JP2012194533A - Method for manufacturing liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a liquid crystal display element having a wide viewing angle, a fast response speed of liquid crystal molecules, excellent display characteristics and long-term reliability.SOLUTION: There is provided a method for manufacturing a liquid crystal display element, which comprises: a step of applying composition containing (A) at least one polymer selected from the group consisting of a polyamide, a polyvinyl alcohol derivative and a poly(meth)acrylate and (B) a polymer composition containing a polymerizable unsaturated compound to form a coating film on conductive films of a pair of substrates having the conductive films; a step of forming a liquid crystal cell by arranging oppositely the pair of substrates on which the coating films are formed so that the coating films oppose each other through a layer of liquid crystal molecules; and a step of irradiating light to the liquid crystal cell in a state that a voltage is applied between the conductive films having the pair of substrates.

Description

  The present invention relates to a method for manufacturing a liquid crystal display element. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having a wide viewing angle and a fast response speed.

Among liquid crystal display elements, an MVA (Multi-Domain Vertical Alignment) type panel conventionally known as a vertical alignment mode forms protrusions in the liquid crystal panel, thereby restricting the tilting direction of the liquid crystal molecules. The viewing angle is expanded. However, according to this method, the lack of transmittance and contrast due to the protrusions is unavoidable, and there is a problem that the response speed of the liquid crystal molecules is slow.
In recent years, a PSA (Polymer Sustained Alignment) mode has been proposed in order to solve the problems of the MVA type panel as described above. The PSA mode is a polymerizable compound in a gap between a pair of substrates composed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern, or between a pair of substrates composed of two substrates with a patterned conductive film. An attempt is made to control the alignment direction of the liquid crystal by expressing a pretilt angle characteristic by irradiating ultraviolet rays in a state where a voltage is applied between the conductive films while sandwiching the liquid crystal composition containing the liquid crystal and polymerizing the polymerizable compound. Technology. According to this technology, it is possible to increase the viewing angle and speed up the liquid crystal molecule response by making the conductive film into a specific configuration, and also solve the problem of lack of transmittance and contrast that was inevitable in the MVA type panel. Is done. However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet light, for example, 100,000 J / m ^2. It becomes clear that the reactive compounds remain in the liquid crystal layer, which together cause display unevenness, adversely affect the voltage holding characteristics, or cause problems in the long-term reliability of the panel.

On the other hand, Non-Patent Document 1 proposes a method using a liquid crystal alignment film formed from a polyimide liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, a liquid crystal display element including a liquid crystal alignment film formed by such a method is said to respond quickly to liquid crystal molecules. However, Non-Patent Document 1 does not provide any guidance on what kind of reactive mesogen should be used, and the amount of necessary ultraviolet irradiation is still large, and there are concerns about display characteristics, particularly voltage holding characteristics. Not wiped out.
By the way, in recent years, the tendency of the liquid crystal display element to increase in size is remarkable, and there is a demand for reducing the weight of the substrate that increases in size. In order to satisfy this, some attempts have been made to use synthetic resin substrates. However, since a liquid crystal alignment film material having a mesogen moiety as described in Non-Patent Document 1 has poor solubility, a specific high-boiling solvent (for example, N-methyl) is required to prepare this as a solution-like composition. -2-pyrrolidone) must be used. Such a liquid crystal aligning agent containing a high-boiling solvent needs to be heated at such a high temperature that the used high-boiling solvent is completely removed by evaporation in the solvent removal step or firing step after coating. Since this heating temperature sometimes exceeds the softening temperature of general-purpose resins, application of the resinous substrate in the PSA mode and its improved mode is hindered.

JP-A-5-107544 JP 2010-97188 A JP 2009-169224 A JP 2011-76065 A

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

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability. To do. Another object of the present invention is to provide a method for producing the above liquid crystal display element, preferably without requiring high-temperature heating.

According to the present invention, the above problem of the present invention is as follows.
On the conductive film of the pair of substrates having the conductive film,
(A) At least one polymer selected from the group consisting of polyamide, polyvinyl alcohol derivative, and poly (meth) acrylate, and (B) a polymer composition containing a polymerizable unsaturated compound, and a coating film Form the
A pair of substrates on which the coating film is formed are arranged to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell,
This is achieved by a method for manufacturing a liquid crystal display element, which includes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between conductive films of the pair of substrates.

The liquid crystal display device manufactured by the method of the present invention has a wide viewing angle, a high response speed of liquid crystal molecules, sufficient transmittance and contrast, excellent display specification, and display characteristics even when driven continuously for a long time. Will not be damaged. In addition, according to the method of the present invention, the amount of light required for irradiation can be reduced, which contributes to a reduction in manufacturing cost of the liquid crystal display element. Furthermore, since the polymer composition used in the method of the present invention does not require the use of a high boiling point solvent, according to a preferred embodiment of the present invention, it can be suitably applied to a resin substrate having poor heat resistance.
Therefore, the liquid crystal display device manufactured by the method of the present invention is superior to the conventionally known liquid crystal display device in both performance and cost, and can be suitably applied to various applications.

It is explanatory drawing which shows the pattern of the transparent conductive film in the liquid crystal cell which has the transparent transparent conductive film manufactured in 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 transparent transparent conductive film manufactured in the Example and the comparative example.

<Polymer composition>
The polymer composition used in the method of the present invention is:
(A) At least one polymer selected from the group consisting of polyamide, polyvinyl alcohol derivative and poly (meth) acrylate, and (B) a polymerizable unsaturated compound.
[(A) Polymer]
(A) The polymer is a polymer selected from polyamide, polyvinyl alcohol derivative and poly (meth) acrylate, preferably a group having a steroid structure, the following formula (A-0)

(In Formula (A-0), a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time, and c is an integer of 1 to 20. )
A group having 4 to 40 carbon atoms (excluding the case where it is included in the group represented by the above formula (A-0)) and a fluoroalkyl group having 4 to 40 carbon atoms. At least one group selected from (hereinafter referred to as “pretilt angle-expressing group”). (A) It is preferable in that the polymer has a pretilt angle developing group, so that the response speed of the liquid crystal becomes higher.
Examples of the group having a steroid structure in the pretilt angle-expressing group include a 3-cholestanyl group, a 3-cholestenyl group, a 3- (7-dehydro) cholestenyl group, and a 3-lanostannyl group.
Specific examples of the group C _c H _{2c + 1} — in the above formula (A-0) include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl. Group, 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-octadecyl group Group, n-nonadecyl group, n-eicosyl group (in the above, "n-" represents a straight chain). Specific examples of the group represented by the above formula (A-0) include, for example, the following formulas (A-0-1) and (A-0-2):

(In the above formula, n-C ₅ H ₁₁ -and n-C ₇ H ₁₅ -represent a linear pentyl group and a linear heptyl group, respectively.)
And groups represented by each of the above.
The alkyl group having 4 to 40 carbon atoms (excluding the case where it is included in the group represented by the above formula (A-0)) is preferably a straight chain, particularly a straight chain having 8 to 20 carbon atoms. Chain alkyl groups are preferred.
As said C4-C40 fluoroalkyl group, a linear thing is preferable. Specific examples of the fluoroalkyl group that is a pretilt angle-expressing group include a 3- (trifluoromethyl) propyl group and a 4- (trifluoromethyl) butyl group.
The polymer (A) in the present invention preferably has the pretilt angle-expressing group as described above at a ratio of 0.05 to 0.7 mmol / g-polymer, preferably 0.1 to 0.5 mmol. It is more preferable to have a ratio of / g-polymer.

