JP5626517B2 - Manufacturing method of liquid crystal display element - Google Patents

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.

JP-A-5-107544 JP 2010-97188 A

Y. -J. Lee et. al. SID 09 DIGEST, p. 666 (2009) Chemical Reviews, Volume 95, p1409 (1995) T. T. et al. J. et al. Scheffer et. al. , J. et al. Appl. Phys. vo. 48, p. 1783 (1977) F. Nakano et. al. , JPN. J. et al. Appl. Phys. vo. 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.

According to the present invention, the above objects and advantages of the present invention are:
On the conductive film of the pair of substrates having the conductive film,
(A) A polymer containing a first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and (B) a second polymer which is at least one selected from the group consisting of polyamic acid and polyimide. Apply the composition to form a coating film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to the liquid crystal layer,
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 element manufactured by the method of the present invention has a wide viewing angle, response speed of the liquid crystal molecules is fast, sufficient transmittance and shows the contrast, after having excellent display characteristics, displayed continuously for a long time driven The characteristics are not impaired.
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.
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 various uses including liquid crystal televisions for two-dimensional display and three-dimensional display. It can be suitably applied to.

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) a first polymer that is a polyorganosiloxane having a (meth) acryloyl group, and (B) a second polymer that is at least one selected from the group consisting of polyamic acid and polyimide.
<(A) First polymer>
The (A) first polymer used in the present invention is a polyorganosiloxane having a (meth) acryloyl group. Since the first polymer has a (meth) acryloyl group, the film formed from the polymer composition containing the first polymer is given the desired pretilt angle developability with a small amount of light irradiation by the method of the present invention. The advantage is that
In addition to the (meth) acryloyl group, the first polymer has the following formula (D ⁰ )

(In the formula (D ⁰ ), R ^I is an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, a cyano group, a fluorine atom, or a 17 to 51 carbon atoms having a steroid skeleton. A hydrocarbon group;
Z ^I represents a single ^bond, * ^-O-, a * -COO- or ^* -OCO- (where bond marked with "*" is ^{R I} side.)
R ^II represents a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms;
n1 is 1 or 2,
However, when n1 is 2, two R ^II may be the same or different from each other,
n2 is 0 or 1;
Z ^II is ^{* -O-,} a * -COO- or ^* -OCO- (where bond marked with "*" is ^{R I} side.)
n3 is an integer of 0 to 2,
n4 is 0 or 1. )
And may further have at least one group selected from the group consisting of an epoxy group and an epoxy group.

Specifically as alkyl group having 1 to 40 carbon atoms of R ^I in the above formula (D ^0), for example a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, dodecyl Groups, hexadecyl groups, stearyl groups, etc .;
Specific examples of the fluoroalkyl group having 1 to 40 carbon atoms include trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group, pentafluoroethylpropyl group, and pentafluoroethylbutyl group. A pentafluoroethyloctyl group, etc .;
Examples of the 17-51 hydrocarbon group having a steroid skeleton may include a cholestanyl group, a cholestenyl group, and a lanostannyl group.
The cyclohexylene group and phenylene group of R ^II in the above formula (D ⁰ ) are preferably 1,4-cyclohexylene group and 1,4-phenylene group, respectively. Examples of the divalent group represented by — (R ^II ) _n1 — in the above formula (D ⁰ ) include those in which n1 is 1, such as a 1,4-phenylene group and a 1,2-cyclohexylene group. ;
As a case where n1 is 2, for example, 4,4′-biphenylene group, 4,4′-bicyclohexylene group,

(In the formula, a bond marked with "*" is R ^I side.)
The groups represented by each of the above can be mentioned as preferred examples.
N3 in the above formula (D ⁰ ) is preferably 2.
When the first polymer has such a group represented by the above formula (D ⁰ ), the film formed from the polymer composition containing the first polymer exhibits a good liquid crystal alignment ability, preferable.
In addition, since the first polymer has an epoxy group, the film formed from the polymer composition containing the epoxy group has tough mechanical properties and excellent performance such as heat resistance and light resistance. It is preferable.
In the present invention, (A) the first polymer is
It preferably has a (meth) acryloyl group of 0.0003 mol / g or more, more preferably 0.0004 to 0.008 mol / g;
It preferably has a group represented by the above formula (D ⁰ ) in a range of 0.005 mol / g or less, more preferably 0.0002 to 0.003 mol / g;
It is preferable to have an epoxy group in the range of 0.004 mol / g or less, and more preferably 0.0009 to 0.003 mol / g.
For the first polymer, the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 1,000 to 50,000. Furthermore, it is preferable that it is 1,000-10,000.

As long as the (A) first polymer has a group as described above, and preferably has a weight average molecular weight within the above range, its production method is not limited. For example, it can be produced by the following method.
The production of the first polymer which is a polyorganosiloxane having a (meth) acryloyl group is, for example, (1) a hydrolyzable silane compound, wherein the hydrolyzable silane compound is a hydrolyzable silane having a (meth) acryloyl group. A method comprising hydrolyzing and condensing a compound (hereinafter also referred to as “compound (a1)”), or (2) a hydrolyzable silane compound, wherein the hydrolyzable silane compound has an epoxy group. Hydrolysis condensate containing a compound (hereinafter also referred to as “compound (a2)”) and a carboxylic acid, provided that the carboxylic acid is a carboxylic acid having a (meth) acryloyl group (hereinafter also referred to as “compound (b1)”). And the like.) Can be reacted. As a polyorganosiloxane having a (meth) acryloyl group, for example, a commercial product such as AC-SQ TA-100 (manufactured by Toagosei Co., Ltd.) may be used.

The production of the first polymer, which is a polyorganosiloxane having both a (meth) acryloyl group and a group represented by the above formula (D ⁰ ), is, for example, (3) a hydrolyzable silane compound, but this hydrolyzable The silane compound includes a hydrolyzable condensate and a carboxylic acid, including a hydrolyzable silane compound having a (meth) acryloyl group (compound (a1)) and a hydrolyzable silane compound having an epoxy group (compound (a2)). A method of reacting the carboxylic acid with a carboxylic acid having a group represented by the above formula (D ⁰ ) (hereinafter also referred to as “compound (b2)”),
(4) Hydrolyzable silane compound, provided that the hydrolyzable silane compound comprises a hydrolyzable condensate containing a hydrolyzable silane compound having an epoxy group (compound (a2)) and a carboxylic acid, wherein the carboxylic acid is ( A method of reacting a carboxylic acid having a methacryloyl group (compound (b1)) and a carboxylic acid having a group represented by the above formula (D ⁰ ) (compound (b2)), or (5) ( At least one nucleophilic compound selected from the group consisting of a polyorganosiloxane having a (meth) acryloyl group and an amine and a thiol, provided that the nucleophilic compound has a group represented by the above formula (D ⁰ ). Including a nuclear compound. The polyorganosiloxane having a (meth) acryloyl group as a raw material used in the above method (5) can be obtained by the above method (1) or (2). For example, AC-SQ TA-100 (Toagosei Co., Ltd.) ))) Or other commercial products may be used.

In this specification, “hydrolysis condensate” means a mixture of a hydrolysis condensate obtained by hydrolysis and condensation of one kind of hydrolyzable silane compound and two or more kinds of hydrolyzable silane compounds. It is a concept including both a co-hydrolysis condensate obtained by hydrolysis and co-condensation.
In the above methods (2) to (4), the hydrolysis condensate has an epoxy group derived from a hydrolyzable silane compound, and the epoxy group of the hydrolysis condensate is further reacted with a predetermined carboxylic acid. As a result, a first polymer which is a polyorganosiloxane having a desired group is obtained.
Here, in the said method (2), the 1st polymer is made into epoxy other than a (meth) acryloyl group by making the usage-amount of carboxylic acid into a ratio smaller than the epoxy group which a hydrolysis-condensation product has. It can be a polyorganosiloxane further having a group. The same applies to the case where the hydrolysis condensate obtained by the method (2) is used as a raw material in the method (5). In the above methods (3) and (4), the carboxylic acid usage rate (the total usage rate of compound (b1) and compound (b2) in the above method (4)) is hydrolytically condensed. By making the ratio less than the epoxy group possessed by the product, the first polymer is converted into a polyorganosiloxane further having an epoxy group in addition to the (meth) acryloyl group and the group represented by the above formula (D ⁰ ) can do.

