KR20110049677A - Process for producing liquid crystal display device, liquid crystal display device produced thereby and related compositions - Google Patents

Abstract

PURPOSE: A manufacturing method of a liquid crystal display device, a liquid crystal display element and related composition which are manufactured by the same are provided to have a wide viewing angle, to have fast responding speed of a liquid crystal molecule, and to have excellent display characteristic and reliability. CONSTITUTION: A manufacturing method of a liquid crystal display device forms a conductive layer by spraying a polymer composition. The polymer composition includes a first polymer and a second polymer. The first polymer is a polyorganosiloxane having (meta)acryloyl on conductive film of a pair of substrate which has a conductive film. The second polymer is at least one type selected from a group comprised of a polyamic acid and polyimide.

Description

The manufacturing method of a liquid crystal display element, the liquid crystal display element manufactured by this, and its related composition TECHNICAL FIELD AND LIQUID CRYSTAL DISPLAY DEVICE PRODUCED THEREBY AND RELATED COMPOSITIONS

TECHNICAL FIELD This invention relates to the manufacturing method of a liquid crystal display element, the liquid crystal display element manufactured by this, and the related composition. More specifically, the present invention relates to a novel method for producing a liquid crystal display device having a wide viewing angle and a fast response speed.

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

Recently, in order to solve the problems of the MVA panel, a PSA (Polymer® Sustained Alignment) mode has been proposed. The PSA mode is polymerizable in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film having no pattern, or a gap of a pair of substrates formed of two substrates with a patterned conductive film. The liquid crystal composition containing the compound is sandwiched, and ultraviolet rays are irradiated in a state where a voltage is applied between the conductive films to polymerize the polymerizable compound, thereby expressing the pretilt angle characteristics. To control the alignment direction of the liquid crystal. According to this technique, by setting the conductive film in a specific configuration, the viewing angle can be increased and the liquid crystal molecular response can be increased, and the problem of lack of transmittance and contrast, which is inevitable in the MVA panel, is also eliminated. However, for the polymerization of the polymerizable compound, a large amount of ultraviolet irradiation, for example, 100,000 J / m 2, is required, and thus, a problem of decomposing the liquid crystal molecules occurs, and the unpolymerized polymer is not polymerized even by ultraviolet irradiation. It is clear that reaction compounds remain in the liquid crystal layer, and these interact with each other to cause display unevenness, which adversely affects voltage integrity characteristics or causes problems in long-term reliability of the panel.

About these, Nonpatent literature 1 has proposed the method of using the liquid crystal aligning film formed from the polyimide-type liquid crystal aligning agent containing a reactive mesogen. According to the nonpatent literature 1, the liquid crystal display element provided with the liquid crystal aligning film formed by such a method says that the response of a liquid crystal molecule is high speed. However, Non-Patent Document 1 does not describe any reactive mesogen in what amount, and there is still a large amount of ultraviolet irradiation required, and there is no concern about display characteristics, especially voltage preservation characteristics. .

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

 Y.-J. Lee et. al. SID 09 DIGEST, p.666 (2009)  Chemical Reviews, Vol. 95, p. 1409 (1995).  T. J. Scheffer et. al., J. Appl. Phys. vo. 48, p. 1783 (1977)  F. Nakano et. al., JPN. J. Appl. Phys. vo. 19, p. 2013 (1980)

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

According to the present invention, the above objects and advantages of the present invention,

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

(A) the first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and also

(B) at least one second polymer selected from the group consisting of polyamic acid and polyimide

A coating film is formed by applying a polymer composition containing

The said coating film of the pair of board | substrates which provided the said coating film forms the liquid crystal cell of the structure arrange | positioned opposingly through the liquid crystal layer,

It is achieved by the manufacturing method of a liquid crystal display element which goes through the process of irradiating light to the said liquid crystal cell in the state which applied the voltage between the conductive films which a pair of board | substrates have.

The liquid crystal display device 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, excellent display characteristics, and no display characteristics are impaired even when continuously driven for a long time. .

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

Therefore, the liquid crystal display element manufactured by the method of this invention is superior to the liquid crystal display element conventionally known in both a performance aspect and a cost aspect, and is various uses including the liquid crystal television of a two-dimensional display and a three-dimensional display. It can be applied very suitably.

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

(Form to carry out invention)

<< polymer composition >>

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

(A) the first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and also

(B) It contains the 2nd polymer which is at least 1 sort (s) chosen from the group which consists of polyamic acid and polyimide.

<(A) First Polymer>

The (A) 1st polymer used by this invention is polyorganosiloxane which has a (meth) acryloyl group. When the first polymer has a (meth) acryloyl group, the film formed of the polymer composition containing the same has the advantage that the desired pretilt angle expression is imparted with a small amount of light irradiation by the method of the present invention.