-Polyamide-
The polyamide in the present invention can be obtained by polycondensation reaction of dicarboxylic acid or dicarboxylic acid halide and diamine.
The polyamide in the present invention preferably has a pretilt angle developing group as described above. A polyamide having a pretilt angle-expressing group can be obtained, for example, by subjecting a dicarboxylic acid or a dicarboxylic acid halide and a diamine having a pretilt angle-expressing group to a polycondensation reaction.
Examples of the dicarboxylic acid used for synthesizing the polyamide in the present invention include oxalic acid, aliphatic dicarboxylic acid, dicarboxylic acid having an alicyclic structure, dicarboxylic acid having an aromatic ring, alicyclic structure, and aromatic ring. The dicarboxylic acid which has both of these can be mentioned.
Examples of the aliphatic dicarboxylic acid include dicarboxylic acid in which two carboxy groups are bonded to a saturated hydrocarbon group having 1 to 20 carbon atoms, and two carboxy groups are bonded to an unsaturated hydrocarbon group having 2 to 20 carbon atoms. Mention may be made of dicarboxylic acids. Examples of the former include, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid , Azelaic acid, sebacic acid, suberic acid, etc .;
Examples of the latter include fumaric acid and muconic acid, for example. Of these, dicarboxylic acids in which two carboxy groups are bonded to a saturated hydrocarbon group having 1 to 12 carbon atoms are preferred.

  Examples of the dicarboxylic acid having the alicyclic structure include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3. -Cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclo Pentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene- 2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1 4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic Acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3.3] heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid and the like;

Examples of the dicarboxylic acid having an aromatic ring include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2, 5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 ″ -terphenyl dicarboxylic acid, 4,4 ′ -Diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid 4,4′-diphenylpropanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-bibenzyldicarboxylic acid, 4,4′-stilbenedicarboxylic acid 4,4′-transicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3 ′ -P-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 '-[4,4'-(methylenedi-p-phenylene)] dipropionic acid, 4,4 '-[ 4,4 ′-(oxydi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi-p-phenylene)] dibutyric acid, (isopropylidene di- -Phenylenedioxy) dibutyric acid, bis (p-carboxyphenyl) dimethylsilane, 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl -4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2 , 4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 3,6-pyridinedicarboxylic acid and the like;

Examples of the dicarboxylic acid having both the alicyclic structure and the aromatic ring include 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, and 3,4. Examples thereof include -bis (2-hydroxyphenyl) -1,2-cyclobutanedicarboxylic acid, 2,4-bis (2-hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid, and the like.
Among these, it is preferable to use one or more selected from the group consisting of oxalic acid and aliphatic dicarboxylic acids.
Examples of the dicarboxylic acid halide include chloride, bromide and iodide of the dicarboxylic acid as exemplified above, and in particular, one or more selected from the group consisting of oxalic acid and aliphatic dicarboxylic acid. Preference is given to using chloride or bromide.

Examples of the diamine used for synthesizing the polyamide in the present invention include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane.
The diamine used for synthesizing the polyamide in the present invention preferably contains a diamine having a pretilt angle developing group. The diamine having a pretilt angle developing group is preferably an aromatic diamine having a pretilt angle developing group. Specific examples thereof include dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, and the like. Pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2, 5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholesta Ruoxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6 -Bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 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, Serial formula (A-1)

(In the formula (A-1), X ^I and X ^II are each a single bond, ^* —O—, ^* —COO— or ^* —OCO— (where the bond marked with “*” is the formula (A -I) is directed to the left, and R ^I is a single bond, a methylene group or an alkylene group having 2 or 3 carbon atoms, and a, b and c are each in the above formula (A-0). Means the same as
The compound etc. which are represented by these can be mentioned.
The formula ^{(A-1) X I -R} I -X II in - a divalent methylene group as a group, an alkylene group having 2 or 3 carbon atoms ^represented, * ^-O-, * -COO- or ^* It is preferably —O—CH ₂ CH ₂ —O— (wherein a bond marked with “*” is bonded to a diaminophenyl group). The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.
Specific examples of the compound represented by the formula (A-1) include, for example, the following formulas (A-1-1-1), (A-1-1-2), and (A-1-2).

(In the above formula, n-C ₅ H ₁₁ -and n-C ₇ H ₁₅ -represent a linear pentyl group and a linear heptyl group, respectively.)
It is preferable that it is a compound represented by each of these.
Among the above, the diamine having a pretilt angle-expressing group includes hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate and the above formula (A- It is preferable to use one or more selected from the group consisting of compounds represented by 1).
The diamine used for synthesizing the polyamide in the present invention may be composed only of a diamine having a pretilt angle developing group, or may have a diamine having a pretilt angle developing group and a pretilt angle developing group. It may be a mixture with diamine not to be used. Examples of the diamine having no pretilt angle-expressing group include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes that do not have a pretilt angle-expressing group.

Among the diamines having no pretilt angle-expressing group, examples of the aliphatic diamine include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;
Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like;

Examples of aromatic diamines having no pretilt angle-expressing group include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, 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′-diaminodiphenyl 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) Xafluoropropane, 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) -pipe Gin, 3,5-diaminobenzoic acid, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5 -Diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholine- 4-yl) benzene-1,3-diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene and the like;

Examples of the diaminoorganosiloxane having no pretilt angle-expressing group include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, respectively.
The diamine described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188) can be used.
Examples of the diamine having no pretilt angle-expressing group include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2, 2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,4-bis- (4-aminophenyl)- It is preferably at least one selected from the group consisting of piperazine and 3,5-diaminobenzoic acid.

The diamine used for synthesizing the polyamide in the present invention preferably contains 1 mol% or more, more preferably 5 to 40 mol% of the diamine having a pretilt angle developing group with respect to the total amount of the diamine. 10 to 30 mol% is more preferable.
The polyamide in the present invention can be synthesized by subjecting the above dicarboxylic acid or dicarboxylic acid halide and diamine to a polycondensation reaction, preferably in the presence of a suitable condensing agent, and preferably in a suitable solvent. it can.
The use ratio of dicarboxylic acid or dicarboxylic acid halide and diamine is preferably 0.9 to 1.1 mol, more preferably as the use ratio of diamine to 1 mol of dicarboxylic acid or dicarboxylic acid halide. 0.95 to 1.05 mol.

The preferred condensing agent depends on whether a dicarboxylic acid or a dicarboxylic acid halide is used. When a dicarboxylic acid is used as the condensing agent, for example, (PhO) ₃ P, (PhO) PCl ₂ , PhPOCl ₂ , (C ₃ H ₇ ) ₃ P (O) O, POCl ₃ , SOCl ₂ / Et ₃ N, Ph ₃ P / C ₂ Cl ₆ , SiCl ₄ , Me ₂ SiCl ₂ etc. are preferably used;
On the other hand, when a dicarboxylic acid halide is used, for example, triethylamine, pyridine, N, N-dimethylaniline and the like are preferably used. The use ratio of the condensing agent is preferably 200 to 400 parts by weight, and more preferably 220 to 300 parts by weight with respect to 100 parts by weight of the dicarboxylic acid halide.
As the solvent, an organic solvent is preferably used. For example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be suitably used. The use ratio of the solvent is preferably 400 to 900 parts by weight, and more preferably 500 to 700 parts by weight with respect to 100 parts by weight of the total of dicarboxylic acid or dicarboxylic acid halide and diamine.
The temperature of the polycondensation reaction is preferably 25 to 200 ° C, more preferably 60 to 100 ° C. The time for the polycondensation reaction is preferably 2 to 10 hours, and more preferably 3 to 6 hours.
The polyamide in the present invention can be synthesized as described above. The polyamide thus synthesized is preferably used after being purified by a known method.