The hydrolytic condensation in the above methods (1) to (4) can be performed by reacting a hydrolyzable silane compound or a mixture thereof with water, preferably in the presence of an appropriate catalyst and an organic solvent. The reaction of the hydrolysis condensate having an epoxy group and the carboxylic acid in the above methods (2) to (4) can be preferably carried out in the presence of a catalyst and an organic solvent. The reaction of the polyorganosiloxane having a (meth) acryloyl group and the nucleophilic compound in the above method (5) is known in the presence or absence of an appropriate catalyst depending on the type of the nucleophilic compound used. It can be carried out according to the Michael addition reaction.
Hereinafter, a hydrolyzable silane compound preferably used for producing the first polymer, its hydrolysis condensation reaction, and a hydrolysis having a carboxylic acid and an epoxy group preferably used for a reaction with a hydrolysis condensate having an epoxy group. The reaction between the decomposition condensate and the carboxylic acid will be described in order.
Thereafter, the reaction between the nucleophilic compound and the nucleophilic compound preferably used in the method (5) and the polyorganosiloxane having a (meth) acryloyl group will be described.

[Hydrolyzable silane compound]
{Compound (a1)}
The compound (a1) is a hydrolyzable silane compound having a (meth) acryloyl group.
As the compound (a1) in the present invention, for example, the following formula (a1-1)

(In the formula (a1-1), R is a hydrogen atom or a methyl group, n is an integer of 1 to 6, X is a halogen atom, an alkoxyl group having 1 to 4 carbon atoms or an alkyl having 1 to 4 carbon atoms. And the three Xs present in the molecule may be the same or different, and two or more of X are a halogen atom or an alkoxyl group having 1 to 4 carbon atoms.)
The compound etc. which are represented by these can be mentioned.
In the above formula (a1-1), n is preferably an integer of 1 to 5. The divalent group —C _n H _2n — may be linear or branched, but is preferably linear. X is preferably a halogen atom or an alkoxyl group having 1 to 4 carbon atoms, and more preferably an alkoxyl group having 1 to 2 carbon atoms. Also in this case, three Xs present in the molecule may be the same or different.

  Specific examples of the preferred compound (a1) in the present invention include, for example, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, α-methacryloxymethyltrimethoxysilane, α-acryloxymethyltrimethoxysilane. , Β-methacryloxyethyltrimethoxysilane, β-acryloxyethyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, δ-acryloxybutyltrimethoxysilane, ε-methacryloxypentyltrimethoxysilane, ε-acryloxy Pentiltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltriethoxysilane, α-methacryloxymethyltriethoxysilane, α-acryloxymethyltriethoxysilane, β Methacryloxyethyltriethoxysilane, β-acryloxyethyltriethoxysilane, δ-methacryloxybutyltriethoxysilane, δ-acryloxybutyltriethoxysilane, ε-methacryloxypentyltriethoxysilane, ε-acryloxypentyltriethoxy Silane, acrylic acid-2-hydroxy-5- (trimethoxysilanyl) -pentyl ester, methacrylic acid-2-hydroxy-5- (trimethoxysilanyl) -pentyl ester, acrylic acid-1-hydroxymethyl-4- (Trimethoxysilanyl) -butyl ester, methacrylic acid-1-hydroxymethyl-4- (trimethoxysilanyl) -butyl ester and the like can be mentioned, and at least one selected from the group consisting of these is preferably used. It is possible . Of these, at least one selected from the group consisting of γ-methacryloxypropyltrimethoxysilane and γ-acryloxypropyltrimethoxysilane is particularly preferable.

{Compound (a2)}
The compound (a2) is a hydrolyzable silane compound having an epoxy group.
The epoxy group in the compound (a2) has the following formula (X ¹ -1) or (X ¹ -2)

It is preferable that it exists as what is contained in group represented by these.
Examples of the compound (a2) in the present invention include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane etc. can be mentioned, At least 1 type selected from the group which consists of these can be used preferably. Among these, it is particularly preferable to use at least one selected from the group consisting of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane.

{Other hydrolyzable silane compounds}
(A) In the hydrolytic condensation reaction of the hydrolyzable silane compound performed to produce the first polymer, as the hydrolyzable silane compound, together with the compound (a1) or (a2) or a mixture thereof, Hydrolyzable silane compounds other than the compounds (a1) and (a2) (hereinafter also referred to as “compound (a3)”) may be used in combination. This compound (a3) is a hydrolyzable silane compound having no (meth) acryloyl group and no epoxy group.
Specific examples of such a compound (a3) include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylic. Roxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldi An ethoxysilane etc. can be mentioned, At least 1 type selected from the group which consists of these can be used.

[Hydrolytic condensation reaction of hydrolyzable silane compound]
The hydrolytic condensation reaction of the hydrolyzable silane compound in the present invention is carried out by reacting each hydrolyzable silane compound or mixture thereof as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. Can do. The preferred use ratio of the hydrolyzable silane compound varies as follows according to the production method employed.
When the production of the first polymer is performed by the above method (1), the proportion of the compound (a1) in the entire hydrolyzable silane compound is preferably 5 mol% or more, and 10 to 70 mol%. More preferably, it is more preferably 20 to 50 mol %. In the method (1), when using another hydrolyzable silane compound in addition to the compound (a1), the other hydrolyzable silane compound is selected from the group consisting of the compound (a2) and the compound (a3). Can be used at least one kind.
When the production of the first polymer is performed by the above method (2), the proportion of the compound (a2) in the entire hydrolyzable silane compound is preferably 70 mol% or more, and more preferably 80 mol% or more. More preferably, it is more preferably 90 mol % or more. In the method (2), when another hydrolyzable silane compound is used in addition to the compound (a2), the other hydrolyzable silane compound is selected from the group consisting of the compound (a1) and the compound (a3). It is preferable to use at least one selected from the group consisting of the above-mentioned compound (a3). When the method (2) is employed, it is most preferable to use only the compound (a2) as the hydrolyzable silane compound.

When the production of the first polymer is performed by the above method (3), the proportion of the compound (a1) in the entire hydrolyzable silane compound is preferably 5 to 90 mol%, and preferably 10 to 70 mol%. More preferably, it is more preferably 20 to 60 mol %;
The proportion of the compound (a2) in the entire hydrolyzable silane compound is preferably 10 to 95 mol%, more preferably 20 to 90 mol% or more, and further 40 to 80 mol %. Is preferred. In the method (3), when other hydrolyzable silane compound is used in addition to the compound (a1) and the compound (a2), the other hydrolyzable silane compound is selected from the group consisting of the compound (a3). Can be used at least one kind.
When the production of the first polymer is carried out by the above method (4), the proportion of the compound (a2) in the entire hydrolyzable silane compound is preferably 10 mol% or more, more preferably 20 mol% or more. Is more preferable, and it is more preferable that it is 40 mol % or more. In the method (4), when other hydrolyzable silane compound is used in addition to the compound (a2), the other hydrolyzable silane compound is selected from the group consisting of the compound (a1) and the compound (a3). It is preferable to use at least one selected from the group consisting of the above-mentioned compound (a3). When the method (4) is employed, it is most preferable to use only the compound (a2) as the hydrolyzable silane compound.
When the production of the first polymer is performed by the above method (5), the polyorganosiloxane having a (meth) acryloyl group used as a raw material thereof can be obtained by the above method (1) or (2).

