TWI526752B - Method for producing liquid crystal display element, polymer composition and liquid crystal display element - Google Patents

Description

Manufacturing method of liquid crystal display element, polymer composition and liquid crystal display element

The present invention relates to a method for producing a liquid crystal display device, a polymer composition, and a liquid crystal display device. In more detail, it relates to a new method for manufacturing a liquid crystal display element having a wide viewing angle and a fast response speed.

Among the liquid crystal display elements, an MVA (Multi-Zone Vertical Alignment) type panel which has been hitherto known as a vertical alignment mode has a projection angle in a liquid crystal panel, thereby controlling the pouring direction of liquid crystal molecules, thereby expanding the viewing angle. However, according to this aspect, it is inevitable that the protrusions cause insufficient transmittance and contrast, and further have a problem that the response speed of the liquid crystal molecules is slow.

In recent years, in order to solve the problem of the MVA type panel as described above, a PSA (Polymer Stabilization Orientation) method has been proposed. The PSA method is a gap between a pair of substrates formed of a substrate having a patterned conductive film and a substrate having a conductive film without a conductive film, or a gap between a pair of substrates formed by two substrates having a patterned conductive film. In a liquid crystal composition containing a polymerizable compound, a technique in which a polymerizable compound is irradiated with ultraviolet rays and a polymerizable compound is polymerized in a state where a voltage is applied between the conductive films, thereby exhibiting a pretilt property and controlling a liquid crystal alignment direction. By using this technique, it is possible to achieve a wide viewing angle and a high-speed response of liquid crystal molecules by making the conductive film have a specific structure, and it is also possible to solve the problem of inevitable transmittance and contrast of the MVA type panel. However, in order to polymerize the polymerizable compound, it is necessary to irradiate a large amount of ultraviolet rays such as 100,000 J/m ² , so that in addition to the problem of decomposition of liquid crystal molecules, an unreacted compound which is irradiated with ultraviolet rays and does not polymerize remains in the liquid crystal layer. Or they are combined with each other to produce display spots, which adversely affect voltage retention, or the long-term reliability of the panel.

In response to these problems, Non-Patent Document 1 proposes a method of using a liquid crystal alignment film formed of a polyimine-based liquid crystal alignment agent containing a reactive liquid crystal group. According to Non-Patent Document 1, a liquid crystal display element having a liquid crystal alignment film formed by the method, the response of the liquid crystal molecules is high speed. However, in Non-Patent Document 1, there is no description as to which reactive liquid crystal group should be used, and the amount of ultraviolet radiation necessary is still large, and the concern for display properties, particularly voltage retention properties, has not been eliminated. .

Prior art literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. Hei 5-170044

Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-97188

Non-patent literature

Non-Patent Document 1 Y.-J. Lee et. al., SID 09 DIGEST, p. 666 (2009)

Non-patent literature 2 Chemical Reviews, Vol. 95, p1409 (1995)

Unauthorized Document 3 T. J. Scheffer et. al., J. Appl. Phys. vo. 48, p. 1783 (1977)

Non-patent literature 4 F. Nakano et. al., JPN. J. Appl. Phys. vo. 19, p. 2013 (1980)

The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a liquid crystal display element which has a wide viewing angle, a fast response speed of liquid crystal molecules, and excellent display properties and long-term reliability.

According to the present invention, the above object and advantages of the present invention are achieved by a method of manufacturing a liquid crystal display element, which comprises the steps of: coating a polymer composition on the conductive film of a pair of substrates having a conductive film, respectively; Forming a coating film comprising: (A) a first polymer, the first polymer being a polyorganosiloxane having a (meth)acryl fluorenyl group, and (B) a second polymer The second polymer is at least one selected from the group consisting of polylysine and polyimine; the coating film of the pair of substrates on which the coating film is formed is disposed opposite to each other via a liquid crystal layer, and is formed. The liquid crystal cell having such a structure emits light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates.

The liquid crystal display element manufactured by the method of the present invention has a wide viewing angle, a fast response speed of liquid crystal molecules, exhibits sufficient transmittance and contrast, and excellent display properties, and the display property is not impaired even if it is continuously driven for a long time.

Further, according to the method of the present invention, the amount of light necessary for irradiation can be reduced, which contributes to a reduction in the manufacturing cost of the liquid crystal display element.

Therefore, the liquid crystal display element manufactured by the method of the present invention is superior to the currently known liquid crystal display element in both performance and cost, and is suitable for various uses of a liquid crystal television including two-dimensional display and three-dimensional display.

<<Polymer composition>>

The polymer composition used in the process of the invention comprises:

(A) a first polymer which is a polyorganosiloxane having a (meth) acrylonitrile group, and

(B) a second polymer which is at least one selected from the group consisting of polyproline and polyimine.

<(A) First Polymer>

The (A) first polymer used in the present invention is a polyorganosiloxane having a (meth) acrylonitrile group. Since the first polymer has a (meth) acrylonitrile group, the film formed of the polymer composition containing the polymer has a desired pretilt angle developability by a method of the present invention with a small amount of light irradiation. This advantage.

The first polymer further has at least one group selected from the group consisting of a group represented by the following formula (D ⁰ ) and an epoxy group, in addition to the (meth) acrylonitrile group.

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 or a fluorine atom, or a carbon atom having a steroid skeleton; a hydrocarbon group of 17 to 51; Z ^I is a single bond, *-O-, *-COO- or *-OCO- (wherein the "*" linkage is the R ^I side); R ^II is a cyclohexyl group or a stretch a phenyl group, wherein the cyclohexyl or phenyl group may be substituted by a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is 1 or 2; wherein, when n1 is 2, The two R ^IIs may be identical to each other or different; n2 is 0 or 1; Z ^II is *-O-, *-COO- or *-OCO- (wherein the connection key with "*" is the R ^I side) ;n3 is an integer from 0 to 2; n4 is 0 or 1.

The alkyl group having 1 to 40 carbon atoms as R ^I in the above formula (D ⁰ ) may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group or a fluorene group. And a fluoroalkyl group having 1 to 40 carbon atoms, and specific examples thereof include a trifluoromethyl propyl group and a trifluoromethyl group. a group having a carbon atom number of 17 to 51 having a steroid skeleton, a trifluoromethylhexyl group, a trifluoromethyl fluorenyl group, a pentafluoroethyl propyl group, a pentafluoroethyl butyl group, a pentafluoroethyl octyl group or the like Examples of the hydrocarbon group include a cholesteryl group, a cholesteryl group, a lanthanyl group, and the like; and a cyclohexylene group and a phenylene group as R ^II in the above formula (D ⁰ ) are preferably 1,4-stretched, respectively. Cyclohexyl and 1,4-phenylene. In the above formula (D ⁰ ), as the divalent group represented by -(R ^II )n ₁ -, when n1 is 1, respectively, for example, 1,4-phenylene and 1,2 are preferably exemplified. - a cyclohexyl group or the like; when n1 is 2, a group represented by, for example, 4,4'-extended biphenyl, 4,4'-dicyclohexyl group, or the following formula is preferable.

In the above formula, the connection key with "*" is the R ^I side.

N3 in the above formula (D ⁰ ) is preferably 2.

Since the first polymer contains a group represented by the above formula (D ⁰ ), a film formed of a polymer composition containing the polymer exhibits good liquid crystal alignment energy, which is preferable.

Further, since the first polymer has an epoxy group, the film formed of the polymer composition containing the polymer has excellent mechanical properties, and is excellent in various properties such as heat resistance and light resistance.

The (A) first polymer in the invention preferably has a (meth) acrylonitrile group of 0.0003 mol/g or more, more preferably a (meth) acrylonitrile group of 0.0004 to 0.008 g/g; good 0.005 mole / g or less by the above formula (D ⁰⁾ a group represented, more preferably having 0.0002 to 0.003 mole / g of the above formula (D ⁰⁾ a group represented.

It is preferably an epoxy group having a range of 0.004 mol/g or less, more preferably an epoxy group of 0.0009 to 0.003 mol/g.

The polystyrene-equivalent weight average molecular weight of the first polymer measured by gel permeation chromatography (GPC) is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, particularly preferably from 1,000 to 10,000.

The (A) first polymer is not particularly limited as long as it has such a group, and preferably has a weight average molecular weight in the above range, and can be produced, for example, by the following method.

The first polymer which is a polyorganosiloxane having a (meth)acryl fluorenyl group can be produced, for example, by the following method:

(1) a method of hydrolytically condensing a hydrolyzable decane compound, wherein the hydrolyzable decane compound comprises a hydrolyzable decane compound having a (meth) acrylonitrile group (hereinafter, also referred to as "compound (a1)");

(2) A method of reacting a hydrolysis condensate of a hydrolyzable decane compound with a carboxylic acid, wherein the hydrolyzable decane compound comprises a hydrolyzable decane compound having an epoxy group (hereinafter also referred to as "compound (a2)"), The carboxylic acid contains a carboxylic acid having a (meth) acrylonitrile group (hereinafter also referred to as "compound (b1)").

As the polyorganosiloxane having a (meth) acrylonitrile group, for example, products such as AC-SQ TA-100 (manufactured by Toago Seisakusho Co., Ltd.) can be used.

The polyorganosiloxane having two groups of a (meth)acryl fluorenyl group and a group represented by the above formula (D ⁰ ), that is, the first polymer can be produced, for example, by the following method:

(3) A method of reacting a hydrolysis condensate of a hydrolyzable decane compound with a carboxylic acid, wherein the hydrolyzable decane compound comprises a hydrolyzable decane compound having a (meth) acrylonitrile group (compound (a1)) and having an epoxy group a hydrolyzable decane compound (compound (a2)), wherein the carboxylic acid comprises a carboxylic acid having a group represented by the above formula (D ⁰ ) (hereinafter, also referred to as "compound (b2)");

(4) A method of reacting a hydrolysis condensate of a hydrolyzable decane compound with a carboxylic acid, wherein the hydrolyzable decane compound comprises a hydrolyzable decane compound having an epoxy group (compound (a2)), wherein the carboxylic acid comprises (a) a carboxylic acid (compound (b1)) having an acrylonitrile group and a carboxylic acid (compound (b2)) having a group represented by the above formula (D ⁰ );

(5) A method of reacting a polyorganosiloxane having a (meth) acryloyl group with at least one nucleophilic compound selected from the group consisting of an amine and a thiol, wherein the nucleophilic compound comprises the above formula (D) ⁰ ) A nucleophilic compound of the group shown.

As the raw material used in the above method (5), the polyorganosiloxane having a (meth)acryl fluorenyl group can be obtained by the above method (1) or (2), and AC-SQ TA-100 (East Asia) can also be used. Commodities such as synthetic (manufacturing).

In the present specification, the "hydrolysis condensate" is a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable decane compound, and is obtained by co-hydrolyzing and co-condensing a mixture of two or more hydrolyzable decane compounds. The concept of two kinds of hydrolysis condensates.

