, a hydroquinone derivative, phenylnaphthylamine, etc. are mentioned.

As said hindered phenol structure, the structure represented by a following formula (C-1);

As said hindered amine structure, the structure represented by a following formula (C-2); And

As said diphenylamine structure, the structure represented by a following formula (C-3) is respectively preferable, and as a hydroquinone or its derivative, the compound represented by a following formula (C-4) can be illustrated preferably.

(In formula (C-1), R <^1> is t-butyl group, R <^2> is a hydrogen atom, a methyl group, t-butyl group, or a bond, R <^3> is a C1-C4 alkyl group, a is 0- An integer of 2;

In formula (C-4), R <^4> is a C1-C4 alkyl group, R <^5> is a hydrogen atom or a C1-C4 alkyl group, b is an integer of 0-4; And

"*" In said formula represents a bond.).

The structure represented by each of said Formula (C-1)-(C-3) may comprise a part of low molecular weight compound, and may comprise a part of side chain structure or terminal structure of a polymer. Examples of the main chain structure of the polymer include polyamic acid, polyamic acid ester, polyimide, polymaleimide, polystyrene, maleimide / styrene copolymer, polyester, polyamide, poly (meth) acrylate and polysiloxane, and among these. The block copolymer which consists of 2 or more types is mentioned. However, it is preferable that the structure represented by each of said Formula (C-1)-(C-3) comprises a part of comparatively low molecular weight compound (compound of about 3,000 or less as molecular weight).

Only one structure may be present in a molecule | numerator, and two or more may exist in a molecule | numerator represented by said Formula (C-1)-(C-3), respectively. However, the structure represented by said formula (C-1) has 1-4 in a molecule | numerator;

One or two structures represented by the above formula (C-2); And

It is preferable that there is only one structure represented by said formula (C-3) in a molecule, respectively.

Two or more types of structures represented by each of the formulas (C-1) to (C-3) may be mixed in one molecule.

As a compound which has one structure represented by said Formula (C-1) in a molecule | numerator, the bond loss in said Formula (C-1), for example, couple | bonded with the monovalent hydrocarbon group which may be interrupted by the ester bond in the middle. The compound can be mentioned. It is preferable that the total number of a carbon atom and an oxygen atom is 1-40, and, as for this monovalent hydrocarbon group, it is more preferable that it is 1-25. As a specific example of such a compound, the compound etc. which are represented by each of following formula (C-1-1)-(C-1-3) are mentioned, for example.

The compound which has two structures represented by said Formula (C-1) in a molecule | numerator can be classified into the following two aspects.

First, it is a case where two (C-1) structures are connected through the bonding hand which attached "*" among the bonding hands in said Formula (C-1). In this case, the linking group is a linking group consisting of a divalent hydrocarbon group which may be interrupted by one or more selected from an ester group, an ether group and an amide group, or an ether bond or an ester bond, and R ² is a methyl group or t It is preferable that it is a -butyl group. It is preferable that the number of the sum total of a carbon atom and a hetero atom (this hetero atom is the concept which does not contain a hydrogen atom, the same below) is 1-50, and, as for the said coupling group, it is more preferable that it is 1-30. As a specific example of such a compound, the compound etc. which are represented by each of following formula (C-1-4)-(C-1-8) are mentioned, for example.

2nd aspect is a case where R <^2> is a bond of the bond in the said Formula (C-1), and two (C-1) structures are connected through this. In this case, it is preferable that the coupling group is a C1-C10, preferably 1-3 alkylene group, and the bond which attached "*" is couple | bonded with a hydrogen atom or a C1-C4 alkyl group. As a specific example of such a compound, the compound etc. which are represented by each of following formula (C-1-9) and (C-1-10) are mentioned, for example.

As a compound which has three structures represented by said Formula (C-1) in a molecule | numerator, For example, the compound etc. which are represented by each of following formula (C-1-11) and (C-1-12);

As a compound which has four structures represented by said Formula (C-1) in a molecule | numerator, the compound etc. which are represented by following formula (C-1-13) are mentioned, respectively.