When a polyorganosiloxane having a (meth) acryloyl group as a raw material used in the above method (5) is produced by the above method (1), the hydrolysis used for the hydrolysis condensation reaction for producing the raw material polyorganosiloxane. The proportion of the compound (a1) in the entire decomposable silane compound is preferably 30 mol% or more, and more preferably 50 mol% or more. In this case, when another hydrolyzable silane compound is used in addition to the compound (a1), the other hydrolyzable silane compound is selected from the group consisting of the compound (a2) and the compound (a3). At least one kind can be used.
When a polyorganosiloxane having a (meth) acryloyl group as a raw material used in the above method (5) is produced by the above method (2), the hydrolysis used for the hydrolysis condensation reaction for producing the raw material polyorganosiloxane. The proportion of the compound (a2) in the entire decomposable silane compound is preferably 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. In this case, when using another hydrolyzable silane compound in addition to the compound (a2), the other hydrolyzable silane compound is selected from the group consisting of the compound (a1) and the compound (a3). At least one kind can be used, and it is preferable to use at least one selected from the group consisting of the compound (a3). When a polyorganosiloxane having a (meth) acryloyl group as a raw material used in the method (5) is produced by the method (2), it is possible to use only the compound (a2) as the hydrolyzable silane compound. Most preferred.
The ratio of water used in the hydrolysis condensation reaction is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, with respect to 1 mol in total of the hydrolyzable silane compound.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
Examples thereof include quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.

As a catalyst for performing the hydrolysis condensation reaction, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis-condensation rate without causing side reactions such as ring opening of the epoxy group. It will be excellent and preferable. In addition, the polymer composition containing the first polymer which is a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst and a carboxylic acid has a storage stability. Is advantageous because it is extremely excellent. The reason for this is that when an alkali metal compound or an organic base is used as a catalyst in the hydrolysis-condensation reaction, as shown in Non-Patent Document 2 (Chemical Reviews, Vol. 95, p1409 (1995)), highly crosslinked 3 It is inferred that the formation of a dimensional structure may result in a polyorganosiloxane having a low silanol group content. That is, since such polyorganosiloxane has a low content of silanol groups, the condensation reaction between silanol groups is suppressed, and further, the condensation reaction with the second polymer contained in the polymer composition in the present invention is suppressed. Therefore, it is presumed that the storage stability is excellent.
As the catalyst, an organic base is particularly preferable. The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. It is -3 mol, More preferably, it is 0.05-1 mol.

Examples of the organic solvent that can be used in carrying out the hydrolysis condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
Examples of the hydrocarbon include toluene and xylene;
Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like. Of these, water-insoluble ones are preferred, and one or more selected from the group consisting of such organic solvents can be preferably used.

The proportion of the organic solvent used in carrying out the hydrolytic condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight based on 100 parts by weight of the total hydrolyzable silane compound. Part.
The hydrolysis-condensation reaction is preferably carried out by dissolving the hydrolyzable silane compound or a mixture thereof as described above in an organic solvent, mixing the solution with an organic base and water, and heating the solution using, for example, an oil bath. .
During the hydrolysis condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferred because the washing operation is facilitated. Washing is carried out until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to remove the solvent. The hydrolysis-condensation product can be obtained.
Here, when the above method (2) or method (4) is adopted as the method for producing the first polymer (A) in the present invention, the product is commercially available as a hydrolysis condensate having an epoxy group. May be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (manufactured by Chisso Corporation).

[carboxylic acid]
{Compound (b1)}
The compound (b1) is a carboxylic acid having a (meth) acryloyl group. The compound (b1) may have any other structure as long as it has a (meth) acryloyl group and a carboxyl group. For example, the following formula (b1-1)

(In formula (b1-1), R is a hydrogen atom or a methyl group, R ¹ is a methylene group, an alkylene group having 2 to 10 carbon atoms, a phenylene group or a cyclohexylene group, and a is 1 to 10) An integer, b and c are each 0 or 1, provided that b is 1 when c is 0.)
The compound represented by these can be mentioned. The phenylene group and cyclohexylene group of R ¹ are preferably 1,2-phenylene group and 1,2-cyclohexylene group, respectively.
Preferable specific examples of such compound (b1) include, for example, acrylic acid, methacrylic acid, 2-acryloxyethyl-2-hydroxyethyl-phthalic acid, 4- (2-methyl-acryloyloxy) benzoic acid, 2-acrylic acid. acryloyloxyethyl ethyl hexahydrophthalic acid, 2-acryloyloxyethyl - succinic acid, methacryloyloxyethyl succinate, 2-methacryloyloxyethyl hexahydrophthalic acid, and the like can be illustrated full barrel acid mono hydroxyethyl acrylate, One or more selected from these can be used. As these commercial products, for example, acrylic acid, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), light ester HO-MS, light ester HO-HH, HOA-MPL, HOA-MS, HOA-HH (and above) And Kyoeisha Chemical Co., Ltd.) and M-5400 (manufactured by Toagosei Co., Ltd.).

{Compound (b2)}
Compound (b2) is a carboxylic acid having a group represented by the formula (D ^0), as long as they have a group and a carboxyl group represented by the formula (D ^0), the remaining structure is optionally is there.
The group represented by the above formula (D ⁰ ) of the carboxylic acid is such that R ^I in the above formula (D ⁰ ) is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, or a cyano group. Alternatively, it is preferably a fluorine atom or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. The alkyl group having 4 to 40 carbon atoms is preferably an alkyl group having 6 to 40 carbon atoms; the fluoroalkyl group having 4 to 40 carbon atoms is a fluoroalkyl group having 4 to 20 carbon atoms. Is preferred. Preferred examples of such R ^I, among those exemplified in the description of R ^I in the group represented by the formula (D ^0), it corresponds to the preferred ranges described above.
As the compound (b2), for example, the following formula (b2-1)
D ⁰ -COOH (b2-1)
(In the formula (b2-1), D ⁰ is a group represented by the above formula (D ⁰ ).)
A compound represented by the formula can be mentioned as a preferable one.

Preferred examples of such a compound (b2) include, for example, a long-chain fatty acid, a benzoic acid derivative having a long-chain alkyl group, a benzoic acid derivative having a long-chain alkoxyl group, a benzoic acid derivative having a steroid skeleton, and a polycyclic structure. Examples thereof include benzoic acid derivatives having a carboxylic acid having a fluoroalkyl group. Specific examples of these are:
Examples of long chain fatty acids include caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, and the like;
Examples of benzoic acid derivatives having a long-chain alkyl group include 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, and 4-n-hexadecylbenzoic acid. Acid, 4-stearylbenzoic acid, etc .;
Examples of benzoic acid derivatives having a long-chain alkoxyl group include 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexade. Siloxybenzoic acid, 4-stearyloxybenzoic acid and the like;
Examples of the benzoic acid derivative having a steroid skeleton include cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, lanostannyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, lanostannyloxycarbonylbenzoic acid, succinic acid. Acid-5ξ-cholestan-3-yl, succinic acid-5ξ-cholesten-3-yl, succinic acid-5ξ-lanostane-3-yl and the like;

Examples of benzoic acid derivatives having a polycyclic structure include 4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-hexyl-cyclohexyl) benzoic acid, 4- (4-heptyl-cyclohexyl) benzoic acid, 4′- Pentyl-bicyclohexyl-4-carboxylic acid, 4′-hexyl-bicyclohexyl-4-carboxylic acid, 4′-heptyl-bicyclohexyl-4-carboxylic acid, 4′-pentyl-biphenyl-4-carboxylic acid, 4 ′ -Hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl-bicyclohexyl-4) -Yl) benzoic acid, 4- (4-heptyl-bicyclohexyl-4-yl) benzoic acid, 6- (4'-cyanobiphenyl-4-iro) Xyl) hexanoic acid, etc .;
Examples of the carboxylic acid having a fluoroalkyl group include the following formulas (b2-1-1) and (b2-1-2)

(In formulas (b2-1-1) and (b2-1-2), d is an integer of 0 to 2, and e is an integer of 3 to 18, respectively.)
The compounds represented by each of the above can be mentioned.

{Other carboxylic acids}
(A) In the reaction of a hydrolysis condensate having an epoxy group and a carboxylic acid, which is carried out to produce the first polymer, the above compound (b1) or (b2) or a mixture thereof as a carboxylic acid In addition, a carboxylic acid other than the compounds (b1) and (b2) (hereinafter also referred to as “compound (b3)”) may be used in combination. This compound (b3) is a carboxylic acid having no (meth) acryloyl group and no epoxy group.
Examples of such carboxylic acid include formic acid, acetic acid, propionic acid, benzoic acid, and methylbenzoic acid.