In the above methods (2) to (4), the hydrolyzable condensation has an epoxy group derived from a hydrolyzable decane compound, and by reacting the epoxy group of the hydrolyzable condensate with a predetermined carboxylic acid, it is possible to obtain The first polymer of the desired polyorganosiloxane.

In the above method (2), the first polymer can be formed to have a (meth) acrylonitrile group by making the ratio of the carboxylic acid used smaller than the ratio of the epoxy group of the hydrolyzable condensate. In addition to this, it also has an epoxy group-containing polyorganosiloxane. In the above method (5), the same applies to the case where the hydrolyzable condensate obtained by the above method (2) is used as a raw material. Further, in the above method (3) and method (4), the ratio of use of the carboxylic acid (in the above method (4), the total ratio of use of the compound (b1) and the compound (b2)) is more than hydrolyzable condensation The content of the epoxy group is less, and the first polymer can be formed into a polysiloxane having an epoxy group in addition to the group represented by the (meth)acryl fluorenyl group and the above formula (D ⁰ ). Organic oxirane.

The hydrolysis condensation in the above methods (1) to (4) can be carried out by reacting a hydrolyzable decane compound or a mixture thereof with water, preferably in the presence of a suitable catalyst and an organic solvent. The reaction of the hydrolyzed condensate having an epoxy group and the carboxylic acid in the above methods (2) to (4) is preferably carried out in the presence of a suitable catalyst and an organic solvent. The reaction of the polyorganosiloxane having a (meth)acrylinyl group and the nucleophilic compound in the above method (5) may be carried out according to the kind of the nucleophilic compound used, in the presence or absence of a suitable catalyst, The well-known Michael addition reaction proceeds.

Hereinafter, a hydrolyzable decane compound preferably used for the production of the first polymer, a hydrolysis condensation reaction thereof, a carboxylic acid preferably used in the reaction with a hydrolysis condensate having an epoxy group, and an epoxy group having an epoxy group are used. The reaction of the hydrolysis condensate and the carboxylic acid will be described in order.

Next, the reaction of the nucleophilic compound preferably used in the above method (5) and the polyorganosiloxane having a (meth)acryl fluorenyl group and a nucleophilic compound will be described.

[hydrolyzable decane compound] {compound (a1)}

The compound (a1) is a hydrolyzable decane compound having a (meth) acrylonitrile group.

The compound (a1) in the present invention may, for example, be a compound represented by 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, and X is a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkane having 1 to 4 carbon atoms. The three Xs in the molecular memory may be the same or different, and two or more of X are a halogen atom or an alkoxy group having 1 to 4 carbon atoms.

In the above formula (a1-1), n is preferably an integer of 1 to 5. The divalent -C _n H _2n - may be linear or branched, and is preferably linear. Preferably, all three of X are a halogen atom or an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms. In this case, the three Xs of the molecular memory may be the same or different.

Specific examples of the preferred compound (a1) in the present invention include, for example, γ-methacryloxypropyltrimethoxydecane, γ-acryloxypropyltrimethoxydecane, and α-甲. Propylene methoxymethyl trimethoxy decane, α-propylene methoxymethyl trimethoxy decane, β-methacryloxyethyl trimethoxy decane, β-propylene methoxyethyl trimethoxy Base decane, δ-methacryloxybutyl trimethoxy decane, δ-propylene methoxy butyl trimethoxy decane, ε-methyl propylene methoxy pentyl trimethoxy decane, ε-acryl oxime Oxypentyl trimethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ-propylene methoxy propyl triethoxy decane, α-methyl propylene methoxymethyl three Ethoxy decane, α-propylene methoxymethyl triethoxy decane, β-methacryloxyethyl triethoxy decane, β-propylene methoxyethyl triethoxy decane, δ -Methyl propylene methoxy butyl triethoxy decane, δ-propylene methoxy butyl triethoxy decane, ε-methyl propylene methoxy pentyl triethoxy decane, ε-propyl Eneoxypentyl triethoxy decane, 2-hydroxy-5-(trimethoxydecyl)-pentyl acrylate, 2-hydroxy-5-(trimethoxydecyl) methacrylate Amyl ester, 1-hydroxymethyl-4-(trimethoxydecyl)-butyl acrylate, 1-hydroxymethyl-4-(trimethoxydecyl)-butyl methacrylate, etc. Preferably, at least one selected from the group consisting of them is used. Among them, it is particularly preferably at least one selected from the group consisting of γ-methacryloxypropyltrimethoxydecane and γ-propyleneoxypropyltrimethoxydecane.

{compound (a2)}

The compound (a2) is a hydrolyzable decane compound having an epoxy group.

The epoxy group in the compound (a2) is preferably present in a group contained in a group represented by the following formula (X ¹ -1) or (X ¹ -2).

The compound (a2) in the present invention may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidoxypropylmethyl. Dimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl dimethyl methoxy decane, 3-glycidoxy propyl dimethyl Ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, etc., preferably used from At least one of the groups they constitute. Among them, at least one selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane and 3-glycidoxypropyltrimethoxydecane is particularly preferably used.

[Other hydrolyzable decane compounds]

In the hydrolysis condensation reaction of the hydrolyzable decane compound for producing the (A) first polymer, the above compound (a1) or (a2) or a mixture thereof and the compound (a1) may be used as the hydrolyzable decane compound. A hydrolyzable decane compound other than (a2) (hereinafter also referred to as "compound (a3)") is used together. This compound (a3) is a hydrolyzable decane compound which does not have a (meth) propylene group and an epoxy group.

Specific examples of such a compound (a3) include, for example, tetramethoxydecane, tetraethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, and 3-(methyl)acrylonitrile. Oxypropyl propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl trimethoxy Decane, 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, etc. At least one selected from the group consisting of them is used.

[Hydrolysis condensation reaction of hydrolyzable decane compound]

The hydrolysis condensation reaction of the hydrolyzable decane compound in the present invention can be carried out by reacting various hydrolyzable decane compounds or a mixture thereof as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. The preferred use ratio of the hydrolyzable decane compound differs depending on the production method employed.

When the first polymer is produced by the above method (1), the proportion of the compound (a1) in the total hydrolyzable decane compound is preferably 5 mol% or more, more preferably 10 to 70 mol%, further preferably. It is 20~50% by mole. In the method (1), when another hydrolyzable decane compound is used in addition to the compound (a1), at least a group selected from the group consisting of the above compound (a2) and the compound (a3) may be used as the other hydrolyzable decane compound. One.

When the first polymer is produced by the above method (2), the proportion of the compound (a2) in the total hydrolyzable decane compound is preferably 70 mol% or more, more preferably 80 mol% or more, further preferably 90% or more. In the method (2), when another hydrolyzable decane compound is used in addition to the compound (a2), at least a group selected from the group consisting of the above compound (a1) and the compound (a3) may be used as the other hydrolyzable decane compound. One is preferably at least one selected from the group consisting of the above compounds (a3). In the case of the method (2), as the hydrolyzable decane compound, it is further preferred to use only the compound (a2).

When the first polymer is produced by the above method (3), the proportion of the compound (a1) in the total hydrolyzable decane compound is preferably from 5 to 90 mol%, more preferably from 10 to 70 mol%, further The ratio of the compound (a2) to the total hydrolyzable decane compound is preferably from 10 to 95 mol%, more preferably from 20 to 90 mol%, still more preferably from 40 to 80. Moer%. In the method (3), when another hydrolyzable decane compound is used in addition to the compound (a1) and the compound (a2), at least a group selected from the group consisting of the above compound (a3) may be used as the other hydrolyzable decane compound. One.

When the first polymer is produced by the above method (4), the proportion of the compound (a2) in the total hydrolyzable decane compound is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 40% or more. In the method (4), when another hydrolyzable decane compound is used in addition to the compound (a2), at least a group selected from the group consisting of the above compound (a1) and the compound (a3) may be used as the other hydrolyzable decane compound. One is preferably at least one selected from the group consisting of the above compounds (a3). When the method (4) is employed, it is preferred to use only the compound (a2) as the hydrolyzable decane compound.

When the first polymer is produced by the above method (5), the polyorganosiloxane having a (meth) acrylonitrile group used as a raw material can be obtained by the above method (1) or (2).

The polyorganosiloxane having a (meth)acryl fluorenyl group as a raw material used in the above method (5), when produced by the above method (1), the compound (a1) occupies a polyorganosiloxane for producing the raw material The proportion of all hydrolyzable decane compounds used in the hydrolysis condensation reaction is preferably 30 mol% or more, more preferably 50 mol% or more. In this case, when another hydrolyzable decane compound is used in addition to the compound (a1), at least one selected from the group consisting of the above compound (a2) and the compound (a3) may be used as the other hydrolyzable decane compound. .

The polyorganosiloxane having a (meth)acryl fluorenyl group as a raw material used in the above method (5) is produced by the above method (2), and the compound (a2) occupies a polyorganosiloxane for producing the raw material. The proportion of all hydrolyzable decane compounds used in the hydrolysis condensation reaction is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more. In this case, when another hydrolyzable decane compound is used in addition to the compound (a2), at least one selected from the group consisting of the above compound (a1) and the compound (a3) may be used as the other hydrolyzable decane compound. It is preferred to use at least one selected from the group consisting of the above compounds (a3). The polyorganosiloxane having a (meth)acryl fluorenyl group as the raw material used in the above method (5), when produced by the above method (2), is preferably a hydrolyzable decane compound, and most preferably only a compound (a2) ).

The proportion of water used in the hydrolysis condensation reaction is 1 mole per mole of the hydrolyzable decane compound, preferably 0.5 to 100 moles, more preferably 1 to 30 moles.

As the above catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

Examples of the above organic bases include, for example, ethylamine, diethylamine, and piperazine. a primary or secondary organic amine such as piperidine, pyrrolidine or pyrrole; like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo A tertiary organic amine such as undecene; a fourth-order organic amine such as tetramethylammonium hydroxide. Among these organic bases, preferred are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; tetramethylammonium hydroxide Grade IV organic amine.

As the catalyst for carrying out the hydrolysis condensation reaction, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, it is possible to obtain a desired polyorganosiloxane at a high hydrolysis condensation rate without causing side reactions such as ring opening of an epoxy group, and therefore it is excellent in production stability and is preferably used. Further, a reaction product of a polyorganosiloxane having an epoxy group synthesized using an alkali metal compound or an organic base as a catalyst, that is, a polymer composition of the first polymer is excellent in storage stability, so that it is suitable . The reason for this is presumed to be that if an alkali metal compound or an organic base is used as a catalyst in the hydrolysis condensation reaction, as described in Non-Patent Document 2 (Chemical Reviews, Vol. 95, p. 409 (1995)), high cross-linking is formed. The three-dimensional structure makes it impossible to obtain a polyorganosiloxane having a small content of a stanol group. That is, it is presumed that the content of the stanol group of the polyorganosiloxane is small, and the condensation reaction between the stanol groups is suppressed, thereby suppressing the second polymer contained in the polymer composition of the present invention. The condensation reaction results in excellent storage stability.