As a compound which has a structure represented by said Formula (C-2) in a molecule | numerator, the bond of the said Formula (C-2) is couple | bonded via the coupling group which consists of a bivalent hydrocarbon group which may be interrupted by the ester bond in the middle. The case may be mentioned. It is preferable that the total number of a carbon atom and a hetero atom is 1-30, and, as for the coupling group in this case, it is more preferable that it is 1-15. As a specific example of such a compound, the compound etc. which are represented by each of following formula (C-2-1) and (C-2-2) are mentioned, for example.

As a compound which has both a structure represented by said formula (C-1) in a molecule | numerator, and a structure represented by said formula (C-2), the compound etc. which are represented by following formula (C-12-1) are mentioned, for example. .

As a compound which has a structure represented by said formula (C-3), For example, bis (4-n-octylphenyl) amine etc .;

As a compound represented by said Formula (C-4), For example, hydroquinone, 4-methoxy phenol, 2-t- butyl hydroquinone etc .;

As phenylnaphthylamine, phenyl-1- naphthylamine etc. are mentioned, respectively.

The use ratio of the (C) radical scavenger in the liquid crystal aligning agent of this invention is 1-50 weight part with respect to 100 weight part of (A) polymers as mentioned above. It is preferable that it is 5-40 weight part with respect to 100 weight part of (A) polymers, and, as for this value, it is more preferable that it is 15-25 weight part.

It is preferable that it is 1-100 weight part with respect to 100 weight part of (B) compounds within the said range, and the use ratio of the (C) radical trapping agent in the liquid crystal aligning agent of this invention is 10-75 weight part It is more preferable, and it is still more preferable that it is 15-45 weight part.

[Polymer Composition]

It is preferable that the polymer composition used in this invention is prepared as a solution which melt | dissolved the above-mentioned (A) polymer, (B) compound, and (C) radical trapping agent in a suitable organic solvent.

As an organic solvent which can be used here, for example, 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, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutylke Tones, isoamyl propionate, isoamyl isobutylate, diisopentyl ether and the like.

As a usage ratio of an organic solvent, it is preferable to set it as the ratio which solid content concentration (the ratio which the total weight of components other than the organic solvent in a polymer composition occupies in the total weight of a polymer composition) of a polymer composition becomes 1 to 15 weight%, and it is 1.5 It is more preferable to set it as the ratio used as -8 weight%.

<Method of Manufacturing Liquid Crystal Display Element>

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

On the said conductive film of a pair of board | substrates which have a conductive film, the above-mentioned polymer composition is apply | coated, respectively, and a coating film is formed,

A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,

And a 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.

Here, as a board | substrate, For example, glass, such as float glass and a soda glass; A transparent substrate made of polyethylene such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used.

As the conductive film, a transparent conductive film is preferably used. For example, an NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO ₂ , and the like may be used. It is preferable that this conductive film is a patterned conductive film partitioned into a plurality of regions, respectively. With such a conductive film configuration, the direction of the pretilt angle of the liquid crystal molecules can be changed in each region by applying a different voltage for each region when applying a voltage between the conductive films (to be described later). It becomes possible to widen.

In order to apply | coat a polymer composition on the said electrically conductive film of such a board | substrate, it can be based on suitable coating methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, for example. After application | coating, the coating surface is formed by preheating (prebaking) and then baking (postbaking). Prebaking conditions are 0.1 to 5 minutes, for example at 40-120 degreeC. It is preferable to make post-baking temperature into 300 degreeC or less exceeding 150 degreeC, More preferably, it is 160-250 degreeC, It is preferable to set it as 170-200 degreeC especially. Post-baking time becomes like this. Preferably it is 5-200 minutes, More preferably, it is 10-100 minutes.

By setting it as such a postbaking condition, a solvent does not remain in the coating film formed and it is preferable at the point which can obtain the liquid crystal display element in which deterioration of the display performance resulting from a residual solvent is suppressed as much as possible.