-Polyvinyl alcohol derivative-
The polyvinyl alcohol derivative in the present invention is selected from, for example, polyvinyl alcohol, a vinyl alcohol / ethylene copolymer, and a polymer obtained by modifying them, and preferably has a pretilt angle developing group described above. .
Polyvinyl alcohol can be obtained by polymerizing vinyl acetate and then saponifying the ester bond. A vinyl alcohol / ethylene copolymer can be obtained by copolymerizing vinyl acetate and ethylene and then saponifying the ester bond of a repeating unit derived from vinyl acetate. A polyvinyl alcohol derivative having a pretilt angle-expressing group is, for example, a compound in which at least one hydrogen atom of vinyl acetate is substituted with a group having a pretilt angle-expressing group (hereinafter referred to as “pretilt angle-expressing group-substituted vinyl acetate”). ") Is homopolymerized (Method 1);
A method of saponifying an ester bond of a repeating unit derived from vinyl acetate after (co) polymerizing a pretilt angle expressing group-substituted vinyl acetate and at least one mixture selected from the group consisting of vinyl acetate and ethylene (Method 2) ); Or a method in which polyvinyl alcohol or a vinyl alcohol / ethylene copolymer is first synthesized, and then a group having a pretilt angle-expressing group is added to the polymer afterwards using the reactivity of the hydroxyl group formed after saponification. (Method 3) and the like can be synthesized.

The pretilt angle-expressing group-substituted vinyl acetate used in the above methods 1 and 2 is, for example, an alcohol having a pretilt angle-expressing group is firstly trifluoromethanesulfonate, which is converted into a C = C double of vinyl acetate under Heck reaction conditions. It can be synthesized by a method of adding to bonded carbon.
In Method 2, the pretilt angle-expressing group-substituted vinyl acetate is preferably used in an amount of 2 mol% or more, more preferably 2 to 60 mol%, and more preferably 5 to 40 mol% based on all monomers. Is more preferable, and it is particularly preferable to use 10 to 30 mol%. In Method 3, vinyl acetate is preferably used in an amount of 10 mol% or more, more preferably 20 to 90 mol%, based on all monomers.
Homopolymerization of pretilt angle-expressing group-substituted vinyl acetate in Method 1 above, copolymerization of pretilt angle-expressing group-substituted vinyl acetate in Method 2 with at least one selected from the group consisting of vinyl acetate and ethylene, and Method 3 The homopolymerization of vinyl acetate for obtaining polyvinyl alcohol and the copolymerization of vinyl acetate and ethylene for obtaining vinyl alcohol / ethylene copolymer can be carried out by known radical polymerization methods, respectively.

As this radical polymerization method, for example, an appropriate method such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like can be adopted.
When radical polymerization is performed by a solution polymerization method, the desired monomer or monomer mixture is preferably added at a temperature of 50 to 150 ° C., more preferably 60 to 100 ° C. in the presence of a suitable solvent and a radical polymerization initiator. Accordingly, the desired polymer or copolymer can be obtained by stirring while supplying ethylene.
Examples of the solvent include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone and ester. Can be mentioned. As a solvent in radical polymerization, it is preferable to use alcohols such as methanol, ethanol and isobutyl alcohol. The use ratio of the solvent is preferably 100 to 900 parts by weight, and more preferably 600 to 800 parts by weight with respect to 100 parts by weight of the total amount of monomers.

Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylpareronitrile, azobis (4-methoxy-2,4-dimethylpareronitrile);
Peroxides such as acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate;
Percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate;
perester compounds such as t-butylperoxyneodecanate, α-cumylperoxyneodecanate, t-butylperoxyneodecanate;
Other radical polymerization initiators such as azobisdimethylvaleronitrile and azobismethoxyvaleronitrile can be listed. The use ratio of the radical polymerization initiator is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of monomers.
The time for radical polymerization is preferably 2 to 10 hours, and more preferably 3 to 5 hours.
After the polymerization, it is preferable to stop the polymerization by cooling the polymerization reaction system to a low temperature. The low temperature for stopping the polymerization may be, for example, 10 ° C. or more and less than 50 ° C., and preferably 20 to 40 ° C.

Saponification performed following the above polymerization can be performed by placing the obtained (co) polymer under alkaline conditions. For this purpose, the (co) polymer is preferably brought into contact with an alkaline compound in a suitable solvent.
Examples of the solvent used for saponification include alcohol. Specific examples thereof include methanol, ethanol, butanol and the like. The use ratio of the solvent is preferably 25 to 900 parts by weight, more preferably 50 to 600 parts by weight with respect to 100 parts by weight of the (co) polymer.
Examples of the alkaline compound used for the saponification include alkali metal hydroxides such as sodium hydroxide, sodium methylate, sodium ethylate, and potassium methylate; alkaline catalysts such as alcoholate. The use ratio of the alkaline compound is preferably 0.001 to 0.01 mol, and preferably 0.002 to 0.008 mol with respect to 1 mol of the vinyl acetate unit of the (co) polymer. More preferred.
The saponification temperature is preferably 10 to 70 ° C, more preferably 30 to 40 ° C. The saponification time is preferably 0.5 to 4 hours, more preferably 1 to 2 hours.
Depending on the composition of the (co) polymer, the saponification reaction system may gel during the saponification process. In such a case, it is preferable to continue the saponification reaction after pulverizing the entire reaction system with an appropriate pulverizer.
After the saponification reaction, it is desirable to neutralize the reaction system with a suitable neutralizing agent. Examples of the neutralizing agent used here include hydrochloric acid and an aqueous ammonium chloride solution. Neutralization is preferably performed under a pH value of 5 to 9, more preferably 6 to 8. The neutralization temperature is preferably 15 to 40 ° C, and more preferably 20 to 30 ° C.

In Method 1 and Method 2, the preferred polyvinyl alcohol derivative in the present invention can be obtained by the method as described above.
In Method 3, polyvinyl alcohol or a vinyl alcohol / ethylene copolymer, which is a preferred precursor polymer of the polyvinyl alcohol derivative in the present invention, can be obtained by the method as described above. In Method 3, a preferred polyvinyl alcohol derivative in the present invention can be obtained by adding a group having a pretilt angle-expressing group to this polyvinyl alcohol or vinyl alcohol / ethylene copolymer (precursor polymer). More specifically, first, a compound having a pretilt angle-expressing group and a carboxyl group (hereinafter referred to as “pretilt angle-expressing carboxylic acid”) is converted into an acid halide with an appropriate halogenating agent, The acid halide and the precursor polymer can be synthesized by an esterification reaction, preferably in the presence of an appropriate condensing agent, and preferably in an appropriate solvent.

  Examples of the pretilt angle-expressing carboxylic acid include a group having a steroid structure, a group represented by the above formula (A-0), and an alkyl group having 4 to 40 carbon atoms (however, represented by the above formula (A-0)). Or a carboxylic acid having a fluoroalkyl group having 4 to 40 carbon atoms, and specific examples thereof include, for example, mono (3- (7-dehydro) cholesteryl) succinate. The following formulas (5-1) to (5-8)

And the like, and the like.
As the halogenating agent, it is preferable to use an acid chloride, as a specific example, for example _{(PhO) PCl 2, PhPOCl 2} , POCl 3, SOCl 2 / Et 3 N, Ph 3 P / C 2 Cl 6 , SiCl ₄ , Me ₂ SiCl ₂ (in the above, Ph is a phenyl group, Et is an ethyl group, and Me is a methyl group). The ratio of the halogenating agent to be used is preferably 2 to 10 parts by weight, more preferably 3 to 6 parts by weight with respect to 100 parts by weight of the pretilt angle-expressing carboxylic acid. This halogenation reaction is preferably carried out in the presence of a suitable solvent such as dichloromethane, chloroform, N, N-dimethylformamide, etc., for example at 20 to 100 ° C., preferably at 40 to 80 ° C., for example for 0.5 to 5 hours. , Preferably it can be performed for 1 to 2 hours.