It is a particularly good organic base as a catalyst. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and should be appropriately set. For example, the total amount of the hydrolyzable decane compound is 1 mole, preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole. ear.

Examples of the organic solvent which can be used in the hydrolysis condensation reaction include a hydrocarbon, a ketone, an ester, an ether, and an alcohol.

Examples of the hydrocarbon include, for example, toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. And the ester may, for example, be ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate or the like; The ether may, for example, be ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran or the like. An alkane or the like; as the above-mentioned alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among them, a water-insoluble solvent is preferred, and one or more selected from the group consisting of these organic solvents are preferably used.

In the case of carrying out the hydrolysis condensation reaction, the use ratio of the organic solvent is preferably from 10 to 10,000 parts by weight, more preferably from 50 to 1,000 parts by weight, per 100 parts by weight of the hydrolyzable decane compound.

The hydrolysis condensation reaction is preferably carried out by dissolving the hydrolyzable decane compound or a mixture thereof as described above in an organic solvent, mixing the solution with an organic base and water, and heating by, for example, an oil bath.

In the hydrolysis condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. When heating, the mixture can be stirred and refluxed.

After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. At the time of the washing, washing with water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like is preferable in terms of easy washing operation. The aqueous layer after washing is neutralized, and then the organic solvent layer is dried with an appropriate desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed to obtain a target hydrolysis condensate.

When the method (2) or the method (4) is used as the method for producing the first polymer (A) in the present invention, a commercially available product can be used as the hydrolysis-condensation product having an epoxy group. Examples of such a product include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, chisso Co., Ltd.).

[carboxylic acid] {compound (b1)}

The compound (b1) is a carboxylic acid having a (meth) acrylonitrile group. The compound (b1) has a (meth) acrylonitrile group and a carboxyl group, and the other structure is arbitrary, and examples thereof include a compound represented by the following formula (b1-1).

(In the 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 phenyl group or a cyclohexylene group, and a is 1 to 10 Integers, b and c are 0 or 1, respectively, but when c is 0, b is 1).

The phenyl and exocyclohexyl groups of R ¹ are preferably a 1,2-phenylene group and a 1,2-extended cyclohexyl group, respectively.

Preferable examples of such a compound (b1) include, for example, acrylic acid, methacrylic acid, 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid, and 4-(2-methyl group). -propenyloxy)benzoic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-propenyloxyethyl-succinic acid, methacryloxyethyl succinic acid, 2-methyl As the acryloyloxyethylhexahydrophthalic acid, phthalic acid monohydroxyethyl acrylate or the like, one or more selected from them can be used. As such a product, for example, acrylic acid, methacrylic acid (above, manufactured by Tokyo Chemical Industry Co., Ltd.), Liqht-ester HO-MS, Light-ester HO-HH, HOA-MPL, HOA-MS, HOA- may be mentioned. HH (above, manufactured by Kyoeisha Chemical Co., Ltd.), M-5400 (manufactured by East Asia Synthetic Co., Ltd.).

{compound (b2)}

Compound (b2) having a (D ⁰⁾ a carboxylic acid group represented by the formula, as long as having the above formula (D ⁰⁾ and a carboxyl group shown, other configurations are arbitrary.

The group represented by the above formula (D ⁰ ) which the carboxylic acid has is preferably R ¹ in the above formula (D ⁰ ), an alkyl group having 4 to 40 carbon atoms, and a fluorine having 4 to 40 carbon atoms. An alkyl group, a cyano group or a fluorine atom, or a hydrocarbon group having a steroidal skeleton having 17 to 51 carbon atoms. The alkyl group having 4 to 40 carbon atoms is preferably an alkyl group having 6 to 40 carbon atoms; and the fluoroalkyl group having 4 to 40 carbon atoms is preferably 4 to 20 carbon atoms. Fluoroalkyl. As specific examples of such preferred R ^I are the above-described formula (D ⁰⁾ R ^I described a group shown in the groups exemplified in the above-described preferred range of equivalent groups.

The compound (b2) is preferably a compound represented by the following formula (b2-1), for example.

D ⁰ -COOH(b2-1)

In the formula (b2-1), D ⁰ is a group represented by the above formula (D ⁰ ).

Preferable examples of such a compound (b2) include long-chain fatty acids, benzoic acid derivatives having a long-chain alkyl group, benzoic acid derivatives having a long-chain alkoxy group, and benzene having a steroid skeleton. A formic acid derivative, a benzoic acid derivative having a polycyclic structure, a carboxylic acid having a fluoroalkyl group, or the like. As specific examples thereof, examples of the long-chain fatty acid include hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, and the like; The benzoic acid derivative may, for example, be 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid or 4-n-hexadecyl group. Benzoic acid, 4-octadecylbenzoic acid, etc.; as a benzoic acid derivative having a long-chain alkoxy group, for example, 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-正a benzoic acid derivative, 4-n-dodecyloxybenzoic acid, 4-n-hexadecaneoxybenzoic acid, 4-octadecyloxybenzoic acid or the like; as a benzoic acid derivative having a steroid skeleton, For example, cholestyloxybenzoic acid, cholestyloxybenzoic acid, lanthanyl benzoic acid, cholestyloxycarbonylbenzoic acid, cholestyloxycarbonylbenzoic acid, lanostinocarbonylcarbonyl group Benzoic acid, succinic acid-5ξ-cholest-3-yl ester, succinic acid-5ξ-cholesten-3-yl ester, succinic acid-5ξ-lanostan-3-yl ester As the benzoic acid derivative having a polycyclic structure, for example, 4-(4-pentyl-cyclohexyl)benzoic acid, 4-(4-hexyl-cyclohexyl)benzoic acid, 4-(4-heptyl) -cyclohexyl)benzoic acid, 4'-pentyl-dicyclohexyl-4-carboxylic acid, 4'-hexyl-dicyclohexyl-4-carboxylic acid, 4'-heptyl-dicyclohexyl-4-carboxylic acid , 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4-(4-pentyl- Dicyclohexyl-4-yl)benzoic acid, 4-(4-hexyl-dicyclohexyl-4-yl)benzoic acid, 4-(4-heptyl-dicyclohexyl-4-yl)benzoic acid, 6- (4'-Cyanobiphenyl-4-yloxy)hexanoic acid, etc.; as a carboxylic acid having a fluoroalkyl group, for example, the following formulas (b2-1-1) and (b2-1-2) ) Compounds and the like respectively indicated.

CF ₃ ─(CF ₂ ) _d ─(CH ₂ ) _e ─COOH (b2-1-1)

In the formulas (b2-1-1) and (b2-1-2), d is an integer of 0 to 2, respectively, and e is an integer of 3 to 18, respectively.

{Other carboxylic acid}

In the reaction of the hydrolysis condensate having an epoxy group and the carboxylic acid carried out for producing the (A) first polymer, as the carboxylic acid, the above compound (b1) or (b2) or a mixture thereof and a compound thereof may be used. A carboxylic acid other than (b1) or (b2) (hereinafter, also referred to as "compound (b3)") is used together. This compound (b3) is a carboxylic acid having no (meth)acryl fluorenyl group and an epoxy group.

Examples of such a carboxylic acid include formic acid, acetic acid, propionic acid, benzoic acid, and methylbenzoic acid.

[Reaction of a hydrolysis condensate having an epoxy group and a carboxylic acid]

The reaction of the hydrolysis condensate having an epoxy group and the carboxylic acid can be carried out by subjecting the hydrolysis condensate having the epoxy group obtained by the hydrolysis condensation reaction of the above methods (2) to (4) and the above carboxylic acid preferably in the catalyst and The reaction proceeds in the presence of an organic solvent.

When the first polymer is produced by the above method (2), it is preferred to use only the compound (b1) as the carboxylic acid or a mixture of the compound (b1) and the compound (b3). The ratio of use of the compound (b1) is preferably 75 mol% or more, and more preferably 90 mol% or more based on the total carboxylic acid.

When the first polymer is produced by the above method (3), it is preferred to use only the compound (b2) as the carboxylic acid or a mixture of the compound (b2) and the compound (b3). The ratio of use of the compound (b2) is preferably 75 mol% or more, and more preferably 90 mol% or more based on the total carboxylic acid.

When the first polymer is produced by the above method (4), a mixture of the compounds (b1) and (b2) or a mixture of the compounds (b1) to (b3) is preferably used as the carboxylic acid. The ratio of use of the compound (b1) is preferably from 30 to 60 mol%, more preferably from 30 to 50 mol%, based on the total of the carboxylic acid.

The use ratio of the compound (b2) is preferably from 40 to 70 mol%, more preferably from 50 to 65 mol%, based on the total of the carboxylic acid.

In the reaction of the hydrolyzed condensate having an epoxy group and the carboxylic acid, the ratio of the use of the carboxylic acid to the epoxy group of the hydrolysis condensate, the ratio of the total number of moles of the carboxylic acid is: in the above method ( 2), preferably 5 mol% or more, more preferably 10 to 80 mol%, further preferably 15 to 60 mol, particularly preferably 20 to 40 mol%; in the above method (3) Preferably, it is 2 mol% or more, more preferably 2-50 mol%, further preferably 5-40 mol, and particularly preferably 10-30 mol%; in the above method (4), it is preferable 7 mol% or more, more preferably 10 mol% or more, further preferably 20 to 80 mol, particularly preferably 30 to 60 mol%; reaction of a hydrolyzed condensate having an epoxy group and a carboxylic acid In addition, as a catalyst which can be used, in addition to an organic base, a compound known as a so-called curing accelerator which accelerates the reaction of an epoxy compound can also be used.

Examples of the above organic base include, for example, ethylamine, diethylamine, and piperazine. a primary-secondary organic amine such as piperidine, pyrrolidine or pyrrole; like triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicyclo A tertiary organic amine such as undecene; a fourth-order organic amine such as tetramethylammonium hydroxide. Among these organic bases, preferred are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; tetramethylammonium hydroxide A quaternary organic amine.