The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

The coating film formed in this way may be used as it is for the manufacture of the liquid crystal cell of a next process, or you may perform a rubbing process with respect to a coating film surface as needed before manufacture of a liquid crystal cell. This rubbing treatment can be carried out by rubbing the coated film surface in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon or cotton. Here, as described in Patent Document 1 (Japanese Patent Laid-Open No. 5-107544), after a rubbing treatment is performed, a resist film is formed on a part of the coating film surface, and rubbing in a direction different from the previous rubbing treatment. By performing the process of removing a resist film after performing a process, and making it into a different rubbing direction for every area | region, it is possible to further improve the field-of-view characteristic of the liquid crystal display element obtained.

Subsequently, a pair of substrates on which the coating film is formed are disposed to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell.

As the liquid crystal molecules used herein, nematic liquid crystals having negative dielectric anisotropy are preferable, for example, dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, sifbase-based liquid crystals, subfamily clock liquid crystals, and biphenyl-based liquid crystals. A liquid crystal, a phenyl cyclohexane type liquid crystal, etc. can be used. It is preferable that the thickness of the layer of liquid crystal molecules shall be 1-5 micrometers.

In order to manufacture a liquid crystal cell using such a liquid crystal, the following two methods are mentioned, for example.

As a 1st method, two board | substrates are opposingly arranged through gap | interval (cell gap) so that each liquid crystal aligning film may oppose, the peripheral part of two board | substrates is joined using a sealing agent, and a board | substrate surface and a sealing agent After the liquid crystal is injected and filled into the cell gap partitioned by, the liquid crystal cell can be manufactured by sealing the injection hole. Or as a 2nd method, after apply | coating an ultraviolet-ray curable sealing compound, for example to the predetermined place on one of the two board | substrates with which the liquid crystal aligning film was formed, and further dropping a liquid crystal on the liquid crystal aligning film surface, Another liquid crystal cell can be manufactured by bonding another board | substrate so that a liquid crystal aligning film may oppose, and then irradiating an ultraviolet-ray to the whole surface of a board | substrate, and hardening a sealing compound.

Thereafter, 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 AC.

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. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

As an irradiation amount of light, Preferably it is 1,000 J / m <2> or less than 100,000 J / m <2>, More preferably, it is 1,000-50,000 J / m <2>. In the manufacture of the liquid crystal display element of the conventionally known PSA mode, it was necessary to irradiate about 100,000 J / m <2> light, but in the method of this invention, the light irradiation amount is 50,000 J / m <2> or less, even 10,000J / m <2> or less Even if it is set as desired, a desired liquid crystal display element can be obtained, and it can help to reduce the manufacturing cost of a liquid crystal display element, and can avoid the fall of the electrical characteristic resulting from strong light irradiation, and the fall of long-term reliability. .

And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above process. As a polarizing plate used here, the polarizing plate etc. which sandwiched the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself are mentioned.

(Example)

Synthesis Example 1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 43 g (0.40 mol) of p-phenylenediamine and 3- (3,5-diaminobenzoyloxy) as diamine 52 g (0.10 mol) of cholestan was dissolved in 830 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The solution viscosity measured as a small amount of the obtained polyamic acid solution, the addition of N-methyl- 2-pyrrolidone, and the solution of polyamic acid concentration of 10 weight% was 60 mPa * s.

Subsequently, 1,900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was substituted with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration ring closure reaction in this operation were removed to the outside of the system, which is the same below). A solution containing about 15% by weight of 50% polyimide (PI-1) was obtained. The obtained polyimide solution was fractionated and N-methyl-2-pyrrolidone was added and the solution viscosity measured as a solution of 10 weight% of polyimide concentration was 47 mPa * s.

Synthesis Example 2

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 11 g (0.10 mol) of p-phenylenediamine as diamine, 15 g (0.10 mol) of 3,5-diaminobenzoic acid 53 g (0.20 mole) and 3- (3,5-diaminobenzoyloxy), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine 52 g (0.10 mol) of cholestan was dissolved in 830 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. The solution viscosity measured as a small amount of the obtained polyamic-acid solution, the addition of N-methyl- 2-pyrrolidone, and making it the solution of 10 weight% of polyamic acid concentration was 52 mPa * s.