The usage ratio of the precursor polymer and the halide of the pretilt angle-expressing carboxylic acid is preferably 0.9 as the ratio of the halide of the pretilt angle-expressing carboxylic acid to 1 mol of the vinyl alcohol unit of the precursor polymer. It is -1.1 mol, More preferably, it is 0.95-1.05 mol.
As the condensing agent, for example, triethylamine, pyridine, N, N-dimethylaniline and the like are preferably used. The use ratio of the condensing agent is preferably 200 to 400 parts by weight, more preferably 220 to 300 parts by weight with respect to 100 parts by weight of the halide.
As the solvent, an organic solvent is preferably used. For example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be suitably used. The use ratio of the solvent is preferably 400 to 900 parts by weight, more preferably 500 to 700 parts by weight with respect to 100 parts by weight in total of the precursor polymer and the pretilt angle-expressing carboxylic acid halide. preferable.
The temperature of the esterification reaction is preferably 35 to 200 ° C, and more preferably 50 to 100 ° C. The time for the esterification reaction is preferably 3 to 10 hours, and more preferably 3 to 6 hours.
As described above, a desired polyvinyl alcohol derivative can be synthesized. The polyvinyl alcohol derivative synthesized as described above is preferably used after being purified by a known method.

-Poly (meth) acrylate-
The poly (meth) acrylate in the present invention is a homopolymer or copolymer of (meth) acrylate, or can be a copolymer of (meth) acrylate and another copolymerizable monomer, Has the pretilt angle developing group described above.
Here, (meth) acrylate is a concept including both acrylate and methacrylate. Similarly, (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid.
The poly (meth) acrylate having a pretilt angle-expressing group is, for example, a homopolymer of (meth) acrylate having a pretilt angle-expressing group, or a (meth) acrylate having a pretilt angle-expressing group, and the others It can be a copolymer with other copolymerizable monomers. Here, examples of the other copolymerizable monomer include (meth) acrylate, (meth) acrylic acid, a maleimide compound, and a vinyl aromatic compound that do not have a pretilt angle developing group. Examples of the (meth) acrylate having no pretilt angle developing group include (meth) acrylates having a cyclic ether structure and other (meth) acrylates having no other pretilt angle developing group.

Examples of the (meth) acrylate having a pretilt-expressing group include 3-cholestanyl (meth) acrylate, 3-cholestenyl (meth) acrylate, 3-ergostenyl (meth) acrylate, 3-ergostanyl (meth) acrylate, and 3-stigmastenyl. Examples include (meth) acrylate, 3-stigmasteryl (meth) acrylate, n-octadecyl (meth) acrylate, 4- (4-n-heptyl-cyclohexyl) phenyl (meth) acrylate, and the like. More than seeds can be used.
Examples of the (meth) acrylate having the cyclic ether structure include glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (3,4-epoxycyclohexyl) propyl (meth) acrylate, and the like;
Examples of other (meth) acrylates having no pretilt angle developing group include methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) ) Acrylate, benzyl (meth) acrylate, etc .;
Examples of the maleimide compound include N-phenylmaleimide and N-cyclohexylmaleimide;
Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, indene, p-hydroxystyrene, and the like, and one kind selected from these and (meth) acrylic acid. Besides being able to use more,
You may use the monomer described in patent document 3 (Unexamined-Japanese-Patent No. 2009-169224).
In the synthesis of the poly (meth) acrylate in the present invention, the proportion of the poly (meth) acrylate having a pretilt angle-expressing group is preferably 2 mol% or more based on the total monomers. It is more preferably 60 mol%, further preferably 5 to 40 mol%, and particularly preferably 10 to 30 mol%.

The poly (meth) acrylate in the present invention can be obtained by a known radical reaction method using the above monomers.
The synthesis of the poly (meth) acrylate in the present invention can be carried out by radical polymerization of the above monomers, preferably in the presence of a suitable polymerization initiator, preferably in a suitable solvent.
As the polymerization initiator, those generally known as radical polymerization initiators can be used without limitation. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2, Azo compounds such as 4-dimethylvaleronitrile) and 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile);
Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane;
Hydrogen peroxide or the like can be used.
Examples of the solvent include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, Esters can be used, and among these, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether. Propylene glycol ethyl ether, it is preferred to use propylene glycol methyl ether acetate or methyl 3-methoxypropionate.
The poly (meth) acrylate synthesized as described above may be used after being purified by a known method.

-(A) polymer-
The (A) polymer in the present invention is at least one selected from the group consisting of the above polyamide, polyvinyl alcohol derivative and poly (meth) acrylate. Two or more of these polymers may be mixed and used.
As the polymer (A) in the present invention, polyamide, polyvinyl alcohol derivative or poly (meth) acrylate is used alone, or one of these is mixed with another polymer described later. It is preferable to do.
[(B) polymerizable unsaturated compound]
The polymerizable unsaturated compound (B) used in the present invention is a group having a polymerizable carbon-carbon double bond, and preferably has the following formula (BI) in the molecule.

(In formula (BI), 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 compound (B-1) which has at least 2 of the monovalent group represented by these is included.
The number of monovalent groups represented by the formula (B-II) in the compound (B-1) is preferably two. Y ² in the above formula (B-II) is preferably an oxygen atom.
Compound (B-1) has the following formula (B-II) in the molecule:
^{-X 1 -Y 1 -X 2 - (} B-II)
(In Formula (B-II), X ¹ and X ² are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and Y ¹ is a single bond having 1 to 4 carbon atoms. A divalent hydrocarbon group, an oxygen atom, a sulfur atom or —COO—, wherein X ¹ and X ² are one or more alkyl groups having 1 to 4 carbon atoms and alkoxyl groups having 1 to 4 carbon atoms. , May be substituted with a fluorine atom or a cyano group.)
It is preferable that it further includes at least one divalent group represented by the divalent group represented by
Examples of the divalent hydrocarbon group having 1 to 4 carbon atoms in the above formula (B-II) include a methylene group and a dimethylmethylene group. Examples of the divalent group represented by the formula (B-II) include the following formulas (B-II-1) to (B-II-6):

And groups represented by each of the above. In each of the above formulas (B-II-1) to (B-II-6), the benzene ring and the cyclohexane ring are respectively an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a fluorine atom, or It may be substituted with a cyano group.
As the compound (B-1) used in the present invention,
Di (meth) acrylate having a biphenyl structure (Y ² and Y ³ in the formula (BI) are each an oxygen atom, and the divalent group represented by the formula (B-II) is (A group represented by (B-II-1)).
Di (meth) acrylate having a phenyl-cyclohexyl structure (Y ² and Y ³ in the above formula (BI) are each an oxygen atom, and a divalent group represented by the above formula (B-II) is A group represented by the above formula (B-II-2)).
Di (meth) acrylate having a 2,2-diphenylpropane structure (Y ² and Y ³ in the above formula (BI) are each an oxygen atom and are represented by the above formula (B-II). Is a group represented by the above formula (B-II-3)).
Di (meth) acrylate having a diphenylmethane structure (Y ² and Y ³ in the above formula (BI) are each an oxygen atom, and the divalent group represented by the above formula (B-II) is the above formula. (A group represented by (B-II-4)) and a di-thio (meth) acrylate having a diphenylthioether structure (Y ² in the above formula (BI) is an oxygen atom, and Y ³ is sulfur. And a divalent group represented by the above formula (B-II) is a group represented by the above formula (B-II-5)) and other compounds (B-1)
Can be mentioned.