The curing accelerator may, for example, be a tertiary amine such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine or triethanolamine. Like 2-methylimidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 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-methyloxazol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanide Benzyl)-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole Benzene trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium phthalate, 1-(2-cyanoethyl)-2-ethyl-4-methyl Imidazolium benzoate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-three 2,4-Diamino-6-(2'-n-undecylimidazolyl)ethyl-s-three 2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-three , isocyanuric acid addition product of 2-methylimidazole, isocyanuric acid addition product of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1 ')] Ethyl-s-three An imidazole compound such as an isocyanuric acid adduct; an organophosphorus compound such as diphenylphosphine, triphenylphosphine or triphenylphosphite; like benzyltriphenylphosphonium chloride, quaternary tetrabromide Butyl hydrazine, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyl Triphenylphosphonium acetate, tetra-n-butyl fluorene O, O-diethylphosphonium dithiosulfate, tetra-n-butylphosphonium benzotriazole salt, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butyl a quaternary phosphonium salt such as butyl phosphonium tetraphenyl borate or tetraphenylphosphonium tetraphenyl borate; such as 1,8-diazobicyclo[5.4.0]undecene-7 and its organic acid salt Diazobicycloolefin; organometallic compound such as zinc octoate, tin octoate, acetonitrile aluminum complex; like tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride a quaternary ammonium salt such as tetra-n-butylammonium chloride; a boron compound such as boron trifluoride or triphenyl borate; a metal halide such as zinc chloride or tin chloride; dicyanoquinone Amines and amines and epoxies a high-melting-point-dispersion latent curing accelerator such as an amine addition accelerator such as an adduct; a microcapsule-type latent curing formed by coating a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound, or a quaternary phosphonium salt Promoter; amine salt type latent curing accelerator; latent curing accelerator such as high temperature decomposing thermal cationic polymerization latent curing accelerator such as Lewis acid salt or Bronsted acid salt.

Among them, a quaternary ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride is preferred.

The catalyst is preferably used in a proportion of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, even more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the carboxylic acid to be used.

In the reaction of the hydrolyzed condensate having an epoxy group and the carboxylic acid, examples of the organic solvent that can be used include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alcohol compound. Among the above, from the viewpoints of the solubility of the raw material and the product and the ease of purification of the product, among them, an ether compound, an ester compound, and a ketone compound are preferable as a specific solvent, and 2-butanone can be mentioned. 2-hexanone, methyl isobutyl ketone and butyl acetate. The solvent is preferably used in a proportion of 0.1% by weight or more, more preferably 5 to 50% by weight, based on the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution).

The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 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 may, for example, be at least one nucleophilic compound selected from the group consisting of an amine and a thiol, wherein the nucleophilic compound has the above formula (D ⁰ ) The group shown.

The group represented by the above formula (D ⁰ ) which the nucleophilic compound has is preferably such that R ^I in the above formula (D ⁰ ) is an alkyl group having 2 to 12 carbon atoms or a carbon number of 2 to 2 12 fluoroalkyl groups. As specific examples of such preferred R ^I are the above-described formula (D ⁰⁾ R ^I described a group shown in the groups exemplified in the above-described preferred range of equivalent groups.

As the 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. The compound (c1) as the primary amine may, for example, be butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine, and ten. Dialkylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, pentadecylamine, 4-( 4-pentylcyclohexyl)-phenylamine, 4-octyloxyphenylamine, etc.; the compound (c1) as a secondary amine may, for example, be diethylamine, dipropylamine or dibutylamine. , dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di(undecyl)amine, di(dodecyl)amine, di( Tridecylamine, di(tetradecyl)amine, dipentadecylamine, dihexadecylamine, di(heptadecyl)amine, di(octadecyl) An amine, a di(nonadecyl)amine or the like; among them, from the viewpoint of being difficult to gel and easy to synthesize when reacted with a polyorganosiloxane having a (meth)acrylinyl group, it is preferably used. a compound of the amine (c1).

The mercaptan (hereinafter referred to as "compound (c2)") having a group represented by the above formula (D ⁰ ) may, for example, be methyl mercaptan, ethyl mercaptan, propyl mercaptan or butyl. Mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, mercapto mercaptan, mercapto mercaptan, undecyl mercaptan, dodecyl mercaptan, tridecyl Mercaptan, tetradecyl mercaptan, pentadecyl mercaptan, cetyl mercaptan, heptadecyl mercaptan, octadecyl mercaptan, nineteen alkyl mercaptan, 4-butylbenzene Mercaptan, 4-pentylphenylthiol, 4-hexylphenylthiol, 4-heptylphenylthiol, 4-octylphenylthiol, 4-nonylphenylthiol, 4- Nonylphenylthiol, 4-undecylphenylthiol, 4-dodecylphenylthiol, 4-tridecylphenylthiol, 4-tetradecylphenylthiol , 4-pentadecylphenylthiol, 4-hexadecylphenylthiol, 4-heptadecylphenylthiol, 4-octadecylphenylthiol, 4-nonadecane Phenyl thiol, 4-butoxyphenyl thiol, 4-pentyloxy phenyl thiol, 4-hexyloxy phenyl thiol, 4-heptyloxy phenyl thiol, 4-octyloxy Phenyl thiol 4-decyloxyphenylthiol, 4-decyloxyphenylthiol, 4-dodecyloxyphenylthiol, 4-undecyloxyphenylthiol, 4-(4'- Butylcyclohexyl)phenylthiol, 4-(4'-pentylcyclohexyl)phenylthiol, 4-(4'-hexylcyclohexyl)phenylthiol, 4-(4'-heptylcyclohexane Hexyl)phenylthiol, 4-(4'-octylcyclohexyl)phenylthiol, and the like.

[Reaction of polyorganosiloxane with (meth)acrylinyl group and nucleophilic compound]

Next, the reaction of the polyorganosiloxane having a (meth)acryl fluorenyl group and a nucleophilic compound is described in the case where the nucleophilic compound is the compound (c1) and the case of the compound (c2).

[The case where the nucleophilic compound is the compound (c1)]

In the case where 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) acrylonitrile group is preferably in the organic The reaction of the two is carried out in the presence of a solvent, optionally in the presence of a catalyst.

In the reaction of the polyorganosiloxane having a (meth) acryloyl group and the compound (c1), the ratio of use of the compound (c1) to the (meth) acrylonitrile group of the polyorganosiloxane is The molar ratio of the compound (c1) is preferably 1 mol% or more, less than 100 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 30 mol%.

As the organic solvent which can be used in the reaction of the polyorganosiloxane having the (meth)acryloyl group and the compound (c1), a polar compound is preferably used, and examples thereof include a nitrile, an anthracene, an ether, an ester, and an alcohol. Wait. Specific examples of the nitrile include, for example, acetonitrile; and the above-mentioned anthracene may, for example, be dimethyl hydrazine; and examples of the ether include diethyl ether. Examples of the ester include, for example, ethyl acetate and butyl acetate; and examples of the alcohol include trifluoroethanol and hexafluoroethanol. Among them, nitrile or anthracene is preferably used from the viewpoint of reaction stability. The solvent is preferably used in a proportion of 40% by weight or more, more preferably 50 to 90% by weight of the solid content (the ratio of the total weight of the components other than the solvent in the reaction solution) to the total weight of the solution. The percentage of % is used.

The catalyst which can be optionally used in the reaction of the polyorganosiloxane having a (meth) acryloyl group and the compound (c1) may, for example, be aluminum chloride or formic acid.

The reaction temperature is preferably from 10 to 100 ° C, more preferably from 60 to 100 ° C. The reaction time is preferably from 0.5 to 8 hours, more preferably from 1 to 6 hours.

On the other hand, in the case where the nucleophilic compound is a thiol having a group represented by the above formula (D0) (compound (c2), a reaction with a polyorganosiloxane having a (meth) acrylonitrile group is compared It is preferred to carry out the reaction in the presence of an organic solvent and a catalyst.

In the reaction of the polyorganosiloxane having a (meth) acrylonitrile group and the compound (c2), the ratio of use of the compound (c2) to the (meth) acrylonitrile group of the polyorganosiloxane is The molar ratio of the compound (c2) is preferably 1 mol% or more, more preferably 3 to 50 mol%, still more preferably 5 to 30 mol%.

As the organic solvent which can be used for the reaction of the polyorganosiloxane having a (meth)acryloyl group and the compound (c2), for example, a polar compound is preferably used, and examples thereof include a nitrile, an anthracene, an ether, an ester, and the like. . Specific examples of the nitrile include, for example, acetonitrile; and the above-mentioned anthracene may, for example, be dimethyl hydrazine; and examples of the ether include diethyl ether. Dipropyl ether or the like; examples of the ester include ethyl acetate and butyl acetate. The solvent is preferably used in a proportion of 40% by weight or more based on the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution) to the total weight of the solution, and more preferably 50 to 90% by weight.

The catalyst which can be preferably used in the reaction of the polyorganosiloxane having a (meth) acrylonitrile group and the compound (c2) may, for example, be an organic base or the like; more specifically, a tertiary amine may be mentioned. The trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, tripropylamine, and the like can be exemplified. The use ratio of the catalyst is preferably 50 parts by weight or less, more preferably 10 to 30 parts by weight, per 100 parts by weight of the compound (c2).

The reaction temperature is preferably from 10 to 100 ° C, more preferably from 40 to 80 ° C. The reaction time is preferably from 0.5 to 8 hours, more preferably from 1 to 6 hours.

[(A) Recommended Manufacturing Method of First Polymer]

In the present invention, the (A) first polymer is preferably produced by the above method (3), method (4) or method (5). In the above method (3) or method (4), it is preferred that the first polymer has (meth) propylene by making the ratio of the carboxylic acid used smaller than the ratio of the epoxy group of the hydrolyzable condensate. A group represented by a thiol group, a group represented by the above formula (D0), and an 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 polyproline and polyimine.

The polylysine may be synthesized by, for example, a reaction of a tetracarboxylic dianhydride and a diamine, and the polyimine may be synthesized by dehydrating the polyamic acid by ring closure.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butane tetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1, 2, and 3, 4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic 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]xin- 2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxa Tricyclo[5.3.1.0 ^2,6 ]undec-3,5,8,10-tetraketone, etc.; as the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc.; The tetracarboxylic dianhydride described in the patent document 2 (JP-A-2010-97188).

As the tetracarboxylic dianhydride for synthesizing the aforementioned polyaminic acid, among them, it is preferred to use only an alicyclic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride. mixture. In the latter case, the alicyclic tetracarboxylic dianhydride occupies a proportion of all tetracarboxylic dianhydrides, preferably 20 mol% or more, more preferably 40 mol% or more.

[diamine]

The diamine used for the synthesis of the polyamic acid may, for example, be a diamine having a group represented by the above formula (D ⁰ ) (hereinafter referred to as "specific diamine") and not having the above formula (D ⁰ ). The diamine of the group shown (hereinafter referred to as "other diamine").

A film formed of a polymer composition containing a second polymer synthesized using a specific diamine having such a group represented by the above formula (D ⁰ ) exerts a good liquid crystal alignment energy.