[Reaction of hydrolysis condensate having epoxy group with carboxylic acid]
The reaction between the hydrolysis condensate having an epoxy group and the carboxylic acid preferably comprises the hydrolysis condensate having an epoxy group obtained by the hydrolysis condensation reaction of the above methods (2) to (4) and the carboxylic acid. Can be carried out by reacting in the presence of a catalyst and an organic solvent.
When the production of the first polymer is carried out by the above method (2), it is preferable to use only the compound (b1) or a mixture of the compound (b1) and the compound (b3) as the carboxylic acid. Here, the ratio of the compound (b1) used is preferably 75 mol% or more, and more preferably 90 mol% or more, based on the entire carboxylic acid.
When the production of the first polymer is carried out by the above method (3), it is preferable to use only the compound (b2) or a mixture of the compound (b2) and the compound (b3) as the carboxylic acid. Here, the use ratio of the compound (b2) is preferably 75 mol% or more, and more preferably 90 mol% or more, based on the entire carboxylic acid.
When the production of the first polymer is performed according to the above method (4), it is preferable to use a mixture of the compounds (b1) and (b2) or a mixture of the compounds (b1) to (b3) as the carboxylic acid. . Here, the use ratio of the compound (b1) is preferably 30 to 60 mol%, more preferably 35 to 50 mol%, based on the total amount of the carboxylic acid;
The proportion of compound (b2) used is preferably 40 to 70 mol%, more preferably 50 to 65 mol%, based on the entire carboxylic acid.

As a use ratio of the carboxylic acid in the reaction of the hydrolysis condensate having an epoxy group and the carboxylic acid, as a ratio of the total number of moles of the carboxylic acid to the epoxy group of the hydrolysis condensate,
In the above method (2), it is preferably 5 mol% or more, more preferably 10 to 80 mol%, still more preferably 15 to 60 mol%, particularly preferably 20 to 40 mol%. Yes;
In the above method (3), it is preferably 2 mol% or more, more preferably 2 to 50 mol%, further preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%. Yes;
In the above method (4), it is preferably 7 mol% or more, more preferably 10 mol% or more, further preferably 20 to 80 mol%, particularly preferably 30 to 60 mol%. .

As a catalyst that can be used in the reaction between the hydrolysis condensate having an epoxy group and a carboxylic acid, an organic base can be used, and a compound known as a so-called curing accelerator that accelerates the reaction of the epoxy compound can be used. Can be used.
Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; quaternary organic amines such as tetramethylammonium hydroxide preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- ( 2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methyl] An imidazole compound such as an isocyanuric acid adduct of loumidazolyl- (1 ′)] ethyl-s-triazine;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Such as over preparative quaternary phosphonium salts;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with a polymer;
Amine salt type latent hardness Ka促 Susumuzai;
Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.
Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

The catalyst is preferably in a proportion of 100 parts by weight or less, more preferably in a proportion of 0.01 to 100 parts by weight, still more preferably in a proportion of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total carboxylic acid used. used.
Examples of the organic solvent that can be used in the reaction between the hydrolysis condensate having an epoxy group and a carboxylic acid include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. . Of these, ether compounds, ester compounds, and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the products, and specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, and methyl. Mention may be made of isobutyl ketone and butyl acetate. The solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 0.1% by weight or more, and more preferably 5 to 5%. The ratio is 50% by weight.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

[Nucleophilic compound]
Next, the nucleophilic compound preferably used in the method (5) will be described.
The nucleophilic compound preferably used in the method (5) of the present invention is at least one nucleophilic compound selected from the group consisting of an amine and a thiol, provided that the nucleophilic compound has the above formula (D ⁰ ). It has the group represented by these.
The group represented by the formula ^{(D 0)} having the the nucleophilic compound, ^{R I} in the above formula ^{(D 0)} is an alkyl group or a fluoroalkyl group having 2 to 12 carbon atoms having 2 to 12 carbon atoms Preferably there is. Preferred examples of such R ^I, among those exemplified in the description of R ^I in the group represented by the formula (D ^0), it corresponds to the preferred ranges described above.

As an amine having a group represented by the above formula (D ⁰ ) (hereinafter referred to as “compound (c1)”), a primary amine or a secondary amine is preferably used. Examples of the primary amine compound (c1) include octylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine Hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, 4- (4-pentylcyclohexyl) -phenylamine, 4-octyloxyphenylamine and the like;
Examples of the secondary amine compound (c1) include diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine. , Ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, and the like. Among these, it is preferable to use the compound (c1) which is a secondary amine from the viewpoint that gelation is difficult when reacting with a polyorganosiloxane having a (meth) acryloyl group and that the synthesis is easy.

Examples of the thiol having a group represented by the above formula (D ⁰ ) (hereinafter referred to as “compound (c2)”) include methylthiol, ethylthiol, propylthiol, butylthiol, pentylthiol, hexylthiol, heptylthiol. , Octylthiol, nonylthiol, decylthiol, undecylthiol, dodecylthiol, tridecylthiol, tetradecylthiol, pentadecylthiol, hexadecylthiol, heptadecylthiol, octadecylthiol, nonadecylthiol, 4-butylphenylthiol, 4-pentylphenylthiol, 4-hexylphenylthiol, 4-heptylphenylthiol, 4-octylphenylthiol, 4-nonylphenylthiol, 4-decylphenylthiol, 4-un Silphenylthiol, 4-dodecylphenylthiol, 4-tridecylphenylthiol, 4-tetradecylphenylthiol, 4-pentadecylphenylthiol, 4-hexadecylphenylthiol, 4-heptadecylphenylthiol, 4-octadecylphenylthiol 4-nonadecylphenylthiol, 4-butoxyphenylthiol, 4-pentyloxyphenylthiol, 4-hexyloxyphenylthiol, 4-heptyloxyphenylthiol, 4-octyloxyphenylthiol, 4-nonyloxyphenylthiol, 4-decyloxyphenylthiol , 4 -undecyloxyphenylthiol , 4 -dodecyloxyphenylthiol, 4- (4′-butylcyclohexyl) phenylthiol, 4- (4′-pentylcyclohexyl) Syl) phenylthiol, 4- (4′-hexylcyclohexyl) phenylthiol, 4- (4′-heptylcyclohexyl) phenylthiol, 4- (4′-octylcyclohexyl) phenylthiol and the like.

[Reaction of polyorganosiloxane having (meth) acryloyl group and nucleophilic compound]
Next, the reaction between the polyorganosiloxane having a (meth) acryloyl group and the nucleophilic compound is divided into a case where the nucleophilic compound is the compound (c1) and a case where the compound is the compound (c2). explain.

{When the nucleophilic compound is the compound (c1)}
When the nucleophilic compound is an amine having the group represented by the above formula (D ⁰ ) (compound (c1)), the reaction with the polyorganosiloxane having a (meth) acryloyl group is preferably both organic The reaction can be carried out in the presence of a solvent, optionally in the presence of a catalyst.
The proportion of the compound (c1) used in the reaction between the polyorganosiloxane having a (meth) acryloyl group and the compound (c1) is the ratio of the number of moles of the compound (c1) to the (meth) acryloyl group of the polyorganosiloxane. Is preferably 1 mol% or more and less than 100 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 30 mol%.
As the organic solvent that can be used in the reaction between the polyorganosiloxane having a (meth) acryloyl group and the compound (c1), a polar compound can be preferably used. For example, nitrile, sulfoxide, ether, ester, alcohol, etc. Can be mentioned. Specific examples thereof include nitriles such as acetonitrile and the like;
Examples of the sulfoxide include dimethyl sulfoxide and the like;
Examples of the ether include diethyl ether and dipropyl ether;
Examples of the ester include ethyl acetate and butyl acetate;
Examples of the alcohol include trifluoroethanol and hexafluoroethanol. Of these, nitrile or sulfoxide is preferably used from the viewpoint of reaction stability. From the viewpoint of reaction rate, the solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 40% by weight or more. The ratio is preferably 50 to 90% by weight.
Examples of the catalyst that can be optionally used in the reaction of the polyorganosiloxane having a (meth) acryloyl group and the compound (c1) include aluminum chloride and formic acid.
The reaction temperature is preferably 10 to 100 ° C, more preferably 60 to 100 ° C. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