Subsequently, 1,900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone to obtain a solution containing about 15% by weight of polyimide (PI-2) having an imidization ratio of about 50%. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 35 mPa · s.

Example 1

<Preparation of a polymer composition>

(A) N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) are added to the solution containing the polyimide (PI-1) obtained by the said synthesis example 1 as a polymer, as an organic solvent, Furthermore, as a compound (B), following formula (B-1):

 20 parts by weight of the compound represented by (A) to 100 parts by weight of the polymer, and (C) 10 parts by weight of the compound represented by the formula (C-1-1) as the radical scavenger to 100 parts by weight of the polymer (A), respectively. In addition, the solvent composition set it as the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 8.0weight%. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

<Production and Evaluation of Liquid Crystal Cells>

Using the polymer composition prepared above, the pattern (two types) and ultraviolet irradiation amount (three levels) of a transparent electrode were changed, six liquid crystal display elements in total were manufactured, and the following evaluation was carried out.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

The polymer composition prepared above was 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 (manufactured by Nippon Shashin Inc.), and on a hotplate at 80 ° C. for 1 minute. After heating (prebaking) and removing a solvent, it heated (postbaking) for 10 minutes on the 180 degreeC hotplate, and formed the coating film of 600 kPa of average film thicknesses.

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 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 to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

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 one liquid crystal aligning film of the said pair of board | substrates, it overlaps and crimps | bonds so that a liquid crystal aligning film surface may face. The adhesive was cured. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern. One of them was used for evaluation of the pretilt angle mentioned later as it was. Each of the remaining two liquid crystal cells was subjected to light irradiation in the state where a voltage was applied between the conductive films by the following method, and then used for evaluation of the pretilt angle and long-term reliability (voltage holding ratio retention after storage).

Two of the liquid crystal cells obtained above were applied with alternating current 10V having a frequency of 60 Hz between the electrodes, respectively, and in the state where the liquid crystal was driven, the ultraviolet light was 10,000 J / using an ultraviolet irradiation device using a metal halide lamp as the light source. Irradiation was carried out at an irradiation dose of 2 m 2 or 100,000 J / m 2. In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference.

[Evaluation of Pretilt Angle]

About each liquid crystal cell manufactured above, Non-Patent Document 2 (TJ Schffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 3 (F. Nakano et al., JPN. Based on the method described in J. Appl. Phys. Vol. 19, p. 2013 (1980)), the value of the inclination angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using the He-Ne laser beam is free. Tilt angle was used.

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

[Evaluation of long-term reliability]

About each liquid crystal cell manufactured above, after applying the voltage of 5V at 23 degreeC in 60 microseconds application time and 167 milliseconds span, the voltage holding ratio (initial voltage preservation rate) 167 milliseconds after application | release cancellation was measured.

Subsequently, after storing each liquid crystal cell after the said initial voltage holding ratio measurement at 23 degreeC, respectively, 5,000 hours, the voltage holding ratio (voltage holding ratio after 5,000 hours) was measured again by said same method.

Table 2 shows the initial voltage holding ratios and the voltage holding ratios after 5,000 hours of the liquid crystal cells having an irradiation amount of 10,000 J / m 2 and the liquid crystal cells having an irradiation amount of 100,000 J / m 2. If the difference between them (the value obtained by subtracting the value (% unit) of the voltage holding ratio after 5,000 hours) from the value of the initial voltage holding ratio (% unit) is within 1% (point), the long-term reliability can be evaluated as good.