The specific diamine in the present invention is preferably an aromatic diamine having a group represented by the above formula (D ⁰ ), and specific examples thereof include, for example, dodecyloxy-2,4-di. Aminobenzene, pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, ten Dialkoxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy- 2,5-Diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteneoxy-3,5-diaminobenzene, 3,5-diaminobenzoic acid cholesteric The alkyl ester, the cholesteryl 3,5-diaminobenzoate, the lanosteryl 3,5-diaminobenzoate, and the like are preferably used. One or more of them are preferably used. The specific diamine in the present invention is particularly preferably selected from the group consisting of cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, and cholestyloxy-3. At least one of the group consisting of 5-diaminobenzene and cholestyloxy-3,5-diaminobenzene.

The other diamine may, for example, be a diamine which is not equivalent to the above specific diamine, such as an aliphatic diamine, an alicyclic diamine, an aromatic diamine or a diamine organosiloxane.

Specific examples thereof include aliphatic diamines, and examples thereof include 1,1-m-xylenediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentane. An amine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,7-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1, 3-di(aminomethyl)cyclohexane; etc.; as the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2' - fluorene (trifluoromethyl)biphenyl, 2,7-diamino hydrazine, 4,4'-diaminodiphenyl ether, 2,2-indole [4-(4-aminophenoxy) Phenyl]propane, 9,9-fluorene (4-aminophenyl) fluorene, 2,2-indole [4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-indole ( 4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropyl) anthracene (aniline), 4,4'-(meta-phenylene diisopropyl)di() Aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-fluorene (4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4-diamine Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diamino Carbazole, N-phenyl-3,6-diaminocarbazole, N,N'-indole (4-aminophenyl)-benzidine, N,N'-indole (4-aminophenyl) -N,N'-dimethylbenzidine or the like; examples of the diamine organooxosiloxane include 1,3-bis(3-aminopropyl)-tetramethyldioxane, and the like, and The diamine described in Patent Document 2 (JP-A-2010-97188) is used.

As the diamine for synthesizing the (B) second polymer in the present invention, it is preferred to use at least one selected from the group consisting of specific diamines and other diamines as described above. More preferably, the diamine used and its use ratio are slightly different depending on the structure of the first polymer (A) described above.

When the first polymer (A) does not have a group represented by the above formula (D ⁰ ), in order to impart a liquid crystal alignment function to the (B) second polymer, it is preferred to use the specific diamine as the diamine. More preferably, the diamine contains 2 mol% or more of the specific diamine relative to all diamines, more preferably 2 to 60 mol%, particularly preferably 5 to 40 mol%, and most preferably contains 10~30% by mole.

On the other hand, when the (A) first polymer does not have a group represented by the above formula (D ⁰ ), it is not necessary to use a specific diamine as a diamine, but the use of a specific diamine is not prohibited. The specific diamine in this case may be used in the range of 90 mol% or less, preferably 70 mol% or less, and more preferably 40 mol% or less, based on the total diamine.

[Molecular weight regulator]

In synthesizing the aforementioned polyaminic acid, a terminally modified polymer can be synthesized using a suitable molecular weight modifier together with the tetracarboxylic acid diamine and the diamine as shown above. By forming the terminal-modified polymer, the coating property (printability) of the polymer composition can be improved without impairing the effects of the present invention.

The molecular weight modifier may, for example, be an acid monoanhydride, a monoamine compound or a monoisocyanate compound. Specific examples thereof include, as the acid monoanhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl salicylic anhydride, n-dodecyl salicylic anhydride, and positive examples. Tetradecyl salicylic anhydride, n-hexadecyl salicylic anhydride, etc.; as the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octyl group Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight modifier is preferably 10 parts by weight or less based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used.

[Synthesis of polyglycine]

The ratio of use of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of polyproline is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group of the diamine. More preferably, it is a ratio of 0.3 to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0 ° C to 100 ° C, preferably for 0.1 to 24 hours, more preferably for 0.5 to 12 hours. .

Among them, examples of the organic solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, and γ-butyl. An aprotic polar solvent such as lactone, tetramethylurea or hexamethylphosphonium triamine; a phenolic solvent such as m-cresol, xylenol, phenol or halogenated phenol. The amount (a) of the organic solvent is preferably an amount of the total amount (b) of the tetracarboxylic dianhydride and the diamine relative to the total amount (a+b) of the reaction solution of 0.1 to 30% by weight.

As described above, a reaction solution in which polylysine is dissolved can be obtained.

The reaction solution can be directly used for preparing a polymer composition, or can be used for preparing a polymer composition after separating the poly-proline acid contained in the reaction solution, or after separating the separated polyamic acid for preparation. Polymer composition. When the poly (proline) is dehydrated and closed to form a polyimine, the above reaction solution can be directly used for the dehydration ring closure reaction; or the polylysine contained in the reaction solution can be separated and used for the dehydration ring closure reaction; or the separation can be carried out. After the polyamic acid is refined, it is used for the dehydration ring closure reaction. The separation and purification of polylysine can be carried out by a known method.

[Synthesis of Polyimine]

The above polyimine can be obtained by subjecting the polylysine synthesized as above to dehydration ring-closing ruthenium.

The polyimine in the present invention may be a complete hydrazine imide of a glycosidic acid structure in which the prolyl acid structure as a precursor thereof is dehydrated and closed; or a part of the proline structure may be dehydrated and closed, and the guanamine A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably 40% or more. The ruthenium imidization ratio is a ratio indicating the number of ruthenium ring structures in the percentage of the amount of the guanidine structure of the polyimine and the total amount of the quinone ring structure.

The dehydration ring closure of the polyamic acid is preferably carried out by heating the polyamic acid or dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating according to the necessity. . Among them, the latter method is preferably carried out.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mols based on the structure of the proline of 1 mol of polylysine. The dehydration ring-closing catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. The amount of the dehydration ring-closure catalyst used is preferably 0.01 to 10 moles per 1 mol of the dehydrating agent. The organic solvent used for the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature as the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

Thus, a reaction solution containing polyimine can be obtained. The reaction solution can be directly used for preparing a polymer composition, or can be used for preparing a polymer composition after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a polymerization after separating the polyimine. The composition of the material; or after the isolated polyimine is refined, used to prepare a polymer composition. These purification operations can be carried out according to a known method.

<(A) Ratio of use of the first polymer and (B) second polymer>

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

<Other ingredients>

The polymer composition used in the method of the present invention contains the (A) first polymer and the (B) second polymer as described above as essential components, and may contain other components.

Examples of other components which can be used herein include other polymers, radical polymer compounds, and compounds having at least one epoxy group in the molecule (wherein the first polymer corresponding to the above (A) is removed. substance). Hereinafter, it is called "epoxy compound", a functional decane compound, etc.

[Other polymers]

The other polymers described above can be used to improve the solution properties of the polymer composition and the electrical properties of the film formed from the polymer composition. The other polymer is a polymer other than the above (A) first polymer and (B) second polymer, and examples thereof include polyphthalate, polyester, polyamine, polyoxane, and A cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like.

The other polymer is preferably used in an amount of 40 parts by weight or less, more preferably 20 parts by weight or less based on 100 parts by weight of the (B) second polymer. In the present invention, it is preferred not to use other polymers.

[Radical Polymerizable Compound]

The above radical 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 preferably has at least one group selected from the group consisting of an acryloyl group and a methacryl group (hereinafter referred to as "radical polymerizable group". The compound of the group ") is more preferably a compound having 1 to 3 radical polymerizable groups and a liquid crystal-like structure at the same time. More preferably, the compound represented by the following formula (d1) (hereinafter referred to as "compound (d1)")) is preferably a compound having one radical polymerizable group.

In the formula (d1), R is a hydrogen atom or a methyl group, and 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 fluorene group. The family skeleton has a hydrocarbon group of 17 to 51; Z ^III is a single bond, *-O-, *-COO- or *-OCO- (wherein the "*" linkage is the R ^III side); ^IV is a cyclohexyl group or a phenyl group, wherein the cyclohexyl or phenyl group may be substituted by a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and n5 is 1 to 3 An integer; wherein, when n5 is 2 or 3, a plurality of R ^{IVs present} may be identical to each other or different; n6 is 0 or 1.

The compound having two radical polymerizable groups may be selected from di(meth)acrylate having a biphenyl structure, di(meth)acrylate having a phenyl-cyclohexyl structure, and having 2 At least one of a group consisting of a di(meth)acrylate of a 2-diphenylpropane structure and a di(meth)acrylate having a diphenylmethane structure (hereinafter, referred to as "compound (d2)") The compound having three radical polymerizable groups may, for example, be a tri(meth)acrylate of a trivalent or higher polyvalent alcohol (hereinafter referred to as "compound (d3)").

Specific examples of the compound (d1) include, for example, 4-(4-octadecylcyclohexyl)phenyl acrylate, 4-(4-butylcyclohexyl)phenyl methacrylate, and methacrylic acid 4 -(4-pentylcyclohexyl)phenyl ester, 4-(4-hexylcyclohexyl)phenyl methacrylate, 4-(4-octylcyclohexyl)phenyl methacrylate, 4-(4) methacrylate -nonylcyclohexyl)phenyl ester, 4-(4-dodecylcyclohexyl)phenyl methacrylate, 4-(4-hexadecylcyclohexyl)phenyl methacrylate, 4-methacrylic acid (4-octadecylcyclohexyl)phenyl ester, 4-(4-butylcyclohexyl)cyclohexyl acrylate, 4-(4-pentylcyclohexyl)cyclohexyl acrylate, 4-(4-hexyl acrylate) Cyclohexyl)cyclohexyl ester, 4-(4-octylcyclohexyl)cyclohexyl acrylate, 4-(4-fluorenylcyclohexyl)cyclohexyl acrylate, 4-(4-dodecylcyclohexyl acrylate) Cyclohexyl ester, 4-(4-hexadecylcyclohexyl)cyclohexyl acrylate, 4-(4-octadecylcyclohexyl)cyclohexyl acrylate, 4-(4-butylcyclohexyl methacrylate Cyclohexyl ester, 4-(4-pentylcyclohexyl)cyclohexyl methacrylate, 4-(4-hexylcyclohexyl)cyclohexyl methacrylate, methacrylic acid 4-(4-octylcyclohexyl)cyclohexyl ester, 4-(4-decylcyclohexyl)cyclohexyl methacrylate, 4-(4-dodecylcyclohexyl)cyclohexyl methacrylate, 4-(4-hexadecylcyclohexyl)cyclohexyl methacrylate, 4-(4-octadecylcyclohexyl)cyclohexyl methacrylate, 5-oxime-cholestane (meth)acrylate- 3-Based ester, (5)-cholesten-3-yl (meth)acrylate, 4-(4'-pentyldicyclohexyl-4-yl)phenyl (meth)acrylate, and the like.