In addition to the (meth) acryloyl group, the first polymer has the following formula (D ⁰ ):

(In 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 hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton;

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

R ^II is a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms,

n1 is 1 or 2,

Provided that when n1 is 2, the 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 bond to which "*" is attached is the R ^I side),

n3 is an integer of 0 to 2,

n4 is 0 or 1)

You may further have at least 1 sort (s) of group chosen from the group which consists of group and epoxy group represented by these.

The expression Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group as an alkyl group having a carbon number of 1 to 40 of the R ^I in the (D ⁰⁾ , Hexadecyl group, stearyl group and the like;

Specific examples of the fluoroalkyl group having 1 to 40 carbon atoms include trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group, and pentafluoroethylpropyl group. A pentafluoroethyl butyl group, a pentafluoroethyl octyl group;

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

The expression (D ⁰⁾ group-cyclohexylene group and a phenylene group of the R in ^II, it is preferred that each 1,4-cyclohexylene group and a 1,4-phenylene group. Examples of the divalent group represented _by- (R ^II ) _n1 -in the formula (D ⁰ ) include a 1,4-phenylene group, a 1,2-cyclohexylene group, and the like, when n1 is 1;

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

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

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

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

As the first polymer having a group represented by the above formula such (D ^0), it is preferable that the film exhibits excellent liquid crystal aligning capability formed from a polymer composition containing the same.

Moreover, when a 1st polymer has an epoxy group, the film | membrane formed from the polymer composition containing this has a strong mechanical characteristic, excellent the performance of heat resistance, light resistance, etc., and is preferable.

(A) 1st polymer in this invention,

It is preferable to have a (meth) acryloyl group 0.0003 mol / g or more, and it is more preferable to have 0.0004-0.008 mol / g;

Preferably having a group represented by the above formula (D ⁰⁾ in the range of more than 0.005 mol / g, and from 0.0002 to 0.003 and more preferably having mole / g;

It is preferable to have an epoxy group in the range of 0.004 mol / g or less, and it is more preferable to have 0.0009-0.003 mol / g.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) with respect to a 1st polymer is 500-100,000, It is more preferable that it is 1,000-50,000, It is further more preferable that it is 1,000-10,000. .

As long as such (A) 1st polymer has such a group, Preferably it has the weight average molecular weight of the said range, its manufacturing method is not limited, For example, it can manufacture by the following method. have.

Production of the 1st polymer which is a polyorganosiloxane which has a (meth) acryloyl group, for example

(1) A method of hydrolytically condensing a hydrolyzable silane compound (wherein the hydrolyzable silane compound contains a hydrolyzable silane compound having a (meth) acryloyl group (hereinafter also referred to as "compound (a1)")) , or

(2) a hydrolytic condensate of a hydrolyzable silane compound (wherein the hydrolyzable silane compound contains a hydrolyzable silane compound having an epoxy group (hereinafter also referred to as "compound (a2)"));

It can be based on the method of reacting carbonic acid (However, this carbonic acid contains the carbonic acid which has a (meth) acryloyl group (henceforth a "compound (b1)".).). As a polyorganosiloxane which has a (meth) acryloyl group, commercial items, such as AC-SQ TA-100 (made by Toagosei Co., Ltd.), can also be used, for example.

(Meth) Preparation of the first polymer of polyorganosiloxane having both a group represented by acryloyl group and the above formula (D ⁰⁾ is, for example,

(3) Hydrolyzable silane compound (However, this hydrolyzable silane compound includes a hydrolyzable silane compound (compound (a1)) having a (meth) acryloyl group and a hydrolyzable silane compound (compound (a2)) having an epoxy group.) Hydrolysis condensate)

A method of reacting a carbonic acid (wherein the carbonic acid contains a carbonic acid having a group represented by the formula (D ⁰ ) (hereinafter also referred to as "compound (b2)")),

(4) a hydrolytic condensate of a hydrolyzable silane compound (wherein the hydrolyzable silane compound contains a hydrolyzable silane compound (compound (a2)) having an epoxy group);

A carbonic acid, provided that the carbonic acid reacts with a carbonic acid having a (meth) acryloyl group (compound (b1)) and a carbonic acid having a group represented by the formula (D ⁰ ) (compound (b2)). How to make or

(5) with polyorganosiloxane having a (meth) acryloyl group

At least one nucleophile compound selected from the group consisting of amines and thiols, provided that the nucleophile compound is reacted with a nucleophilic compound having a group represented by the above formula (D ⁰ ). Can be. The polyorganosiloxane which has the (meth) acryloyl group of the raw material used by the said method (5) is obtained by the said method (1) or (2), For example, AC-SQ TA-100 (Toa Kosei Co., Ltd. product) etc. can also be used.