On the other hand, when the nucleophilic compound is a thiol (compound (c2)) having a group represented by the above formula (D ⁰ ), the reaction with the polyorganosiloxane having a (meth) acryloyl group preferably Can be carried out by reacting in the presence of an organic solvent and a catalyst.
The proportion of the compound (c2) used in the reaction between the polyorganosiloxane having a (meth) acryloyl group and the compound (c2) is the ratio of the number of moles of the compound (c2) to the (meth) acryloyl group of the polyorganosiloxane. Is preferably 1 mol% or more, more preferably 3 to 50 mol%, still more preferably 5 to 30 mol%.
As the organic solvent that can be used in the reaction between the polyorganosiloxane having a (meth) acryloyl group and the compound (c2), for example, a polar compound can be preferably used, for example, nitrile, sulfoxide, ether, ester, etc. Can be mentioned. Specific examples thereof include nitriles such as acetonitrile and the like;
Examples of the sulfoxide include dimethyl sulfoxide and the like;
Examples of the ether include diethyl ether and dipropyl ether;
Examples of the ester include ethyl acetate and butyl acetate. The solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 40% by weight or more, more preferably 50 to 90% by weight. %.
Examples of the catalyst preferably used in the reaction of the polyorganosiloxane having a (meth) acryloyl group and the compound (c2) include organic salt bases, and more specifically, tertiary amines, specifically trimethylamine. , Diethylmethylamine, ethyldimethylamine, triethylamine, tripropylamine and the like. The ratio of the catalyst to be used is preferably 50 parts by weight or less, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the compound (c2).
The reaction temperature is preferably 10 to 100 ° C, more preferably 40 to 80 ° C. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

[(A) Recommended Method for Producing the First Polymer]
In the present invention, it is preferable according to (A) producing the above method of the first polymer (3), the method (4) or method (5). In the method (3) or the method (4), the first polymer is converted to a (meth) acryloyl group, the above formula by setting the proportion of carboxylic acid used to be smaller than the epoxy group of the hydrolysis condensate. It is preferable to have all of the group represented by (D ⁰ ) and the epoxy group.

<(B) Second polymer>
The (B) second polymer 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 polyamic acid can be synthesized by, for example, reacting tetracarboxylic dianhydride and diamine, and the polyimide can be synthesized by dehydrating and ring-closing the polyamic acid to imidize.

[Tetracarboxylic dianhydride]
Examples of tetracarboxylic dianhydrides used to synthesize the polyamic acid include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. be able to. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 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- No 1,2-dicarboxylic acid Things, 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10-tetraone and the like;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like, respectively, and tetracarboxylic dianhydride described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188). May be used.
Among these, as the tetracarboxylic dianhydride used for synthesizing the polyamic acid, only alicyclic tetracarboxylic dianhydride is used, or alicyclic tetracarboxylic dianhydride and aromatic tetra Preference is given to using mixtures with carboxylic dianhydrides. In the latter case, the ratio of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 20 mol% or more, and more preferably 40 mol% or more.

[Diamine]
Examples of the diamine used for synthesizing the polyamic acid include a diamine having a group represented by the above formula (D ⁰ ) (hereinafter referred to as “specific diamine”) and a group represented by the above formula (D ⁰ ). Diamines that do not have (hereinafter referred to as “other diamines”).
The film formed from the polymer composition containing the second polymer synthesized using the specific diamine having the group represented by the above formula (D ⁰ ) exhibits good liquid crystal alignment ability. Will be.
Specific diamines in the present invention, the above formula (D ⁰⁾ is preferably an aromatic diamine having a group represented by, for example, dodecanoxy-2,4-diaminobenzene as a specific example, Pentadekanokishi 2,4 Diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5 -Diaminobenzoic acid Etc. can be mentioned Nosutaniru, it is preferable to use one or more of them. The specific diamine in the present invention is composed of hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene and cholestenyloxy-3,5-diaminobenzene. It is preferably at least one selected from the group.

Examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like that do not correspond to the specific diamines.
Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;
Examples of aromatic diamines include 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) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 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 diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and the diamine described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188). There may be.

The diamine used for synthesizing the second polymer (B) in the present invention is preferably at least one selected from the above specific diamines and other diamines. More preferably used diamines and their proportions are slightly different depending on the structure of the first polymer (A).
In the case where the (A) first polymer does not have the group represented by the formula (D ⁰ ), in order to impart a liquid crystal alignment function to the (B) second polymer, It is preferable to use a diamine containing the above specific diamine as the diamine, more preferably 2 mol% or more, more preferably 2 to 60 mol% of the specific diamine, more preferably 2 to 60 mol%. It is preferable to contain 5-40 mol%, and it is especially preferable to contain 10-30 mol%.
On the other hand, when the (A) first polymer does not have the group represented by the above formula (D ⁰ ), it is not necessary to use the specific diamine as the diamine, but the use of the specific diamine is not recommended. It is not prohibited. In this case, the specific diamine can be used in a range of 90 mol% or less, preferably in a range of 70 mol% or less, and in a range of 40 mol% or less, based on the total diamine. More preferred.

[Molecular weight regulator]
When synthesizing the polyamic acid, a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and dimian as described above. By using such a terminal-modified polymer, the applicability (printability) of the polymer composition can be improved without impairing the effects of the present invention.
Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples of these acid monoanhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic acid. Nic acid anhydride, n-hexadecyl succinic acid anhydride, etc .;
Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
It is preferable that the usage-amount of a molecular weight modifier shall be 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 ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0-100 ° C, preferably 0.1-24 hours, more preferably 0.5-12 hours. Done.
Here, examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like. Protic polar solvents; mention may be made of phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol. The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained.
This reaction solution may be used for the preparation of the polymer composition as it is, may be used for the preparation of the polymer composition after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid may be used. You may use for preparation of a polymer composition, after refine | purifying. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to a known method.

[Synthesis of polyimide]
The polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize.
The polyimide in the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure that the polyamic acid that is a precursor thereof has, or by dehydrating and cyclizing only a part of the amic acid structure, A partially imidized product in which a structure and an imide ring structure coexist may be used. The polyimide in the present invention preferably has an imidization rate of 40% or more. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage.
The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating if necessary. . Of these, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or 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 amic acid structure of a polyamic acid. As the dehydration ring closure 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-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. 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 polyimide is obtained. This reaction solution may be used for the preparation of the polymer composition as it is, or may be used for the preparation of the polymer composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. In addition, the polymer composition may be used for preparation, or the isolated polyimide may be purified and then used for preparation of the polymer composition. These purification operations can be performed according to known methods.

<Use ratio of (A) first polymer and (B) second polymer>
In the polymer composition used in the method of the present invention, the use ratio of (A) the first polymer and (B) the second polymer is (B) relative to 100 parts by weight of the second polymer ( A) The proportion of the first polymer used is preferably 1 to 90 parts by weight, more preferably 2 to 60 parts by weight, and particularly preferably 5 to 40 parts by weight.

<Other ingredients>
The polymer composition used in the method of the present invention contains (A) the first polymer and (B) the second polymer as essential components as described above, but contains other components. Also good.
Examples of other components that can be used here include other polymers, radically polymerizable compounds, and compounds having at least one epoxy group in the molecule (however, the above (A) corresponds to the first polymer). (Hereinafter referred to as “epoxy compound”), functional silane compounds, and the like.

[Other polymers]
These other polymers can be used to improve the solution properties of the polymer composition and the electrical properties of the film formed from the polymer composition. Such other polymers are polymers other than the above (A) first polymer and (B) second polymer, such as polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene. Derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like can be mentioned.
The use ratio of the other polymer is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the second polymer (B). In the present invention, it is preferable not to use other polymers.

[Radically polymerizable compound]
The radically polymerizable compound can be contained in the polymer composition of the present invention for the purpose of improving sensitivity to radiation.
The radical polymerizable compound is a compound having at least one, preferably 1 to 3, at least one group selected from an acryloyl group and a methacryloyl group (hereinafter also referred to as “radical polymerizable group”). Preferably, it is a compound having both 1 to 3 radical polymerizable groups and a liquid crystal similar structure. More preferably, the compound having one radical polymerizable group is represented by the following formula (d1).