Specific examples thereof include di (meth) acrylate having a biphenyl structure, such as 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,
Diacrylate of biphenyl ethylene oxide adduct,
Dimethacrylate of biphenyl ethylene oxide adduct,
Diacrylate of biphenyl propylene oxide adduct,
Dimethacrylate of propylene oxide adduct of biphenyl, etc .;
Examples of di (meth) acrylate having a phenyl-cyclohexyl structure include 4- (4-acryloyloxy-phenyl) -cyclohexyl acrylate,
4- (4-methacryloyloxy-phenyl) -cyclohexyl methacrylate, etc .;

As a di (meth) acrylate having a 2,2-diphenylpropane structure, for example, 4- [1- (4-acryloyloxy-phenyl) -1-methyl-ethyl] -phenyl acrylate,
4- [1- (4-methacryloyloxy-phenyl) -1-methyl-ethyl] -phenyl methacrylate,
Diacrylate of ethylene oxide adduct of bisphenol A,
Dimethacrylate of ethylene oxide adduct of bisphenol A,
Diacrylate of propylene oxide adduct of bisphenol A,
Dimethacrylate of propylene oxide adduct of bisphenol A, etc .;
As di (meth) acrylate having a diphenylmethane structure, for example, diacrylate of ethylene oxide adduct of bisphenol F,
Dimethacrylate of ethylene oxide adduct of bisphenol F,
Diacrylate of propylene oxide adduct of bisphenol F,
Dimethacrylate of propylene oxide adduct of bisphenol F;
Examples of the other compound (B-1) include 2,5-bis {4- (3-acryloyloxy-propoxy) -benzoic acid} toluene and the like, respectively, and Patent Document 4 (Japanese Patent Laid-Open No. 2011-76065). No.) can be used.

The compound (B-1) as described above can be synthesized by appropriately combining organic chemistry methods, or can be obtained as a commercial product. Examples of commercially available compounds (B-1) include bishydroxyethoxy BP diacrylate and bishydroxyethoxy Bis-A diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.);
Aronix M-208, M-210 (manufactured by Toagosei Co., Ltd.);
SR-349, SR-601, SR-602 (manufactured by Sartomer);
KAYARAD R-712, 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 (manufactured by Nippon Shibel Hegner 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 Organic Chemical Industry Co., Ltd.);
FA-321M (manufactured by Hitachi Chemical Co., Ltd.);
MPSMA (manufactured by Sumitomo Seika);
Lipoxy VR-77 (manufactured by Showa Polymer Co., Ltd.) can be exemplified.
As the compound (B-1) used in the present invention, it is preferable to use at least one selected from the group consisting of the compounds exemplified above.

(B) As a polymerizable unsaturated compound, only a compound (B-1) may be used and a compound (B-1) and another unsaturated compound may be used together.
The other unsaturated compounds can be contained in the polymer composition of the present invention for the purpose of bringing the pretilt angle closer to 90 ° and thereby more effectively expressing the desired effect of the present application. Such other unsaturated compound is preferably a compound having one carbon-carbon double bond, more preferably one of the carbon-carbon double bonds and the above formula (A-1). And a group. Specific examples of such other unsaturated compounds include, for example, methacrylic acid-5ξ-cholestan-3-yl, methacrylic acid 4- (4′-phenyl-bicyclohexyl-4-yl) phenyl ester, and the like. it can.
(B) As a polymerizable unsaturated compound, when using another unsaturated compound with a compound (B-1), as the use ratio, it is 80 weight% or less with respect to the whole quantity of (B) polymerizable unsaturated compound. It is preferable that the content is 50% by weight or less. The other unsaturated compound can exhibit its expected effect by using 2% by weight or more of the unsaturated compound (B) based on the total amount of the polymerizable unsaturated compound.
The proportion of the polymerizable unsaturated compound (B) used in the polymer composition used in the present invention is the sum of the polymers (the sum of the polymer (A) and other polymers that are optionally used as described later). It is preferable to set it as 1-100 weight part with respect to 100 weight part of the following.

[Other ingredients]
The polymer composition used in the present invention comprises the (A) polymer and the (B) polymerizable unsaturated compound as essential components as described above, but other than these, other effects may be used as long as the effects of the present invention are not diminished. It may contain components. Examples of other components that can be used here include other polymers, photopolymerization initiators, radical scavengers, and light stabilizers.

-Other polymers-
Said other polymer can be contained in the polymer composition in this invention for the purpose of improving the electrical property of the coating film obtained more.
The other polymer is a polymer other than the polymer (A), and can be one or more selected from polymers other than polyamide, polyvinyl alcohol derivative and poly (meth) acrylate. Specific examples of the other polymer include, for example, polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, cellulose derivative, polyacetal, and polystyrene derivative (excluding cases corresponding to (A) polymer). Examples thereof include poly (styrene-phenylmaleimide) derivatives. When other polymer is used, it is preferable to use at least one selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane as the other polymer, from the group consisting of polyamic acid and polyimide. It is more preferable to use one or more selected.
When the polymer composition in the present invention contains another polymer, the ratio is preferably 50% by weight or less, and preferably 30% by weight or less, with respect to the total of the polymers. More preferred.

-Photopolymerization initiator-
The said photoinitiator can be contained in the polymer composition in this invention for the purpose of making the response speed of the liquid crystal display element obtained higher.
Examples of the photopolymerization initiator include α-diketone, acyloin, acyloin ether, benzophenone compound, acetophenone compound, quinone compound, halogen compound, acylphosphine oxide, and organic peroxide. Specific examples thereof include α-diketone such as benzyl and diacetyl;
For example, benzoin as acyloin;
Examples of acyloin ethers include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;
Examples of benzophenone compounds include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, phenyl- (4- p-tolylsulfanyl-phenyl) -methanone and the like;
Examples of the acetophenone compound include acetophenone, p-dimethylaminoacetophenone, 4- (α, α′-dimethoxyacetoxy) benzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-2-morpholino- 1- (4-methylthiophenyl) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like;
Examples of quinone compounds include anthraquinone and 1,4-naphthoquinone;
Examples of halogen compounds include phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine, and the like;
Examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) phenyl. Phosphine oxide, etc .;
Examples of the organic peroxide include di-t-butyl peroxide, and one or more selected from these can be used.

Commercially available products may be used as the photopolymerization initiator. For example, IRGACURE-124, -149, -184, -369, -500, -651, -819, -907, and -1000 -1700, -1800, -1850, -1959, Darocur-1116, -1173, -1664, -2959, and -4403 (above, manufactured by Ciba Specialty Chemicals);
KAYACURE-BMS, same-DETX, same-MBP, same-DMBI, same-EPA, same-OA (above, Nippon Kayaku Co., Ltd.);
LUCIRIN TPO (BASF);
VICURE-10, -55 (above, manufactured by STAUFER);
TRIGONALP1 (manufactured by AKZO);
SANDORAY 1000 (manufactured by SANDOZ);
DEAP (manufactured by APJOHN);
QUANTACURE-PDO, the same -ITX, the same -EPD (manufactured by WARD BLEKINSSOP) and the like can be preferably used.
As the photopolymerization initiator, a benzophenone compound is preferably used from the viewpoint of high thermal stability.
The use ratio of the photopolymerization initiator is preferably 30 parts by weight or less, more preferably 0.1 to 30 parts by weight, and particularly preferably 0 to 100 parts by weight of the (B) polymerizable unsaturated compound. It is preferable to set it as 5-20 weight part.

-Radical scavenger-
The radical scavenger avoids an undesirable reaction of the polymerizable unsaturated compound (B) due to heating preferably performed when the polymer composition of the present invention is applied onto a substrate to form a coating film. Therefore, it can be contained in the liquid crystal aligning agent of the present invention.
Specific examples of such radical scavengers include, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,
N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide),
3,3 ′, 3 ″, 5 ′, 5 ″ -hexa-tert-butyl-α, α ′, α ″-(mesitylene-2,4,6-triyl) tri-p-cresol,
4,6-bis (octylthiomethyl) -o-cresol,
4,6-bis (dodecylthiomethyl) -o-cresol,
Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate,
Hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione,
1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ,
2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol can be mentioned, and 1 selected from these More than seeds can be used.

A commercially available product may be used as the radical scavenger. ADK STAB AO-80, ADK STAB AO-330;
Sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd .;
IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1326, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX3456, IRGANOX3114, IRGANOX3114, IRGANOX3114, manufactured by Ciba Japan
Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314, manufactured by API Corporation
Etc. can be preferably used.
The use ratio of the radical scavenger in the polymer composition in the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the (B) polymerizable unsaturated compound. .