As used herein, the term "hydrolysis-condensation product" refers to the hydrolysis-condensation of a hydrolysis-condensation product obtained by hydrolyzing and condensing one type of hydrolyzable silane compound and a mixture of two or more types of hydrolyzable silane compounds. It is a concept including both with the co-hydrolysis condensate obtained by combining.

In the above methods (2) to (4), the hydrolyzed condensate has an epoxy group derived from a hydrolyzable silane compound, and the polyorgano having a desired group by further reacting the epoxy group of the hydrolyzed condensate with a predetermined carbonic acid. A first polymer is obtained which is a siloxane.

Here, in the said method (2), by making the use rate of a carbonic acid into a ratio less than the epoxy group which a hydrolysis-condensation product has, the 1st polymer is made into the polyorganosiloxane which further has an epoxy group other than a (meth) acryloyl group. can do. The same applies when using the hydrolysis-condensation product obtained by the said method (2) as a raw material in the said method (5). In addition, in the said method (3) and the method (4), the hydrolysis-condensation product uses the carbonic acid use ratio (the ratio of the sum total of a compound (b1) and a compound (b2) in the said method (4)). by having a small percentage of all the epoxy group it can be a first polymer with (meth) acryloyl group and the above formula (D ⁰⁾ polyorganosiloxane has additionally an epoxy group in addition to groups represented by.

The hydrolytic condensation in the above methods (1) to (4) can be carried out by reacting the hydrolyzable silane compound or a mixture thereof with water, preferably in the presence of a suitable catalyst and an organic solvent. Reaction of the hydrolysis-condensation product which has an epoxy group in said method (2)-(4), and a carboxylic acid, Preferably it can carry out in presence of a catalyst and an organic solvent. The reaction between the polyorganosiloxane having a (meth) acryloyl group and the nucleophilic compound in the method (5) is known in the presence or absence of a suitable catalyst depending on the type of nucleophilic compound to be used. Can be carried out according to the Michael addition reaction.

Hereinafter, a hydrolyzable silane compound preferably used for producing the first polymer, a hydrolytic condensate having a carbonic acid and an epoxy group, which is preferably used for the hydrolysis condensation reaction thereof, a reaction with a hydrolysis condensate having an epoxy group, and The reaction with the carboxylic acid will be described in turn.

Then, reaction of the polyorganosiloxane which has the nucleophilic compound and (meth) acryloyl group which are used preferably in the said method (5), and a nucleophilic compound is demonstrated.

Hydrolyzable Silane Compound

{Compound (a1)}

Compound (a1) is a hydrolyzable silane compound having a (meth) acryloyl group.

As a compound (a1) in this invention, it is following formula (a1-1), for example:

(In formula (a1-1), R is a hydrogen atom or a methyl group, n is an integer of 1-6, X is a halogen atom, a C1-C4 alkoxyl group, or a C1-C4 alkyl group, However, a molecule | numerator X present in three may be the same or different, and two or more of X is a halogen atom or an alkoxyl group having 1 to 4 carbon atoms.)

The compound etc. which are represented by are mentioned.

In said Formula (a1-1), it is preferable that it is an integer of 1-5 as n. Bivalent

The group -C _n H _2n -may be linear or branched, but is preferably linear. As X, it is preferable that all three are a halogen atom or a C1-C4 alkoxyl group, and it is more preferable that it is a C1-C2 alkoxyl group. Also in this case, three X's in the molecule may be the same or different.

As a specific example of a preferable compound (a1) in this invention, (gamma)-methacryloxypropyl trimethoxysilane, (gamma) -acryloxypropyl trimethoxysilane, (alpha)-methacryloxymethyl trimethoxysilane, (alpha), for example -Acryloxymethyltrimethoxysilane, β-methacryloxyethyltrimethoxysilane, β-acryloxyethyltrimethoxysilane, б-methacryloxybutyltrimethoxysilane, б-acryloxybutyltrimethoxysilane , (epsilon) -methacryloxy pentyl trimethoxysilane, (epsilon) -acryloxy pentyl trimethoxysilane, (gamma)-methacryloxypropyl triethoxysilane, (gamma) -acryloxypropyl triethoxysilane, (alpha)-methacryloxymethyl tri Ethoxysilane, (alpha) -acryloxymethyl triethoxysilane, (beta) -methacryloxyethyl triethoxysilane, (beta) -acryloxyethyl triethoxysilane, б-methacryloxy butyl triethoxysilane, б-acryloxy Butyltriethoxysilane, ε-methacryloxyphene Tyltriethoxysilane, (epsilon) -acryloxypentyl triethoxysilane, 2-hydroxy-5- (trimethoxy silanyl) -pentyl ester, methacrylic acid 2-hydroxy-5- (trimethoxy Silanyl) -pentyl ester, acrylic acid-1-hydroxymethyl-4- (trimethoxysilanyl) -butyl ester, methacrylic acid-1-hydroxymethyl-4- (trimethoxysilanyl) -butyl ester These etc. are mentioned, At least 1 sort (s) chosen from the group which consists of these can be used preferably. Especially preferably, it is at least 1 sort (s) chosen from the group which consists of (gamma) -methacryloxypropyl trimethoxysilane and (gamma) -acryloxypropyl trimethoxysilane.