Specific examples of the compound (d2) include, as a di(meth)acrylate having a biphenyl structure, for example, 4'-(meth)acryloyloxy-biphenyl-4 -yl ester, 2-[4'-(2-(methyl)propenyloxy-ethoxy)-biphenyl-4-yloxy]-ethyl (meth)acrylate, 2-(2-acrylic acid) 2-{4'-[2-(2-(methyl)acryloxy-ethoxy)-ethoxy]-biphenyl-4-yloxy}-ethoxy)-ethyl ester, Dihydroxyethylbiphenyl di(meth)acrylate; etc.; as the di(meth)acrylate of the phenyl-cyclohexyl structure, for example, 4-(4-(methyl)(meth)acrylate Propylene methoxy-phenyl)-cyclohexyl ester, 2-{4-[4-(2-(methyl) propylene oxy-ethoxy)-phenyl]-cyclohexyloxy (meth) acrylate And the like; as the di(meth)acrylate having a 2,2-diphenylpropane structure, for example, 4-[1-(4-(methyl)propene oxime (meth)acrylate) Oxy-phenyl)-1-methyl-ethyl]phenyl ester, 2-(4-{1-[4-(2-(methyl)propenyloxy-ethoxy)(meth)acrylate -Phenyl]-1-methyl-ethyl}-phenoxy)-ethyl ester, ethoxy-bisphenol A di(A) Acrylate or the like; as the di(meth)acrylate having a diphenylmethane structure, for example, 4-(4-(methyl)propenyloxy-benzyl)-phenyl (meth)acrylate , 2-{4-[4-(2-(methyl)propenyloxy-ethoxy)-benzyl]-phenyl}-ethyl (meth)acrylate, ethylene oxide of bisphenol F The di(meth)acrylate of the adduct, and the like.

Specific examples of the compound (d3) include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Ester, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, two Pentaerythritol hexamethacrylate, tris(2-propenyl methoxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate, and the like.

The radical polymerizable compound used in the present invention is preferably a compound (d1) or a compound (d2), and particularly preferably a compound (d1) wherein n5 in the above formula (d1) is 2 or 3 and n6 is 1. In the above formula (d1), R ^III is a compound (d1) having a hydrocarbon group of 17 to 51 having a steroid skeleton or a compound (d2) having a biphenyl structure of a biphenyl structure.

The use ratio of the radically polymerizable compound is preferably 50 parts by weight or less, more preferably 1 to 50 parts by weight, still more preferably 3 to 30 parts by weight, based on 100 parts by weight of the (B) second polymer. It is 5 to 15 parts by weight. By selecting such a use ratio, the liquid crystal display element produced does not cause such a problem that the voltage holding ratio is low, and the desired effect of the compound can be exhibited.

[epoxy compound]

The epoxy compound is preferably a compound having at least two epoxy groups in the molecule, and examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidyl Aminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine and the like are preferred.

The mixing ratio of these epoxy compounds is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of the (B) second polymer.

[functional decane compound]

The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropylamine. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, 3-guanidinopropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxylate Carbonyl-3-aminopropyltriethoxydecane, N-triethoxycarbenylpropyltriethylamine, N-trimethoxycarbamidopropyltriethylamine, 10 -trimethoxycarbamido-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamidinyl -3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazadecyl acetate, 9-trimethoxycarbamimidin-3,6- Methyl diazepine, methyl 9-triethoxycarbamilide-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl 3-aminopropyltriethyl Baseline, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidoxymethyltrimethoxydecane, glycidoloxy Methyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3 - glycidoxypropyl triethoxy decane, and the like.

The mixing ratio of these functional decane-containing compounds is preferably 2 parts by weight or less, more preferably 0.2 parts by weight or less, based on 100 parts by weight of the (B) second polymer.

<Polymer composition>

The polymer composition used in the present invention is preferably prepared by dissolving the (A) first polymer and (B) the second polymer as described above and other components used arbitrarily in a suitable organic solvent to form a solution.

Examples of the organic solvent which can be used herein include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-. Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxylate Propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol Methyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether Wait.

The ratio of use of the organic solvent to the solid content of the polymer composition (the ratio of the total weight of the components other than the organic solvent in the polymer composition to the total weight of the polymer composition) is preferably from 1 to 15% by weight. The ratio is preferably from 1.5 to 8% by weight.

<<Manufacturing method of liquid crystal display element>>

The method for producing a liquid crystal display device of the present invention is characterized in that the polymer composition as described above is applied to the conductive film of a pair of substrates having a conductive film to form a coating film; The coating film of the pair of substrates of the film is opposed to each other with the liquid crystal molecules interposed therebetween to form a liquid crystal cell, and the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

Here, as the substrate, for example, glass such as float glass or soda glass; plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate can be used. A transparent substrate or the like formed.

As the conductive film, a transparent conductive film is preferable, and for example, a NESA film formed of SnO ₂ , an ITO film formed of In ₂ O ₃ —SnO _{2 ,} or the like can be used. Each of the conductive films is preferably a patterned conductive film that is divided into a plurality of regions. With such a conductive film structure, when a voltage is applied between the conductive films (described later), by applying different voltages to the respective regions, the direction of the pretilt angle of the liquid crystal molecules in each region can be changed, whereby the viewing angle property can be broadened.

When the polymer composition is applied onto the conductive film of the substrate, it can be carried out by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. After coating, the coated surface is formed by preheating (prebaking) and then firing (post-baking). The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, more preferably 5 to 200 minutes, and more preferably 10 to 30 minutes. 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

The coating film thus formed can be directly supplied to the production of the liquid crystal cell of the later-described step, or the coating film can be subjected to a rubbing treatment as needed before the production of the liquid crystal cell. This rubbing treatment is performed by rubbing a roll of a cloth formed of a fiber such as nylon, rayon, or cotton onto a coating film surface in a certain direction. In the case of performing one rubbing treatment, a resist film is formed on a part of the surface of the coating film, and then rubbing treatment is performed in a direction different from the previous rubbing treatment, as described in Japanese Laid-Open Patent Publication No. H5-107544. By removing the resist film, by performing such a treatment, different rubbing methods are formed for the respective regions, and the viewing angle properties of the obtained liquid crystal display element can be further improved.

Next, the coating film of the pair of substrates on which the coating film is formed is disposed to face each other with the liquid crystal molecules interposed therebetween to form a liquid crystal cell.

As the liquid crystal molecule used herein, a nematic liquid crystal having a negative dielectric anisotropy is preferably used, and for example, a dicyanobenzene liquid crystal or a ruthenium can be used. Liquid crystal, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like. The layer of the liquid crystal molecules is preferably from 1 to 5 μm.

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

In the first method, in order to align the liquid crystal alignment films, the two substrates are opposed to each other with a gap (cell gap) interposed therebetween, and the peripheral portions of the two substrates are bonded together using a sealant. After filling the liquid crystal into the cell gap separated by the surface and the sealant, the injection hole is sealed to manufacture a liquid crystal cell. Alternatively, as a second method, a sealing agent such as an ultraviolet curable layer is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and then liquid crystal is dropped on the liquid crystal alignment film surface, and then laminated. The other substrate is opposed to the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent, whereby the liquid crystal cell can be manufactured.

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

The voltage applied here may be, for example, a direct current or an alternating voltage of 5 to 50 volts.

As the light to be irradiated, ultraviolet rays and visible rays including light having a wavelength of, for example, 150 to 800 nm, and ultraviolet rays of light having a wavelength of 300 to 400 nm are preferably used. As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength region can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, or the like.

The irradiation amount of light is preferably 1,000 J/m ² or more, less than 100,000 J/m ² , and more preferably 1,000 to 50,000 J/m ² . In the production of a liquid crystal display element of a PSA mode which is known in the prior art, it is necessary to irradiate light of 100,000 J/m ² , but in the present invention, even if the amount of light irradiation is 50,000 J/m ² or less, further 10,000 J/m ² In the following, a desired liquid crystal display element can be obtained, and in addition to contributing to reduction in the manufacturing cost of the liquid crystal display element, it is possible to avoid deterioration of electrical properties due to strong light irradiation and low long-term reliability.

Then, a liquid crystal display element can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell after the above-described treatment. The polarizing plate used herein includes a polarizing film formed by sandwiching a polarizing film called absorbing iodine called "H film" with a cellulose acetate protective film, and a polarizing film formed by the H film itself. Film and so on.

<<Liquid crystal display element>>

The liquid crystal display element manufactured by the method of the present invention has a wide viewing angle, extremely fast response speed of liquid crystal molecules, excellent display properties and long-term reliability, and is reduced in manufacturing cost and low in cost, so it is suitable for application including two-dimensional display and Three-dimensional display of various uses of LCD TVs.

[Examples] <(A) Synthesis of First Polymer> Synthesis Example S-1 [Hydrolysis condensation reaction]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 73.9 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) as a hydrolyzable decane compound was added. And 24.8 g of γ-methacryloxypropyltrimethoxydecane (GMPTS) (ECETS: GMPTS=75:25 (mole ratio)) and 500 g of methyl isobutyl ketone as a solvent and as a catalyst 10.0 g of triethylamine was mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred at reflux for 6 hours at 80 ° C under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to obtain a hydrolyzed condensate having an epoxy group, which was viscous. Transparent liquid.

The hydrolysis condensate was subjected to ¹ H-NMR analysis, and an epoxy group-based peak having a theoretical strength was obtained in the vicinity of the chemical shift (d) = 3.2 ppm, and it was confirmed that no epoxy reaction occurred in the epoxy group during the reaction.

[Reaction of a hydrolysis condensate having an epoxy group and a 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 hydrolyzed condensate having an epoxy group obtained above. (corresponding to the epoxy group of the hydrolysis condensate, equivalent to 30 mol%) and 0.10 g of UCAT 18X (trade name, curing accelerator of epoxy compound manufactured by Sanapro) as a catalyst, at 100 The reaction was carried out by stirring at ° C for 48 hours. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times, dried over magnesium sulfate, and then evaporated to give 100.2 g of polyorganooxane as the (A) first polymer ( PS-1). The polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography (GPC) of the polyorganosiloxane (PS-1) was 7,100.

Synthesis Examples S-2 to S-6, S-10, S-11 and S-16 [Hydrolysis condensation reaction] and [Reaction of a hydrolysis condensate having an epoxy group and a carboxylic acid]

In the same manner as in Synthesis Example S-1 except that the hydrolyzable decane compound and the carboxylic acid of the type and amount described in Table 1 were used, the hydrolysis condensation reaction and the hydrolysis condensate and the carboxylic acid were carried out in the same manner as in the above Synthesis Example S-1. The reaction was carried out to obtain polyorganosiloxane (PS-2) to (PS-6), (PS-10), (PS-11) and (PS-16) as the first polymer of (A), respectively. The yield and Mw of these polyorganosiloxanes are combined and shown in Table 1. Further, in Synthesis Examples S-3 to S-5 and S-16, two carboxylic acids were used for each. Synthesis Example S-6 is a comparative synthesis example.