[Polymer composition]
The polymer composition used in the present invention is a solution in which the above-mentioned (A) polymer and (B) polymerizable unsaturated compound and other optional additives are dissolved in a suitable organic solvent. It is preferable to be prepared.
Examples of the organic solvent include a high boiling point solvent and other solvents. The high boiling point solvent is an organic solvent having a boiling point of 180 ° C. or higher at normal pressure (1.013 × 10 ⁵ Pa). For example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, methylmethoxypropyi Examples thereof include one, ethyl ethoxypropionate, ethylene glycol-n-butyl ether (butyl cellosolve), and the like. The other solvent is an organic solvent not corresponding to the high boiling point solvent, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol monomethyl ether. , Butyl lactate, butyl acetate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, 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 Over DOO, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, and the like di-isopentyl ether.

Since the (A) polymer in the present invention has high solubility in a general-purpose organic solvent, it can be prepared as a solution-like composition without using the high boiling point solvent. Therefore, as a solvent contained in the polymer composition in the present invention, by using only other solvents without using a high boiling point solvent, in the solvent removing step or the baking step after applying the polymer composition, Even when the heating temperature is set to a low temperature, the solvent is easily removed from the coating film, and this makes it possible to suitably apply the method of the present invention to a synthetic resinous substrate having a low heat-resistant temperature.
As the use ratio of the organic solvent, the solid content concentration of the polymer composition (the ratio of the total weight of components other than the organic solvent in the polymer composition to the total weight of the polymer composition) is 1 to 15% by weight. It is preferable to set it as the ratio which becomes 1.5 to 8 weight%.

<Method for manufacturing liquid crystal display element>
The method for producing the liquid crystal display element of the present invention comprises:
On each of the conductive films of a pair of substrates having a conductive film, a coating film is formed by applying the polymer composition as described above,
A pair of substrates on which the coating film is formed are arranged to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell,
A step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates is characterized.
Here, examples of the substrate include glass such as float glass and soda glass; synthesis such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyethylene naphthalate, polyimide, fluorene-based polyether resin, and triacetyl cellulose (TAC). A transparent substrate made of a resin or the like can be used.
As the conductive film, a transparent conductive film is preferably used. For example, a NESA (registered trademark) film made of SnO _{2 or} an ITO film made of In ₂ O ₃ —SnO ₂ can be used. Each of the conductive films is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film configuration, when a voltage is applied between the conductive films (described later), the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region. This makes it possible to further widen the viewing angle characteristics.

In order to apply the polymer composition onto the conductive film of such a substrate, for example, an appropriate application method such as a roll coater method, a spinner method, a printing method, or an ink jet method can be used. After coating, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The prebaking condition is, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the postbaking condition is preferably 100 to 300 ° C, more preferably 120 to 250 ° C, particularly preferably 150 to 180 ° C, preferably 5 to 200 minutes, more preferably 10 to 100 minutes. When the polymer composition to be used does not contain a high-boiling solvent, the effect of the present invention can be sufficiently exhibited even if the maximum temperature of pre-baking and post-baking is 180 ° C. or lower. The method of the invention can be suitably applied to a synthetic resin substrate having low heat resistance. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
The coating film thus formed may be used as it is for the production of a liquid crystal cell in the next step, or may be subjected to a rubbing treatment on the coating surface as necessary prior to the production of the liquid crystal cell. The rubbing treatment can be performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Here, as described in Patent Document 1 (Japanese Patent Laid-Open No. 5-107544), a resist film is formed on a part of the coating surface after once rubbing, and is different from the previous rubbing. By performing a process of removing the resist film after performing the rubbing process in the direction and setting the rubbing direction to be different for each region, it is possible to further improve the visual field characteristics of the obtained liquid crystal display element.

Next, a pair of substrates on which the coating film has been formed are arranged to face each other with the coating film facing each other through a layer of liquid crystal molecules to form a liquid crystal cell.
The liquid crystal molecules used here are preferably nematic liquid crystals having negative dielectric anisotropy, such as dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals. Etc. can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.
To manufacture a liquid crystal cell using such a liquid crystal, for example, the following two methods can be mentioned.
As a first method, two substrates are arranged to face each other through 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 together using a sealant, A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap defined by the substrate surface and the sealing agent and then sealing the injection hole. Alternatively, as a second method, for example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and then a predetermined position on the liquid crystal alignment film surface is applied. After dropping the liquid crystal in several places, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. Thus, a liquid crystal cell can be manufactured.

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 direct current or alternating current.
As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, for example, 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, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
The amount of light irradiation is preferably 1,000 J / m ² or more and less than 100,000 J / m ² , more preferably 1,000 to 50,000 J / m ² . In the manufacture of a conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In} the method of the present invention, the amount of light irradiation was set to 50,000 J / M ² or less, and even if it is 10,000 J / m ² or less, a desired liquid crystal display element can be obtained, which contributes to a reduction in manufacturing cost of the liquid crystal display element and is caused by irradiation with strong light. It is possible to avoid deterioration of electrical characteristics and 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-mentioned treatment. As a polarizing plate used here, a polarizing plate formed by sandwiching a polarizing film called an “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself, etc. Can be mentioned.

<(A) Synthesis of polymer>
Synthesis Example A-1
In a 2000 mL three-necked flask, 83.07 g (0.50 mol) of terephthalic acid as dicarboxylic acid, 54.07 g (0.40 mol) of p-phenylenediamine as diamine, and 3,5-diaminobenzoic acid-3- Cholestanyl (0.10 mol) was mixed with 310.0 g (0.50 mol) of triphenyl phosphite, 42.4 g (1.00 mol) of lithium chloride, 250 ml of pyridine and 500 ml of N-methyl-2-pyrrolidone. The reaction was conducted with stirring at 100 ° C. for 3 hours. After the reaction, the reaction mixture was poured into a large amount of ethanol and reprecipitated, and 90 g of the polymer (A-1) (polyamide) was collected by filtration.
A small amount of the obtained polymer (A-1) was dissolved in N-methyl-2-pyrrolidone and measured as a solution having a polymer concentration of 10% by weight, and the solution viscosity was 60 mPa · s.

Synthesis Example A-2
(1) Synthesis of Vinyl Monomer Having Pretilt Angle Expression Site Compound (a-2) was synthesized according to the following scheme 1.

In a 2000 mL three-necked flask, 384.64 g (1.00 mol) of 7-dehydrocholesterol represented by the formula (a-2-0), 338.56 g (1.20 mol) of trifluoromethanesulfonic anhydride, and 202. 2 g (2.0 mol) was dissolved in 840 mL of dichloromethane, and the reaction was performed with stirring at −30 ° C. for 1 hour in a nitrogen atmosphere. Next, after adding distilled water little by little to the reaction mixture to stop the reaction, 300 mL of ethyl acetate was added, and the mixture was washed successively with dilute hydrochloric acid and distilled water. The organic layer was dehydrated with magnesium sulfate, and then the solvent was removed to obtain a solid.
In a 500 mL three-necked flask, in a nitrogen atmosphere, the above solid was mixed with palladium acetate 0.112 g (0.0005 mol), tri (o-toluyl) phosphorus 0.608 g (0.002 mol), dimethylacetamide (dehydrated product) 100 mL, triethylamine (dehydrated product) 27.7 mL (0.20 mol) and 51.65 g (0.6 mol) vinyl acetate were mixed and reacted at 115 ° C. with stirring for 8 hours. After the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the mixture was washed successively with dilute hydrochloric acid and distilled water. The organic layer was dehydrated with magnesium sulfate, and then the solvent was removed to obtain a solid. The obtained solid was recrystallized from ethanol to obtain 373.4 g of white crystals of the compound represented by the formula (a-2).