(In the formula (d1), R is a hydrogen atom or a methyl group,
R ^III is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, a cyano group or a fluorine atom, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton;
Z ^III is a single bond, ^* —O—, ^* —COO— or ^* —OCO— (where the bond marked with “*” is on the R ^III side);
R ^IV is a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted by a cyano group, a fluorine atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms,
n5 is an integer of 1 to 3,
However, when n5 is 2 or 3, a plurality of R ^IV may be the same or different from each other,
n6 is 0 or 1. )
Di (meth) acrylate having a biphenyl structure and di (meth) acrylate having a phenyl-cyclohexyl structure as a compound having two radical polymerizable groups (hereinafter referred to as “compound (d1)”) , At least one selected from the group consisting of di (meth) acrylate having a 2,2-diphenylpropane structure and di (meth) acrylate having a diphenylmethane structure (hereinafter referred to as “compound (d2)”). Examples of the compound having three polymerizable groups include tri (meth) acrylic acid esters of trihydric or higher polyhydric alcohols (hereinafter referred to as “compound (d3)”).

  Specific examples of the compound (d1) include 4- (4-octadecylcyclohexyl) phenyl acrylate, 4- (4-butylcyclohexyl) phenyl methacrylate, 4- (4-pentylcyclohexyl) phenyl methacrylate, 4- (4- Hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) phenyl methacrylate, 4- (4-decylcyclohexyl) phenyl methacrylate, 4- (4-dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecylcyclohexyl) phenyl methacrylate 4- (4-octadecylcyclohexyl) phenyl methacrylate, 4- (4-butylcyclohexyl) cyclohexyl acrylate, 4- (4-pentylcyclohexyl) silane Rohexyl acrylate, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclohexyl) cyclohexyl acrylate, 4- (4-decylcyclohexyl) cyclohexyl acrylate, 4- (4-dodecylcyclohexyl) cyclohexyl acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl acrylate, 4- (4-octadecylcyclohexyl) cyclohexyl acrylate, 4- (4-butylcyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexylcyclohexyl) ) Cyclohexyl methacrylate, 4- (4-octylcyclohexyl) cyclohexyl methacrylate, 4- (4 Decylcyclohexyl) cyclohexyl methacrylate, 4- (4-dodecylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl methacrylate, 4- (4-octadecylcyclohexyl) cyclohexyl methacrylate, (meth) acrylic acid-5ξ-cholestane- Examples include 3-yl, (meth) acrylic acid-5ξ-cholesten-3-yl, (meth) acrylic acid 4- (4′-pentylbicyclohexyl-4-yl) phenyl ester, and the like.

Specific examples of the compound (d2) include di (meth) acrylate having a biphenyl structure, such as 4 ′-(meth) acryloyloxy-biphenyl-4-yl-acrylate, 2- [4 ′-(2- (meta ) Acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl (meth) acrylate, 2- (2- {4 '-[2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-iroxy } -Ethoxy) -ethyl acrylate, bishydroxyethoxybiphenyl di (meth) acrylate and the like;
Examples of the di (meth) acrylate having a phenyl-cyclohexyl structure include 4- (4- (meth) acryloyloxy-phenyl) -cyclohexyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy). ) -Phenyl] -cyclohexyloxy} -ethyl (meth) acrylate and the like;
Examples of the di (meth) acrylate having a 2,2-diphenylpropane structure include 4- [1- (4- (meth) acryloyloxy-phenyl) -1-methyl-ethyl] -phenyl (meth) acrylate, 2- (4 -{1- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl (meth) acrylate, ethoxy-bisphenol A di (meth) acrylate and the like;
Examples of the di (meth) acrylate having a diphenylmethane structure include 4- (4- (meth) acryloyloxy-benzyl) -phenyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy)- Benzyl] -phenyl} -ethyl (meth) acrylate, di (meth) acrylate of an ethylene oxide adduct of bisphenol F, and the like.

  Specific examples of the compound (d3) include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, Examples thereof include dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, and tri (2-methacryloyloxyethyl) phosphate.

As the radically polymerizable compound used in the present invention, the compound (d1) or the compound (d2) is preferable, and in particular, the compound (d1) in which n5 is 2 or 3 and n6 is 1 in the above formula (d1). The compound (d1) in which R ^III in the above formula (d1) is a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton or the di (meth) acrylate having a biphenyl structure is preferable.
The use ratio of the radical polymerizable compound is preferably 50 parts by weight or less, more preferably 1 to 50 parts by weight, and further preferably 3 to 30 parts by weight with respect to 100 parts by weight of the (B) second polymer. Parts by weight, particularly 5 to 15 parts by weight. By setting it as such a use ratio, the effect expected of this compound can be effectively expressed, without producing the problem of the fall of the voltage holding rate of the liquid crystal display element manufactured.

[Epoxy compound]
The epoxy group compound is preferably a compound having at least two epoxy groups in the molecule, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N , N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane Sun, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine Etc. can be mentioned as preferred.
The blending ratio of these epoxy compounds is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the (B) second polymer.

[Functional silane compounds]
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7 Toriazadekan, 10-triethoxysilyl-1,4,7 Toriazadekan, 9-trimethoxysilyl-3,6-diaza-nonyl acetate, 9 - triethoxysilyl-3,6-diaza-nonyl acetate, 9- Methyl trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3 Glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl triethoxy silane and the like.
The blending ratio of these functional silane-containing compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less with respect to 100 parts by weight of the (B) second polymer.

<Polymer composition>
The polymer composition used in the present invention is a solution in which the above-mentioned (A) first polymer and (B) second polymer and other optional components are dissolved in a suitable organic solvent. It is preferable to be prepared as
Examples of the organic solvent that can be used here include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, and 4-hydroxy-4-methyl. -2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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 Ter, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.
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,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to each other through a layer of liquid crystal molecules,
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, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.
As the conductive film, a transparent conductive film is preferably used. For example, a NESA 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 the 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 pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. 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 liquid crystal cell having a configuration in which the coating film of the pair of substrates on which the coating film is formed is disposed to face each other through a layer of liquid crystal molecules is formed.
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.
In order to form 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 the liquid crystal is applied onto the liquid crystal alignment film surface. After the dropping, the other substrate is bonded so that the liquid crystal alignment films face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be produced.

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 aligning polyvinyl alcohol with a cellulose acetate protective film, or a polarizing plate made of the H film itself, etc. Can be mentioned.

<< Liquid crystal display element >>
The liquid crystal display device manufactured as described above by the method of the present invention has a wide viewing angle, extremely high response speed of liquid crystal molecules, excellent both display characteristics and long-term reliability, and has a low manufacturing cost. Since it is reduced and inexpensive, it can be suitably applied to various uses including liquid crystal televisions for two-dimensional display and three-dimensional display.

<(A) Synthesis of first polymer>
Synthesis Example S-1
[Hydrolysis condensation reaction]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 73.9 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) as a hydrolyzable silane compound and γ-methacrylate. 14.8 g of roxypropyltrimethoxysilane (GMPTS) (ECETS: GMPTS = 75: 25 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent and 10.0 g of triethylamine as a catalyst were charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to hydrolyze having an epoxy group. The condensate was obtained as a viscous transparent liquid.
When this hydrolyzed condensate was subjected to ¹ H-NMR analysis, a peak based on an epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and a side reaction of the epoxy group occurred during the reaction. It was confirmed that this was not happening.

[Reaction of hydrolysis condensate having epoxy group with carboxylic acid]
In a 200 mL three-necked flask, 30.0 g of methyl isobutyl ketone as a solvent and 30.0 g of 4-octyloxybenzoic acid (OCTBA) as a carboxylic acid were added to the hydrolysis condensate having the epoxy group obtained above. 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd., an epoxy compound curing accelerator) as a catalyst, and 48 at 100 ° C. The reaction was performed with stirring for a period of time. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried using magnesium sulfate, and then the solvent was distilled off to obtain (A) the first polymer, which is a polymer. 100.2g of organosiloxane (PS-1) was obtained. About this polyorganosiloxane (PS-1), the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography (GPC) was 7,100.