In the above description, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as the measuring device.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode]

The polymer composition prepared above is patterned in a slit shape as shown in FIG. 1 and has a liquid crystal aligning film printer (Nihonshashin Insatsu Co., Ltd.) on each electrode surface of glass substrates A and B each having an ITO electrode partitioned into a plurality of regions. Co., Ltd.) was applied, and the solvent was removed by heating (prebaking) for 1 minute on a hot plate at 80 ° C, and then heated (postbaking) for 10 minutes on a hot plate at 180 ° C to obtain an average film thickness of 600 kPa. Formed. About this coating film, after performing ultrasonic cleaning in ultrapure water for 1 minute, it dried in a 100 degreeC clean oven for 10 minutes, and the board | substrate which has a liquid crystal aligning film was obtained. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

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

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

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

[Evaluation of response speed]

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

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

Table 2 shows the response speeds of the non-irradiated liquid crystal cell, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2>, respectively.

Examples 2 to 26 and Comparative Examples 1 to 6

In Example 1, except that the kind and amount of the (A) polymer, the (B) compound and the (C) radical scavenger, and the postbaking temperature at the time of coating film formation were as described in Table 1, respectively, In the same manner as in 1, a polymer composition was prepared, and various liquid crystal cells were produced and evaluated using the same. The evaluation results are shown in Table 2.

In addition, the polymer composition used by the comparative example 6 is the same as that used by the comparative example 1.

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

[(B) COMPOUND]

B-1: the compound represented by said formula (B-1)

B-2: The mixture of compounds in which n is 2-4 in following formula (B-2)

[(C) radical scavengers]

C-1-1: the compound represented by said formula (C-1-1)

C-1-2: the compound represented by said formula (C-1-2)

C-1-3: compound represented by the above formula (C-1-3)

C-1-4: the compound represented by said formula (C-1-4)

C-1-5: the compound represented by said formula (C-1-5)

C-1-6: the compound represented by said formula (C-1-6)

C-1-7: the compound represented by said formula (C-1-7)

C-1-8: compound represented by the above formula (C-1-8)

C-1-9: compound represented by the above formula (C-1-9)

C-1-10: compound represented by the above formula (C-1-10)

C-1-11: the compound represented by said formula (C-1-11)

C-1-12: the compound represented by said formula (C-1-12)

C-1-13: the compound represented by said formula (C-1-13)

C-2-1: the compound represented by said formula (C-2-1)

C-2-2: the compound represented by said formula (C-2-2)

C-12-1: the compound represented by said formula (C-12-1)

C-3-1: bis (4-n-octylphenyl) amine

C-4-1: hydroquinone 2-t-butylhydroquinone

C-4-2: 4-methoxyphenol

C-4-3: 2-t-butylhydroquinone

C-5-1: Phenyl-1-naphthylamine

c-1: the compound represented by following formula (c-1)

c-2: the compound represented by a following formula (c-2)

In the comparative example 3, since the formed coating film did not have liquid crystal aligning ability, neither the pretilt angle of the liquid crystal cell which has a patternless electrode, and the response speed of the liquid crystal cell which has a patterned electrode could be measured.

From the results of Table 1 and Table 2, in the method of the present invention, when the ultraviolet irradiation amount is set to 100,000 J / m 2 (the value conventionally employed in the PSA mode), the degree of pretilt angle obtained is excessive, and 10,000 J / It turns out that it becomes an appropriate pretilt angle in the irradiation amount of m <2> or less. In addition, even when the irradiation amount was small, a sufficiently fast response speed was obtained, and the initial voltage holding ratio and the voltage holding ratio after 500 hours storage were also excellent.

Therefore, according to the method of the present invention, since the advantages of the PSA mode can be realized with a small amount of light irradiation, the viewing angle can be reduced without fear of occurrence of display unevenness due to the high light irradiation amount, deterioration of voltage integrity characteristics and lack of long-term reliability. A liquid crystal display device having a wide, fast response speed of liquid crystal molecules, high transmittance, and high contrast can be manufactured.

In addition, the various liquid crystal cells were produced and evaluated similarly to Example 1 except having changed the pattern of the ITO electrode which a glass substrate has using each polymer composition used in the said Examples 1-26. Also in the case of using any polymer composition, the same effects as in Examples 1 to 26 were obtained in both of the pattern shown in FIG. 2 and the pattern shown in FIG. 3.