(2) Synthesis of polyvinyl alcohol derivative In a 2000 mL three-necked flask, 46.7 g (0.1 mol) of white crystals of the compound represented by the formula (a-2) obtained above and 77.5 g of vinyl acetate. (0.9 mol) was dissolved in 500 mL of methanol, 50.0 mg of azobisisobutyronitrile was added thereto, and the mixture was stirred at 60 ° C. for 5 hours to perform a radical polymerization reaction.
After the reaction, 250 mL of a normal aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was stirred for 1 hour at 40 ° C. to saponify, and the reaction solution was poured into excess water to precipitate the product. The precipitated solid content was collected by filtration and dried under reduced pressure to obtain 58 g of polymer (A-2) (polyvinyl alcohol derivative).
The solution viscosity measured by dissolving a small amount of the polymer (A-2) in N-methyl-2-pyrrolidone as a solution having a polymer concentration of 10% by weight was 60 mPa · s.

Synthesis Example A-3
In a 300 mL four-necked flask equipped with a stir bar, three-way cock and thermometer, 15 g (0.033 mol) of cholestanyl methacrylate, 13 g (0.090 mol) of glycidyl methacrylate, 7.2 g (0.084 mol) of methacrylic acid ), 7.2 g (0.069 mol) of styrene and 7.2 g (0.044 mol) of N-cyclohexylmaleimide, 53 g of ethanol as a solvent, and 2,2′-azobis (2,4- Dimethylvaleronitrile) 2.2 g and α-methylstyrene dimer 0.96 g as a molecular weight modifier were added. A solution containing 48% by weight of the polymer (A-3) is obtained by bubbling this in a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system and then reacting at 70 ° C. for 5 hours in a nitrogen atmosphere. Got.

Synthesis Example A-4
(1) Synthesis of Precursor Polymer A 1,000 mL four-necked flask equipped with a stirrer, a three-way cock and a thermometer was charged with 420 g (5 mol) of vinyl acetate and stirred at 80 ° C. with a nitrogen stream. The system was purged with nitrogen by bubbling for 10 minutes. Thereafter, 12,512 kpa of ethylene gas was sealed in the flask, and then 5.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator.
The temperature in the flask was raised to 80 ° C., and this temperature was maintained for 3 hours to carry out a copolymerization reaction, and then the reaction was stopped by cooling to 30 ° C.
After the reaction was stopped, 250 mL of 1N aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was saponified by stirring at 40 ° C. for 1 hour. Thereafter, the reaction mixture after saponification was poured into excess water to precipitate the product. The precipitated product was collected by filtration and dried under reduced pressure to obtain 288 g of a polyvinyl alcohol / ethylene copolymer (vinyl alcohol content = 50 mol%).
(2) Synthesis of Pretilt Angle Expressing Carboxylic Acid In a 5,000 mL three-necked flask, 389 g (1 mol) of 7-dehydro-3-cholesterol, 200 g (2 mol) of succinic anhydride, 2.0 L of ethyl acetate, dimethylaminopyridine 1.47 g (12.0 mmol) and 167 mL (1.2 mol) of triethylamine were charged and mixed, and the mixture was stirred under reflux conditions at 80 ° C. for 8 hours.
About half of the stirred mixture was transferred to a separatory funnel and 700 mL of tetrahydrofuran was added, followed by sequential extraction and washing with 250 mL of diluted hydrochloric acid and 3 times with 250 mL of distilled water. The remaining half of the mixture was extracted and washed in the same manner. The washed organic layers were combined and dried over magnesium sulfate. Thereafter, magnesium sulfate was filtered off, and then concentrated by an evaporator until the liquid volume became about 1.2 L.
When the concentrated solution was allowed to stand at room temperature for about 10 hours, crystals were precipitated. The crystals were collected by filtration, washed well with ethyl acetate, and the solvent was removed under reduced pressure to obtain 266.5 g (54.5 mmol) of white crystals of mono (3- (7-dehydro) cholesteryl) succinate. (Yield 54.5%)

(3) Halogenation of Pretilt Angle Expressing Carboxylic Acid In a 100 mL three-necked flask, take 4.89 g (10 mmol) of mono (3- (7-dehydro) cholesteryl) succinate obtained in (2) above. Then, 1 mL of an N, N-dimethylformamide solution containing 0.654 g (5.5 mmol) of thionyl chloride was added dropwise thereto, and the mixture was stirred at 80 ° C. for 60 minutes to carry out a halogenation reaction. After the reaction, 4.56 g of solid succinic acid mono (3- (7-dehydro) cholesteryl) chloride was obtained by removing the solvent and excess thionyl chloride using an aspirator.
(4) Synthesis of polyvinyl alcohol derivative A solution obtained by dissolving the total amount (4.56 g, 9 mmol) of succinic acid mono (3- (7-dehydro) cholesteryl) chloride obtained in (3) above in 25 mL of tetrahydrofuran, triethylamine 1 .82 g (18 mmol) and 0.648 g (corresponding to 9 mmol in terms of vinyl alcohol unit) of the precursor polymer obtained in (1) above were mixed, and the reaction was allowed to proceed with stirring at room temperature for 2 hours. went. After the reaction, 150 mL of ethyl acetate was added to the reaction mixture and washed with distilled water. The organic layer was dehydrated with magnesium sulfate, and then the solvent was removed under reduced pressure to obtain 3.81 g of a polymer (A-4). A small amount of the obtained polymer (A-4) was dissolved in N-methyl-2-pyrrolidone and measured as a solution having a polymer concentration of 10% by weight, and the solution viscosity was 60 mPa · s.

Example 1
<Preparation of polymer composition>
(A) The polymer (A-1) obtained in Synthesis Example A-1 as a polymer is dissolved in butyl cellosolve, and (B) a polymerizable unsaturated compound is used as a polymerizable unsaturated compound (formula (B-1-1) described later). 10 parts by weight of the compound represented by formula (A) was added to 100 parts by weight of the polymer to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture and evaluation of liquid crystal cells>
Using the polymer composition prepared above, a total of nine liquid crystal cells were produced by changing the transparent electrode pattern (three types) and the ultraviolet irradiation amount (three levels), and evaluated as follows.

[Production of liquid crystal cell having transparent electrode without pattern]
The polymer composition prepared above was applied onto a transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and hot at 80 ° C. After removing the solvent by heating (pre-baking) on the plate for 1 minute, heating (post-baking) on a hot plate at 150 ° C. for 10 minutes to form a coating film having an average film thickness of 600 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, followed by drying 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 (two) of substrates having a liquid crystal alignment film.
Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, and the liquid crystal alignment film surface is then applied to the pair of substrates. The adhesive was cured by overlapping and pressing so as to face each other. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. did.
The above operation was repeated to produce three liquid crystal cells having unpatterned transparent electrodes. One of them was used for the evaluation of the pretilt angle described later. The remaining two liquid crystal cells were irradiated with light in a state where a voltage was applied between the conductive films by the following method, and then subjected to evaluation of a pretilt angle and a voltage holding ratio.
For two of the liquid crystal cells obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet gland irradiation device using a metal halide lamp as the light source, UV was irradiated at dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} This irradiation amount is a value measured using a light meter that is measured on the basis of a wavelength of 365 nm.

[Evaluation of pretilt angle]
About each liquid crystal cell manufactured above, nonpatent literature 2 (TJ Scheffer et.al., J.Appl.Phys.vol.48, p.1783 (1977)) and nonpatent literature 3 (F. In accordance with the method described in Nakano, et.al., JPN.J.Appl.Phys.vol.19, p.2013 (1980), liquid crystal molecules measured by a crystal rotation method using He-Ne laser light. The value of the tilt angle from the substrate surface was defined as the pretilt angle.
The liquid crystal cell of not irradiated with light, the respective pre-tilt angle of the liquid crystal cell and the liquid crystal cells of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} are shown in Table 2.
[Evaluation of voltage holding ratio]
For each of the liquid crystal cells produced above, a voltage of 5 V was applied at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured. As a measuring device, VHR-1 manufactured by Toyo Corporation was used.
Table 2 shows voltage holding ratios of the liquid crystal cell with the irradiation amount of 10,000 J / m ^{2 and} the liquid crystal cell with the irradiation amount of 10,000 J / m ² .