Synthesis Examples S-2 to S-6, S-10, S-11 and S-16
[Hydrolysis condensation reaction] and [Reaction of hydrolysis condensation product having epoxy group with carboxylic acid]
In the synthesis example S-1, the hydrolytic condensation reaction and hydrolysis condensate were the same as in the synthesis example S-1, except that the types and amounts of hydrolyzable silane compounds and carboxylic acids described in Table 1 were used. and by carrying out the reaction of a carboxylic acid, (a) a polyorganosiloxane which is a first polymer (PS-2) ~ (PS -6), (P S-10), and (P S-11) the (P S- 16) were obtained, respectively. The yield and Mw of these polyorganosiloxanes are shown in Table 1. In Synthesis Examples S-3 to S-5 and S-16, two carboxylic acids were used. Synthesis Example S-6 is a comparative synthesis example.

Synthesis Examples S-7 to S-9
[Hydrolysis condensation reaction]
In the synthesis example S-1, a hydrolytic condensation reaction was performed in the same manner as in the synthesis example S-1 except that the kind and amount of the hydrolyzable silane compound described in Table 1 were used. Polyorganosiloxanes (PS-7) to (PS-9) as one polymer were obtained. The yield and Mw of these polyorganosiloxanes are shown in Table 1.

Synthesis Example S-12
[Hydrolysis condensation reaction]
In the above Synthesis Example S-1, the hydrolysis and condensation reaction was carried out in the same manner as in Synthesis Example S-1 except that the kind and amount of the hydrolyzable silane compound described in Table 1 were used. The decomposition condensate was obtained as a viscous transparent liquid.
[Reaction of hydrolysis condensate having acryloyl group with nucleophilic compound (thiol)]
In a 500 mL three-necked flask equipped with a stirrer and a thermometer, 165.3 g of the above hydrolysis condensate, 60.7 g of n-dodecyl-1-thiol (DT) as a nucleophilic compound, 160 mL of acetonitrile as a solvent, and triethylamine as a catalyst 22.3g was prepared, it heated up at 50 degreeC and stirred for 90 minutes, and reaction was implemented. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and catalyst were distilled off under reduced pressure, whereby (A) the first a polymer polyorganosiloxane (P S-12) was obtained 225.3g as a viscous clear liquid. About this polyorganosiloxane (PS-12), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 7,400.

Synthesis Example S-13
[Hydrolysis condensation reaction]
In the above Synthesis Example S-1, the hydrolysis and condensation reaction was carried out in the same manner as in Synthesis Example S-1 except that the kind and amount of the hydrolyzable silane compound described in Table 1 were used. The decomposition condensate was obtained as a viscous transparent liquid.
[Reaction of hydrolysis condensate having acryloyl group with nucleophilic compound (amine)]
In a 500 mL three-necked flask equipped with a stirrer and a thermometer, 165.3 g of the hydrolysis condensate obtained above, 48.3 g of di-n-octylamine (DOA) as a nucleophilic compound (amine) and acetonitrile as a solvent 160 mL was charged, heated to 50 ° C. and stirred for 6 hours to carry out the reaction. After completion of the reaction, the organic layer is taken out and washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent is distilled off under reduced pressure to have a dioctylamino group (A) the polyorganosiloxane (P S- 13) a first polymer was obtained 212.2g as a viscous clear liquid. The polyorganosiloxane per siloxane (P S- 13), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 7,200.

Synthesis Examples S-14 and S-15
[Hydrolysis condensation reaction] and [Reaction between hydrolysis condensation product having acryloyl group and nucleophilic compound (thiol)]
In the above Synthesis Example S-12, the hydrolysis and condensation reaction was carried out in the same manner as in Synthesis Example S-12 except that the types and amounts of the hydrolyzable silane compound and nucleophilic compound (thiol) described in Table 1 were used. and by performing the reaction with the hydrolysis-condensation product with a nucleophilic compound, was obtained, respectively (a) a polyorganosiloxane which is a first polymer (PS-14) and (P S-15). The yield and Mw of these polyorganosiloxanes are shown in Table 1.

Synthesis Example S-17
[Reaction of silsesquioxane having acryloyl group with nucleophilic compound (thiol)]
In Synthesis Example S-12, have use synthesized AC-SQ TA-100 (manufactured by Toagosei Co., Ltd.) is a silsesquioxane having an acryloyl group in place of the hydrolysis condensate of 165.0G, nucleophilic Except that the amount used of n-dodecyl-1-thiol (DT), which is a functional compound, was 40.5 g, was carried out in the same manner as in the reaction of the hydrolytic condensate with the nucleophilic compound in Synthesis Example S-12, (A) A polyorganosiloxane (PS-17) as the first polymer was obtained. The yield and Mw of this polyorganosiloxane are shown in Table 1.

Abbreviations of each compound in Table 1 have the following meanings.
{Hydrolyzable silane compound}
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane GMPTS: γ-methacryloxypropyltrimethoxysilane GAPTS: γ-acryloxypropyltrimethoxysilane {silsesquioxane having an acryloyl group}
ACSQ: Product name “AC-SQ TA-100”, manufactured by Toagosei Co., Ltd. {carboxylic acid}
OCTBA: 4-octyloxybenzoic acid ACYA: acrylic acid AEHEP: 2-acryloxyethyl-2-hydroxyethyl-phthalic acid MACBA: 4- (2-methyl-acryloyloxy) benzoic acid The amount of carboxylic acid used is hydrolysis It is mol% with respect to the epoxy group which a condensate has. In Synthesis Examples S-3 to S-5 and S-16, two types of carboxylic acids were used.
{Nucleophilic compound}
Thiol DT: n-dodecyl-1-thiol PCBT: 4- (4′-pentylcyclohexyl) phenylthiol BT: n-butyl-1-thiol amine DOA: di-n-octylamine “-” in Table 1 The notation indicates that the compound corresponding to the column was not used.

<(B) Synthesis of second polymer>
Synthesis Example P-1
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine as diamine and 3 (3,5-diaminobenzoyl) 52 g (0.10 mol) of oxy) cholestane was dissolved in 830 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid solution was collected, and N-methyl-2-pyrrolidone was added to measure the solution viscosity as a solution having a polyamic acid concentration of 10% by weight of 60 mPa · s.
Next, 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 dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration ring closure reaction were removed from the system by this operation) ( B) A solution containing about 15% by weight of polyimide (PI-1) having an imidization ratio of about 50%, which is the second polymer, was obtained. A small amount of the obtained polyimide solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 47 mPa · s.

Synthesis Example P-2
200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g of 2,2′-dimethyl-4,4′-diaminobiphenyl as diamine (1. 0 mol) is dissolved in 3,670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours, whereby (B) 10% by weight of polyamic acid (PA-1) as the second polymer is obtained. A solution containing was obtained. The solution viscosity of this polyamic acid solution was 160 mPa · s.

Synthesis Example P-3
1,2,3,4-Cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) and pyromellitic dianhydride 110 g (0.50 mol) as tetracarboxylic dianhydride and 4,4 ′ as diamine -After 200 g (1.0 mol) of diaminodiphenylmethane was dissolved in 2,330 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours, N-methyl-2-pyrrolidone 1 was added to the resulting reaction mixture. , 350 g was added to obtain a solution containing 10% by weight of (B) the second polymer polyamic acid (PA-2). The solution viscosity of this polyamic acid solution was 125 mPa · s.

Example 1
<Preparation of polymer composition>
(B) In a solution containing 100 parts by weight of the polyimide (PI-1) obtained in Synthesis Example P-1 as the second polymer, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC And 5 parts by weight of the polyorganosiloxane (PS-1) obtained in Synthesis Example S-1 as the first polymer, and the solvent composition is NMP: BC = 50: 50 (weight) Ratio), and a solution having a solid content concentration of 6.0% 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 six liquid crystal display elements were manufactured and evaluated by changing the transparent electrode pattern (two types) and the ultraviolet irradiation amount (three levels) 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, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure bonded. The adhesive was cured. 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]
Regarding each of the liquid crystal cells manufactured as described above, Non-Patent Document 3 (T. J. Scheffer et. Al., J. Appl. Phys. Vo. 48, p. 1783 (1977)) and Non-Patent Document 4 (F. Substrate of liquid crystal molecules measured by a crystal rotation method using a He-Ne laser beam in accordance with the method described in Nakano et.al., JPN, J. Appl., Phys., Vo.19, p.2013 (1980)). The value of the tilt angle from the 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 3.
[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 3 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 100,000 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 edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure-bonded so as to face each other. The adhesive was cured. 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 3.