Synthesis Example S-7~S-9 [Hydrolysis condensation reaction]

In the same manner as in the synthesis example S-1 except that the hydrolyzable decane compound of the type and amount described in Table 1 was used, the hydrolysis condensation reaction was carried out in the same manner as in the synthesis example S-1, and the polymer as the first (A) was obtained. Polyorganosiloxane (PS-7) ~ (PS-9). The yield and Mw of these polyorganosiloxanes are combined and shown in Table 1.

Synthesis Example S-12 [Hydrolysis condensation reaction]

In the same manner as in Synthesis Example S-1 except that the hydrolyzable decane compound of the type and amount described in Table 1 was used, the hydrolysis-condensation reaction was carried out in the same manner as in Synthesis Example S-1 to obtain a hydrolyzable condensate having an acrylonitrile group. It is a viscous transparent liquid.

[Reaction of a hydrolyzed condensate having an acrylonitrile group and a 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 22.3 were added. g The triethylamine as a catalyst was heated to 50 ° C and stirred for 90 minutes to carry out a reaction. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and the catalyst were distilled off under reduced pressure to obtain 225.3 g of a polymer as the (A) first polymer. Organic germanium oxide (PS-12) is a viscous transparent liquid. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the polyorganosiloxane (PS-12) was 7,400.

Synthesis Example S-13 [Hydrolysis condensation reaction]

In the same manner as in Synthesis Example S-1 except that the hydrolyzable decane compound of the type and amount described in Table 1 was used, the hydrolysis-condensation reaction was carried out in the same manner as in Synthesis Example S-1 to obtain a hydrolyzable condensate having an acrylonitrile group. It is a viscous transparent liquid.

[Reaction of a hydrolyzed condensate having an acrylonitrile group and a nucleophilic compound (amine)]

In a 500 mL three-necked flask equipped with a stirrer and a thermometer, 165.3 g of the above-mentioned hydrolysis condensate, 48.3 g of di-n-octylamine (DOA) as a nucleophilic compound (amine), and 160 mL of acetonitrile as a solvent were added, and the temperature was raised to 50. The reaction was carried out by stirring at ° C for 6 minutes. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and the solvent was distilled off under reduced pressure to obtain 212.2 g of polyorganooxyl as the (A) first polymer. Alkane (PS-13), a viscous transparent liquid. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the polyorganosiloxane (PS-13) was 7,200.

Synthesis Examples S-14 and S-15 [Hydrolysis condensation reaction] and [Reaction of a hydrolysis condensate having an acrylonitrile group with a nucleophilic compound (thiol)]

Hydrolysis condensation reaction and hydrolysis condensation were carried out in the same manner as in Synthesis Example S-12, except that the hydrolyzable decane compound and the nucleophilic compound (thiol) of the type and amount described in Table 1 were used in the above Synthesis Example S-12. The reaction with the nucleophilic compound gives polyorganosiloxane (PS-14) and (PS-16) as the first polymer of (A), respectively. The yield and Mw of these polyorganosiloxanes are combined and shown in Table 1.

Synthesis Example S-17 [Reaction of a sesquiterpene oxide having a propylene fluorenyl group and a nucleophilic compound (thiol)]

In addition to the above-mentioned Synthesis Example S-12, 165.0 g of AC-SQ TA-100 (manufactured by Toagos Corporation) having a sesquiterpene oxide having an acrylonitrile group was used instead of the synthesized hydrolysis condensate to be used as a nucleophile. The amount of the n-dodecyl-1-thiol (DT) compound used was 40.5 g, and the reaction was carried out in the same manner as in the reaction of the hydrolysis condensate and the nucleophilic compound in Synthesis Example S-12, and the first was obtained as (A). Polymeric polyorganosiloxane (PS-17). The yield and Mw of the polyorganooxane are shown in Table 1.

[Table 1]

[Table 2]

The abbreviations of the respective compounds in Table 1 are respectively the following meanings.

{hydrolyzable decane compound}

ECETS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

GMPTS: γ-methacryloxypropyltrimethoxydecane

GAPTS: γ-propylene methoxypropyl trimethoxy decane

{sesquioxane having an acryloyl group}

ACSQ: trade name "AC-SQ TA-100", East Asia Synthetic (Stock) Manufacturing

{carboxylic acid}

OCTBA: 4-octyloxybenzoic acid

ACRYA: Acrylic

AEHEP: 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid

MACBA: 4-(2-methyl-acryloxy)benzoic acid

Further, the amount of the carboxylic acid used is the molar % of the epoxy group which is present with respect to the hydrolysis condensate. In Synthesis Examples S-3 to S-5 and S-16, two carboxylic acids were used for each.

{nucleophilic compound} Mercaptan

DT: n-dodecyl-1-thiol

PCBT: 4-(4'-pentylcyclohexyl)phenylthiol

BT: n-butyl-1-thiol

amine

DOA: di-n-octylamine

The mark of "--" in Table 1 means that the compound corresponding to the column is not used.

<(B) Synthesis of Second Polymer> Synthesis Example P-1

110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride of tetracarboxylic dianhydride, 43 g (0.40 mol) as diamine phenylenediamine, 52 g (0.10 Mo) The ear) 3-(3,5-diaminobenzylideneoxy)cholesterane was dissolved in 830 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 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 the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new N-methyl-2-pyrrolidone (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system), thereby obtaining about 15 % by weight of a solution of the polyethylenimine (PI-1) having a ruthenium iodide ratio of about 50% as the (B) second polymer. A small amount of the obtained polyimine solution was added, and N-methyl-2-pyrrolidone was added to form a solution having a concentration of 10% by weight of polyimine, and the measured solution viscosity 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 (1.0 mol) of 2,2'-dimethyl as a diamine -4,4'-diaminobiphenyl, dissolved in 3,670 g of N-methyl-2-pyrrolidone, and reacted at 40 ° C for 3 hours to obtain a polymer containing 10% by weight of (B) a second polymer A solution of proline (PA-1). The solution viscosity of the polyamic acid solution was 160 mPa ‧ s.

Synthesis Example P-3

98 g (0.50 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 110 g (0.50 mol) of benzenetetracarboxylic dianhydride and 200 g of diamine as tetracarboxylic dianhydride (1.0 mol) 4,4'-diaminophenylmethane, dissolved in 2,330 g of N-methyl-2-pyrrolidone, reacted at 40 ° C for 3 hours, and added 1,350 to the obtained reaction mixture. The N-methyl-2-pyrrolidone of g gave a solution containing 10% by weight of polyamine (PA-2) as the (B) second polymer. The solution viscosity of the polyaminic acid solution was 125 mPa ‧ s.

Example 1 <Preparation of polymer composition>

N-methyl-2-pyrrolidone (NMP) as an organic solvent was added to a solution containing 100 parts by weight of the polyimine (PI-1) obtained in the above Synthesis Example P-1 as the (B) second polymer. And butyl cellosolve (BC), and then 5 parts by weight of the polyorganosiloxane (PS-1) obtained in the above Synthesis Example S-1 as the (A) first polymer to form a solvent composition NMP: BC = 50 : 50 (weight ratio), a solution having a solid content concentration of 6.0% by weight. This solution was filtered using a screening procedure having a pore size of 1 μm to prepare a polymer composition.

<Manufacture and evaluation of liquid crystal cells>

Using the polymer composition prepared above, a total of six liquid crystal display elements were produced and evaluated by changing the pattern (two types) of the transparent electrodes and the ultraviolet irradiation amount (three standards) as described below.

[Manufacture of liquid crystal cell with non-patterned transparent electrode]

The above-prepared polymer composition was applied onto a transparent electrode surface of a glass substrate having a transparent electrode formed of an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photographic Co., Ltd.), and a hot plate at 80 ° C was used. After heating for 1 minute (prebaking), the solvent was removed, and heated on a hot plate at 150 ° C for 10 minutes (post-baking) to form an average film thickness of 600. Coating film.

The coating film was subjected to a rubbing treatment under the conditions of a roll rotation number of 400 rpm, a platen moving speed of 3 cm/s, and a pile press-in length of 0.1 mm using a friction device having a roll of rayon cloth wound thereon. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying 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 pieces) of substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive having a diameter of 5.5 μm is applied to each of the outer edges of the pair of substrates having the liquid crystal alignment film, and then the pressure is bonded to make the liquid crystal alignment film face opposite, and the adhesive is applied. Cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

The above operation was repeated to fabricate three liquid crystal cells having a pattern-free transparent electrode. One of them is directly used for the pretilt angle evaluation described later. The remaining two liquid crystal cells were used to evaluate the pretilt angle and the voltage holding ratio after light irradiation in a state where a voltage was applied between the conductive films by the following method.

For the two of the liquid crystal cells obtained above, an alternating current voltage of 60 Hz was applied between the electrodes, and in the state where the liquid crystal was driven, an ultraviolet irradiation device using a metal halide lamp as a light source at 10,000 J/m was used. ² or 100,000 J/m ² irradiation. Further, the irradiation amount is a value measured by a photometer measured on the basis of a wavelength of 365 nm.

[Evaluation of pretilt angle]

Each of the liquid crystal cells manufactured as described above is according to Non-Patent Document 3 (TJ Scheffer et. al., J. Appl. Phys. vo. 48, p. 1783 (1977)) and Non-Patent Document 4 (F. Nakano et. al, respectively). The method described in JPN. J. Appl. Phys. vo. 19, p. 2013 (1980)), by using a He-Ne laser crystal rotation method, measuring the value of the angle from the liquid crystal molecule to the substrate surface. This value is the pretilt angle.

The pretilt angles of the liquid crystal cells which were not irradiated with light, the liquid crystal cells having an irradiation amount of 10,000 J/m ² , and the liquid crystal cells having an irradiation amount of 100,000 J/m ² are shown in Table 3.

[Evaluation of voltage retention rate]

Each of the liquid crystal cells produced as described above was applied with a voltage of 5 V at an application time of 60 μsec and an interval of 167 msec at 23 ° C, and then the voltage holding ratio after the application was released for 167 msec was measured. As the measuring device, VHR-1 of TOYO Technica Co., Ltd. was used.

Each voltage holding ratio of the liquid crystal cell is irradiated with an amount of 10,000J / m ² of the liquid crystal cell and an amount of irradiation 100,000J / m ₂ are shown in Table 3.

[Manufacture of liquid crystal cell having patterned transparent electrode (1)]

A liquid crystal alignment film printer (Japanese Photographic Printing Co., Ltd.) is used on each of the electrode surfaces of the glass substrates A and B which are formed into the slit-shaped pattern shown in FIG. Manufactured, the polymer composition prepared above was applied, heated on a hot plate at 80 ° C for 1 minute (prebaking), and after removing the solvent, it was heated on a hot plate at 150 ° C for 10 minutes (post-baking) to form an average. Film thickness 600 Coating film. The coating film was ultrasonically washed in ultrapure water for 1 minute, 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 pieces) of substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive having a diameter of 5.5 μm is applied to each of the outer edges of the pair of substrates having the liquid crystal alignment film, and then the pressure is bonded to make the liquid crystal alignment film face opposite, and the adhesive is applied. Cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

The above operation was repeated to fabricate three liquid crystal cells having a patterned transparent electrode. One of them is directly used for the response speed evaluation described later. The remaining two liquid crystal cells are irradiated by 10,000 J/m ² or 100,000 J/m ² in the same manner as in the production of the liquid crystal cell having the transparent electrode having no pattern, by applying a voltage between the conductive films. After the amount of light is irradiated, it is used to evaluate the response speed.