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

Claims (9)

A process for producing a liquid crystal display device, characterized by the following process:
On the said conductive film of a pair of board | substrates which have a conductive film, respectively,
(A) 100 parts by weight of at least one polymer selected from the group consisting of polyamic acid and polyimide,
(B) 10 to 100 parts by weight of a compound having two or more polymerizable unsaturated bonds, and
(C) 1 to 50 parts by weight of radical scavenger
Applying a polymer composition containing, and then heating it to form a coating film,
Forming a liquid crystal cell by 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 layer of liquid crystal molecules;
Irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates. The method of claim 1,
Said (C) radical scavenger is a compound which has at least 1 sort (s) of structure chosen from the group which consists of a hindered phenol structure, a hindered amine structure, and a diphenylamine structure, or is a hydroquinone or its derivative, or phenyl naphthylamine. The manufacturing method of a liquid crystal display element. The method of claim 2,
The hindered phenol structure in the said (C) radical trapping agent is a structure represented by a following formula (C-1), a hindered amine structure is a structure represented by a following formula (C-2), and a diphenylamine structure is The manufacturing method of the liquid crystal display element which is a structure represented by Formula (C-3), and a hydroquinone or its derivative is a compound represented by following formula (C-4):

(In formula (C-1), R <^1> is t-butyl group, R <^2> is a hydrogen atom, a methyl group, t-butyl group, or a bond, R <^3> is a C1-C4 alkyl group, a is 0- An integer of 2;
In formula (C-4), R <^4> is a C1-C4 alkyl group, R <^5> is a hydrogen atom or a C1-C4 alkyl group, b is an integer of 0-4; And
"*" In said formula represents a bond.). The method of claim 1,
The compound (B) in the polymer composition is
In the molecule, the following formula (BI):
-X ¹ -Y ¹ -X ^2- (BI)
(In formula (BI), X <^1> and X <^2> are respectively independently a 1, 4- phenylene group or a ¹ , 4- cyclohexylene group, Y <^1> is a single bond and a C1-C4 bivalent hydrocarbon group. , An oxygen atom, a sulfur atom or -COO-, provided that X ¹ and X ² may be substituted with one or a plurality of C 1-4 alkyl groups, C 1-4 alkoxyl groups, fluorine atoms or cyano groups )
At least one of the divalent groups represented by the following formula (B-II):

(In formula (B-II), R is a hydrogen atom or a methyl group, and Y ² and Y ³ are each independently an oxygen atom or a sulfur atom.)
The manufacturing method of the liquid crystal display element which is a compound which has at least two of monovalent groups represented by these. 5. The method of claim 4,
The compound (B) is a di (meth) acrylate having a biphenyl structure, a di (meth) acrylate having a phenyl-cyclohexyl structure, a di (meth) acrylate having a 2,2-diphenylpropane structure, The manufacturing method of the liquid crystal display element which is at least 1 sort (s) of compound chosen from the group which consists of di (meth) acrylate which has a diphenylmethane structure, and di-thio (meth) acrylate which has a diphenylthioether structure. The method according to any one of claims 1 to 5,
A method for producing a liquid crystal display element, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions. As a polymer composition used for the manufacturing method of the liquid crystal display element of Claim 1,
(A) 100 parts by weight of at least one polymer selected from the group consisting of polyamic acid and polyimide,
(B) 10 to 100 parts by weight of a compound having two or more polymerizable unsaturated bonds, and
(C) 1 to 50 parts by weight of radical scavenger
The polymer composition characterized in that it contains. (A) 100 parts by weight of at least one polymer selected from the group consisting of polyamic acid and polyimide,
(B) 10 to 100 parts by weight of a compound having two or more polymerizable unsaturated bonds, and
(C) 1 to 50 parts by weight of radical scavenger
A polymer composition, comprising: It was manufactured by the manufacturing method of the liquid crystal display element in any one of Claims 1-5, The liquid crystal display element characterized by the above-mentioned.

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