[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 3.

Examples 2-23 and 27-29
In Example 1 above, the weight and amount of (A) the first polymer and (B) the second polymer were set as shown in Table 2, respectively. A combined composition was prepared, and various liquid crystal cells were produced and evaluated using the combined composition. In Examples 11, 12, 15 to 17, 22, 28, and 29, two types of (B) second polymers were used.
The evaluation results are shown in Table 3.

Example 24
<Preparation of polymer composition>
(B) In a solution containing 100 parts by weight of the polyimide (PI-1) obtained in Synthesis Example P-1 as the second polymer, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC ), And (A) 6 parts by weight of the polyorganosiloxane (PS-1) obtained in Synthesis Example S-1 as the first polymer and methacrylic acid-5ξ-cholestane-3- 5 parts by weight of yl (MACY) was added to obtain a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 6.0% 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 polymerizable compound prepared above was used.
The evaluation results are shown in Table 3.

Examples 25 and 26
In Example 24, a polymer composition was prepared in the same manner as in Example 24 except that the type and amount of the radical polymerizable compound were as shown in Table 2, and various liquid crystals were prepared using this. The cell was manufactured and evaluated. In Example 25, two types of radical polymerizable compounds were used.
The evaluation results are shown in Table 3.

Comparative Example 1
In Example 1, except that (A) the first polymer was not used, a polymer composition was prepared in the same manner as in Example 1, and various liquid crystal cells were produced and evaluated using this. .
The evaluation results are shown in Table 3.

Comparative Examples 2-4
Example 1 In the same manner as in Example 1 except that (A) the other polymer or compound shown in Table 2 was used in the amount shown in Table 2 instead of the first polymer. A polymer composition was prepared, and various liquid crystal cells were produced and evaluated using the polymer composition.
The evaluation results are shown in Table 3.

Abbreviations in Table 2 have the following meanings.
[Other compounds]
ra-1: Compound represented by the following formula (ra-1) ra-2: Compound represented by the following formula (ra-2)

[Radically polymerizable compound]
MACY: methacrylic acid-5ξ-cholestan-3-yl PBCHPM: methacrylic acid 4- (4′-pentylbicyclohexyl-4-yl) phenyl ester HEIXA: dipentaerythritol hexaacrylate A-BP-2EO: 2- [4 '-(2-acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl acrylate The notation "-" in Table 1 indicates that the compound corresponding to the column was not used.

From the results of Table 3, in the method of the present invention, when the ultraviolet irradiation amount is 100,000 J / m ² (which is a value conventionally employed in the PSA mode), the degree of the pretilt angle obtained becomes excessive, It can be seen that an appropriate pretilt angle is obtained at an irradiation dose of 10,000 J / m ² or less. Moreover, even when the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage holding ratio is also excellent.
Therefore, according to the method of the present invention, the merits of the PSA mode can be realized with a small amount of light irradiation. Therefore, display unevenness due to a high amount of light irradiation, deterioration of voltage holding characteristics, and long-term reliability are insufficient. Thus, a liquid crystal display device having a wide viewing angle, a high response speed of liquid crystal molecules, a high transmittance, and a high contrast can be manufactured.

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

Claims (14)

On the conductive film of the pair of substrates having the conductive film,
(A) A polymer containing a first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and (B) a second polymer which is at least one selected from the group consisting of polyamic acid and polyimide. Apply the composition to form a coating film,
The coating film of the pair of substrates on which the coating film is formed forms a liquid crystal cell having a configuration in which the coating film is opposed to the liquid crystal layer,
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 above (A) first polymer is further represented by the following formula (D ⁰ )
(In the formula (D ⁰ ), R ^I represents hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, stearyl group , trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group. A group, a pentafluoroethylpropyl group, a pentafluoroethylbutyl group or a pentafluoroethyloctyl group, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton;
Z ^I represents a single ^bond, * ^-O-, a * -COO- or ^* -OCO- (where bond marked with "*" is ^{R I} side.)
R ^II represents a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms;
n1 is 1 or 2,
However, when n1 is 2, two R ^II may be the same or different from each other,
n2 is 0 or 1;
Z ^II is ^{* -O-,} a * -COO- or ^* -OCO- (where bond marked with "*" is ^{R I} side.)
n3 is an integer of 0 to 2,
n4 is 0 or 1. )
The manufacturing method of the liquid crystal display element of Claim 1 which has group represented by these.   The (A) first polymer is a hydrolyzable condensate, wherein the hydrolyzable silane compound includes a hydrolyzable silane compound having a (meth) acryloyl group. 2. A method for producing a liquid crystal display element according to 1. The first polymer (A) is a hydrolyzable silane compound, provided that the hydrolyzable silane compound contains a hydrolyzable silane compound having an epoxy group, and a carboxylic acid, provided that the carboxylic acid is used. The manufacturing method of the liquid crystal display element of Claim 1 which is a reaction product with carboxylic acid which has a (meth) acryloyl group. The (A) first polymer is
At least one nucleophilic compound selected from the group consisting of a polyorganosiloxane having a (meth) acryloyl group and an amine and thiol, provided that the nucleophilic compound has a group represented by the above formula (D ⁰ ). The manufacturing method of the liquid crystal display element of Claim 2 which is a reaction product with a nucleophilic compound. The polyorganosiloxane having the (meth) acryloyl group is
The method for producing a liquid crystal display element according to claim 5, wherein the hydrolyzable silane compound is a hydrolyzed condensate containing a hydrolyzable silane compound having a (meth) acryloyl group. The polyorganosiloxane having the (meth) acryloyl group is
Hydrolyzable silane compound, provided that this hydrolyzable silane compound comprises a hydrolyzable condensate containing a hydrolyzable silane compound having an epoxy group and a carboxylic acid, provided that the carboxylic acid is a carboxylic acid having a (meth) acryloyl group. The manufacturing method of the liquid crystal display element of Claim 5 which is a reaction product with these. The nucleophilic compound is an amine, R ^I in the formula (D ⁰ ) is an alkyl group having 2 to 12 carbon atoms or a fluoroalkyl group having 2 to 12 carbon atoms, and n2 and n4 are each 0. The manufacturing method of the liquid crystal display element as described in any one of Claims 5-7. The nucleophilic compound is a thiol, and R ^I in the formula (D ⁰ ) is an alkyl group having 2 to 12 carbon atoms or a fluoroalkyl group having 2 to 12 carbon atoms. The manufacturing method of the liquid crystal display element of one term. The (A) first polymer is
Hydrolyzable silane compound, provided that the hydrolyzable silane compound comprises a hydrolyzable condensate and a carboxylic acid, including a hydrolyzable silane compound having a (meth) acryloyl group and a hydrolyzable silane compound having an epoxy group. The method for producing a liquid crystal display element according to claim 2, wherein the carboxylic acid is a reaction product of containing a carboxylic acid having a group represented by the formula (D ⁰ ). The (A) first polymer is
Hydrolyzable silane compound, wherein the hydrolyzable silane compound comprises a hydrolyzable condensate containing a hydrolyzable silane compound having an epoxy group, and a carboxylic acid, wherein the carboxylic acid is a carboxylic acid having a (meth) acryloyl group and containing a carboxylic acid having a group represented by the formula (D ^0), the reaction products of, a method of manufacturing a liquid crystal display device according to claim 2. R ^I in the above formula (D ⁰ ) is an alkyl group having 4 to 40 carbon atoms or a fluoroalkyl group having 4 to 40 carbon atoms, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, The manufacturing method of the liquid crystal display element of Claim 10 or 11.   The method of 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.