In addition, the electrode pattern used here is the same pattern as the electrode pattern in the PSA mode.

[evaluation of response speed]

No voltage was applied to each of the liquid crystal cells manufactured as described above, and a visible light lamp was irradiated, and the brightness of light transmitted through the liquid crystal cell was measured by a photo multimeter, and the value was 0% relative to the transmittance. Next, the transmittance at the time of applying a voltage of 60 V alternating current for 5 seconds between the electrodes of the liquid crystal cell was measured in the same manner as described above, and this value was made into a relative transmittance of 100%.

At this time, when a voltage of 60 V was applied to each liquid crystal cell, the time when the relative transmittance was changed from 10% to 90% was measured, and this time was defined as the response speed.

The respective response speeds of liquid crystal cells which were not irradiated with light, liquid crystal cells having an irradiation amount of 10,000 J/m ² , and liquid crystal cells having an irradiation amount of 100,000 J/m ² are shown in Table 3.

[Manufacture of liquid crystal cell having patterned transparent electrode (2)]

In addition to the use of the polymer composition prepared above, the production of liquid crystal cells other than the glass substrates A and B each having the ITO electrode of the fishbone pattern shown in Fig. 2, and the transparent electrode having the above-described pattern was used (1) In the same manner, a liquid crystal cell in which light was not irradiated, a liquid crystal cell having an irradiation amount of 10,000 J/m ^{2 , and} a liquid crystal cell having an irradiation amount of 100,000 J/m ² were produced, and the response speed was evaluated in the same manner as described above. The evaluation results are shown in Table 3.

Examples 2~23 and 27~29

A polymer composition was produced in the same manner as in Example 1 except that the types and amounts of the (A) first polymer and the (B) second polymer were as described in Table 2, respectively, and the same was used. Various liquid crystal cells were evaluated. Further, in Examples 11, 12, 15 to 17, 22, 28 and 29, two (B) second polymers were each used respectively.

The evaluation results are shown in Table 3.

Example 24 <Preparation of polymer composition>

N-methyl-2-pyrrolidone (NMP) as an organic solvent was added to a solution containing 100 parts by weight of the polyimine (PI-1) obtained in the above Synthesis Example P-1 as the (B) second polymer. And butyl cellosolve (BC) to which 6 parts by weight of the polyorganosiloxane (PS-1) obtained in the above Synthesis Example S-1 as the (A) first polymer and 5 parts by weight are added as a radical polymerization The compound 5-methyl-cholest-3-yl methacrylate (MACY) was formed into a solvent having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid concentration of 6.0% by weight. This solution was filtered using a screening procedure having a pore size of 1 μm to prepare a polymer composition.

<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

The polymer composition was prepared in the same manner as in Example 24 except that the type and amount of the radically polymerizable compound were as described in Table 2, and various liquid crystal cells were produced and evaluated. Further, in Example 25, two kinds of radical polymerizable compounds were used.

The evaluation results are shown in Table 3.

Comparative example 1

A polymer composition was prepared in the same manner as in Example 1 except that the (A) first polymer was not used, and various liquid crystal cells were produced and evaluated.

The evaluation results are shown in Table 3.

Comparative example 2~4

A polymer composition was prepared in the same manner as in Example 1 except that the other polymer or compound shown in Table 2 was used instead of the (A) first polymer in the amounts shown in Table 2, respectively. It was evaluated by using it to manufacture various liquid crystal cells.

The evaluation results are shown in Table 3.

[table 3]

[Table 4]

The abbreviations in Table 2 are respectively the following meanings.

[other compounds]

Ra-1: a compound represented by the following formula (ra-1)

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

[Radical Polymerizable Compound]

MACY: 5-ξ-cholest-3-yl methacrylate

PBCHPM: 4-(4'-pentyldicyclohexyl-4-yl)phenyl methacrylate

HEIXA: dipentaerythritol hexaacrylate

A-BP-2EO: 2-[4'-(2-propenyloxy-ethoxy)-biphenyl-4-yloxy]-ethyl acrylate

The mark of "--" in Table 1 means that the compound corresponding to the column is not used.

[table 5]

[Table 6]

As is clear from the results of Table 3, in the method of the present invention, if the ultraviolet irradiation amount is made 100,000 J/m ² (which is the value currently used in the PSA mode), the degree of the pretilt angle obtained is excessive, at 10,000 J. A suitable pretilt angle is formed at an irradiation dose of /m ² or less. Further, even when the amount of irradiation is small, a sufficiently fast response speed can be obtained, and the voltage holding ratio is also excellent.

Therefore, according to the method of the present invention, since the advantage of the PSA mode can be realized with a small amount of light irradiation, it is possible to manufacture a problem of occurrence of display spots caused by no high-light irradiation amount, low voltage holding ratio, and insufficient long-term reliability, and a viewing angle. Wide liquid crystal display elements with fast response, high transmittance, and high contrast.

1. . . ITO electrode

2. . . Slit

3. . . Sunscreen

1 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film produced in Examples and Comparative Examples.

2 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film produced in Examples and Comparative Examples.

Claims (15)

A method for producing a liquid crystal display device, characterized in that the method comprises the steps of: coating a polymer composition on the conductive film of a pair of substrates having a conductive film to form a coating film, the polymer composition containing : (A) a first polymer, which is a polyorganosiloxane having a (meth) acrylonitrile group, and (B) a second polymer selected from the group consisting of polyamines At least one of the group consisting of an acid and a polyimine; and (A) the first polymer is used in an amount of 2 to 60 parts by weight with respect to 100 parts by weight of the (B) second polymer; The coating film of the pair of substrates of the film is opposed to each other with the liquid crystal layer facing each other to form a liquid crystal cell having such a configuration, and the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The method for producing a liquid crystal display device according to the first aspect of the invention, wherein the (A) first polymer further has a group represented by 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 or a fluorine atom, or a carbon atom having a steroid skeleton; a hydrocarbon group of 17 to 51; Z ^I is a single bond, *-O-, *-COO- or *-OCO-, wherein a bond having a "*" is a R ^I side; and R ^II is a cyclohexylene group or a benzene stretching group. a group wherein the cyclohexyl or phenyl group may be substituted by a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms, and n1 is 1 or 2; wherein, when n1 is 2, two R ^II may be the same as or different from each other; n2 is 0 or 1; Z ^II is *-O-, *-COO- or *-OCO-, wherein the linkage with "*" is the R ^I side; n3 Is an integer from 0 to 2; n4 is 0 or 1. The method for producing a liquid crystal display device according to the first aspect of the invention, wherein the (A) first polymer is a hydrolysis condensate of a hydrolyzable decane compound, wherein the hydrolyzable decane compound comprises a (meth) acrylonitrile group. Hydrolyzable decane compound. The method for producing a liquid crystal display element according to claim 1, wherein the (A) first polymer is a reaction product of a hydrolysis condensate of a hydrolyzable decane compound and a carboxylic acid, wherein the hydrolyzable decane compound comprises an epoxy group. A hydrolyzable decane compound comprising a carboxylic acid having a (meth) acrylonitrile group. The method for producing a liquid crystal display element according to claim 2, wherein the (A) first polymer is a polyorganosiloxane having a (meth)acryl fluorenyl group and a group selected from the group consisting of an amine and a thiol. A reaction product of at least one nucleophilic compound, wherein the nucleophilic compound comprises a nucleophilic compound having a group represented by the above formula (D ⁰ ). The method for producing a liquid crystal display device according to claim 5, wherein the polyorganosiloxane having a (meth)acryl fluorenyl group is a hydrolysis condensate of a hydrolyzable decane compound, wherein the hydrolyzable decane compound comprises ( A hydrolyzable decane compound of a methyl) acrylonitrile group. The method for producing a liquid crystal display device according to claim 5, wherein the polyorganosiloxane having a (meth)acryl fluorenyl group is a reaction product of a hydrolysis condensate of a hydrolyzable decane compound and a carboxylic acid, wherein the hydrolysis The decane compound contains a hydrolyzable decane compound having an epoxy group containing a carboxylic acid having a (meth) acrylonitrile group. The method for producing a liquid crystal display device according to any one of claims 5 to 7, wherein the nucleophilic compound is an amine, and R ^I in the above 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 method for producing a liquid crystal display device according to any one of claims 5 to 7, wherein the nucleophilic compound is a thiol, and R ^I in the above formula (D ⁰ ) is an alkane having 2 to 12 carbon atoms. A fluoroalkyl group having 2 to 12 carbon atoms or a carbon atom. The method for producing a liquid crystal display device according to the second aspect of the invention, wherein the (A) first polymer is a reaction product of a hydrolysis condensate of a hydrolyzable decane compound and a carboxylic acid, wherein the hydrolyzable decane compound comprises (a) A hydrolyzable decane compound having an acrylonitrile group and a hydrolyzable decane compound having an epoxy group containing a carboxylic acid having a group represented by the above formula (D ⁰ ). The method for producing a liquid crystal display element according to the second aspect of the invention, wherein the (A) first polymer is a reaction product of a hydrolysis condensate of a hydrolyzable decane compound and a carboxylic acid, wherein the hydrolyzable decane compound comprises an epoxy group. A hydrolyzable decane compound comprising a carboxylic acid having a (meth) acrylonitrile group and a carboxylic acid having a group represented by the above formula (D ⁰ ). The method for producing a liquid crystal display device according to claim 10, wherein RI in the above formula (D ⁰ ) is an alkyl group having 4 to 40 carbon atoms or a fluoroalkane having 4 to 40 carbon atoms. a base or a hydrocarbon group having a steroidal skeleton having 17 to 51 carbon atoms. The method for producing a liquid crystal display device according to any one of claims 1 to 7, wherein the conductive film is a patterned conductive film which is divided into a plurality of regions. A polymer composition which is a polymer composition for producing a liquid crystal display element according to claim 1 of the invention, characterized in that it comprises: (A) a first polymer, the first polymerization Is a polyorganosiloxane having a (meth) acrylonitrile group, and (B) a second polymer selected from the group consisting of polylysine and At least one of the group consisting of polyimine; and (A) the first polymer is used in a proportion of 2 to 60 parts by weight with respect to 100 parts by weight of the (B) second polymer. A liquid crystal display element manufactured by the method for producing a liquid crystal display element according to any one of claims 1 to 13.