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (1)]
The polymer composition prepared above is patterned into a slit shape as shown in FIG. 1, and a liquid crystal alignment film is printed on each electrode surface of glass substrates A and B each having an ITO electrode partitioned into a plurality of regions. Apply using a machine (Nissha Printing Co., Ltd.), heat on a hot plate at 80 ° C for 1 minute (pre-bake) to remove the solvent, then heat on a hot plate at 150 ° C for 10 minutes (post-bake) ) To form a coating film having an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. did.
The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal cells, 10,000 J / m ² or 100,000 J / m 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 pattern. After irradiating with light at an irradiation amount of m ² , the response speed was evaluated.
The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

[Evaluation of response speed]
For each of the liquid crystal cells produced above, first, the luminance of light transmitted through the liquid crystal cell by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was defined as a relative transmittance of 0%. . Next, the transmittance when AC 60 V was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%.
At this time, when 60 V AC 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 liquid crystal cell of not irradiated with light, each of the response speed of the liquid crystal cell and the liquid crystal cells of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} are shown in Table 2.
[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (2)]
A liquid crystal having the patterned transparent electrode except that glass substrates A and B each having ITO electrodes patterned in a fishbone shape as shown in FIG. 2 were used using the polymer composition prepared above. in the same manner as in preparation of the cell (1), a liquid crystal cell of not irradiated with light, a liquid crystal cell and a liquid crystal cell of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} was produced, respectively in the same manner as described above The response speed was evaluated. The evaluation results are shown in Table 2.

Examples 2, 4, 5 and 7 and Comparative Example 1
In Example 1 above, the polymer composition was the same as Example 1 except that the type and amount of (A) polymer and (B) polymerizable unsaturated compound were as shown in Table 1. Were prepared, and various liquid crystal cells were produced and evaluated using the liquid crystal cells.
In the preparation of the polymer composition, in Example 5, (B) the unsaturated unsaturated compound of the type and amount shown in Table 1 was used in combination with the polymerizable unsaturated compound,
In Example 7, in addition to (A) polymer and (B) polymerizable unsaturated compound, the types and amounts of photopolymerization initiators shown in Table 1 were used, and in Comparative Example 1, (B ) No polymerizable unsaturated compound was used.
The evaluation results are shown in Table 2.

Example 3
<Preparation of polymer composition>
(A) As a polymer, butyl cellosolve is added to the solution containing the polymer (AI-3) obtained in Synthesis Example A-3 and diluted, and (B) a polymerizable unsaturated compound described below ( B-1-2-1) was added in an amount of 15 parts by weight to 100 parts by weight of the polymer (A) to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture and evaluation of liquid crystal cells>
Various liquid crystal cells were produced and evaluated in the same manner as in Example 1 except that the polymer composition prepared above was used.
The evaluation results are shown in Table 2.

Example 6
<Preparation of polymer composition>
(A) As a polymer, butyl cellosolve is added to the solution containing the polymer (A-3) obtained in Synthesis Example A-3 and diluted, and (B) a polymerizable unsaturated compound is represented by the following formula ( 10 parts by weight of the compound represented by B-1-1) is added to 100 parts by weight of the polymer (A), and methacrylic acid-5ξ-cholestan-3-yl is added as another polymerizable unsaturated compound. 5 parts by weight with respect to 100 parts by weight of the polymer (A) was added to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture of liquid crystal cells>
Various liquid crystal cells were produced and evaluated in the same manner as in Example 1 except that the polymer composition prepared above was used.
The evaluation results are shown in Table 2.

Example 8
<Preparation of polymer composition>
(A) As a polymer, the polymer (A-4) obtained in Synthesis Example A-4 is dissolved in butyl cellosolve, and (B) a polymerizable unsaturated compound is used as formula (B-1-1) described later. 15 parts by weight of the compound represented by the formula (A) was added to 100 parts by weight of the polymer to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture of liquid crystal cells>
Various liquid crystal cells were produced and evaluated in the same manner as in Example 1 except that the polymer composition prepared above was used.
The evaluation results are shown in Table 2.

Comparative Example 2
<Preparation of polymer composition>
(A) A polymer was not used, and a compound represented by the following formula (B-1-1) as a polymerizable unsaturated compound (B) was dissolved in butyl cellosolve to obtain a solution having a concentration of 15% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture of liquid crystal cells>
Various liquid crystal cells were manufactured in the same manner as in Example 1 except that the polymer composition prepared above was used. However, when the polymer composition was applied, a large amount of coating repellency occurred, and the liquid crystal that can be evaluated. The cell could not be manufactured.

In said Table 1, the abbreviation of each component in a polymer composition has the following meaning, respectively.
[(B) polymerizable unsaturated compound]
Compound (B-1)
B-1-1: Compound represented by the following formula (B-1-1) B-1-2-1: Mixture of compounds in which n is 2 to 4 in the following formula (B-1-2) B -1-2-2: In the following formula (B-1-2), a mixture in which the average of the total value of two n is 2.6 B-1-3: represented by the following formula (B-1-3) Compound

[Other unsaturated compounds]
B-2-1: Methacrylic acid 4- (4′-phenyl-bicyclohexyl-4-yl) phenyl ester B-2-2: Methacrylic acid-5ξ-cholestan-3-yl [photoinitiator]
C-1: Phenyl- (4-p-tolylsulfanyl-phenyl) -methanone

1: ITO electrode 2: Slit part 3: Light shielding film

Claims (8)

On the conductive film of the pair of substrates having the conductive film,
(A) At least one polymer selected from the group consisting of polyamide, polyvinyl alcohol derivative, and poly (meth) acrylate, and (B) a polymer composition containing a polymerizable unsaturated compound, and a coating film Form the
A pair of substrates on which the coating film is formed are arranged to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell,
A method for producing a liquid crystal display element, comprising a step of irradiating the liquid crystal cell with light while applying a voltage between conductive films of the pair of substrates. The group (A) is a group having a steroid structure, the following formula (A-0)
(In Formula (A-0), a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time, and c is an integer of 1 to 20. )
A group having 4 to 40 carbon atoms (excluding the case where it is included in the group represented by the above formula (A-0)) and a fluoroalkyl group having 4 to 40 carbon atoms. The manufacturing method of the liquid crystal display element of Claim 1 which has at least 1 sort (s) of group selected from these. The polymerizable unsaturated compound (B) has the following formula (BI) in the molecule:
(In formula (BI), 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 of Claim 1 which contains the compound (B-1) which has at least 2 of monovalent group represented by these. The compound (B-1) has the following formula (B-II) in the molecule:
^{-X 1 -Y 1 -X 2 - (} B-II)
(In Formula (B-II), X ¹ and X ² are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and Y ¹ is a single bond having 1 to 4 carbon atoms. A divalent hydrocarbon group, an oxygen atom, a sulfur atom or —COO—, wherein X ¹ and X ² are one or more alkyl groups having 1 to 4 carbon atoms and alkoxyl groups having 1 to 4 carbon atoms. , May be substituted with a fluorine atom or a cyano group.)
The manufacturing method of the liquid crystal display element of Claim 3 which further contains at least 1 of the bivalent group represented by these.   The compound (B-1) 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, and a di (meth) acrylate having a diphenylmethane structure. The manufacturing method of the liquid crystal display element of Claim 4 which is at least 1 type of compound selected from the group which consists of (meth) acrylate and di-thio (meth) acrylate which has a diphenyl thioether structure.   The method for manufacturing a liquid crystal display element according to claim 1, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions.   A liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element according to claim 1. (A) Polymer composition comprising at least one polymer selected from the group consisting of polyamide, polyvinyl alcohol derivative and poly (meth) acrylate, and (B) polymerizable unsaturated compound .