{Compound (a2)}

Compound (a2) is a hydrolyzable silane compound having an epoxy group.

Compound to the epoxy group, of the (a2) formula (X ¹ -1) or (X ¹ -2):

　

It is preferable to exist as what is contained in the group represented by these.

Examples of the compound (a2) in the present invention include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, At least 1 sort (s) chosen from the group which consists of these can be used preferably. Among these, it is particularly preferable to use at least one selected from the group consisting of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane.

{Other Hydrolyzable Silane Compounds}

(A) In the hydrolytic condensation reaction of the hydrolyzable silane compound carried out to produce the first polymer, the compound (a1), together with the compound (a1) or (a2) or a mixture thereof as the hydrolyzable silane compound, A hydrolyzable silane compound (hereinafter also referred to as "compound (a3)") other than (a2) can also be used together. This compound (a3) is a hydrolysable silane compound which does not have a (meth) acryloyl group and an epoxy group.

As a specific example of such a compound (a3), for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyl trimethoxysilane, 3- ( Meta) acryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, Mercaptomethyl triethoxysilane, dimethyldimethoxysilane, dimethyl diethoxysilane, etc. are mentioned, At least 1 sort (s) chosen from the group which consists of these can be used.

[Hydrolytic Condensation Reaction of Hydrolyzable Silane Compound]

The hydrolytic condensation reaction of the hydrolyzable silane compound in the present invention can be carried out by reacting each of the hydrolyzable silane compounds or mixtures thereof and water in the presence of a suitable catalyst and an organic solvent. The preferable use ratio of a hydrolyzable silane compound differs as follows according to the manufacturing method employ | adopted.

In the case of producing the first polymer by the above method (1), the proportion of the compound (a1) in the whole hydrolyzable silane compound is preferably 5 mol% or more, more preferably 10 to 70 mol%. More preferably, it is 20-50 mol%. In the method (1), when using a hydrolyzable silane compound other than the compound (a1), at least one selected from the group consisting of the compound (a2) and the compound (a3) can be used as another hydrolyzable silane compound. have.

When the production of the first polymer is carried out by the above method (2), the proportion of the compound (a2) in the whole hydrolyzable silane compound is preferably 70 mol% or more, more preferably 80 mol% or more. It is more preferable to set it as 90 mol% or more. In the method (2), in the case of using other hydrolyzable silane compounds in addition to the compound (a2), at least one selected from the group consisting of the compound (a1) and the compound (a3) can be used as another hydrolyzable silane compound. It is preferable to use at least 1 sort (s) chosen from the group which consists of said compound (a3). When employing the method (2), it is most preferable to use only the compound (a2) as the hydrolyzable silane compound.

When manufacturing a 1st polymer by the said method (3), it is preferable that the ratio of the compound (a1) which occupies for the whole hydrolysable silane compound shall be 5-90 mol%, and it shall be 10-70 mol% or more. It is more preferable, It is further more preferable to set it as 20-60 mol%;

The proportion of the compound (a2) in the total of the hydrolyzable silane compound is preferably 10 to 95 mol%, more preferably 20 to 90 mol% or more, and even more preferably 40 to 80 mol%. . In the method (3), in the case of using other hydrolyzable silane compounds in addition to the compound (a1) and the compound (a2), at least one selected from the group consisting of the compound (a3) can be used as the other hydrolyzable silane compounds. have.

When the production of the first polymer is carried out by the above method (4), the proportion of the compound (a2) in the whole hydrolyzable silane compound is preferably 10 mol% or more, more preferably 20 mol% or more. It is more preferable to set it as 40 mol% or more. In the method (4), in the case of using other hydrolyzable silane compounds in addition to the compound (a2), at least one selected from the group consisting of the compound (a1) and the compound (a3) can be used as another hydrolyzable silane compound. It is preferable to use at least 1 sort (s) chosen from the group which consists of said compound (a3). When employing the method (4), it is most preferable to use only the compound (a2) as the hydrolyzable silane compound.

When manufacturing a 1st polymer by the said method (5), the polyorganosiloxane which has a (meth) acryloyl group used as its raw material can be obtained by the said method (1) or (2).

Polyorgano which has a (meth) acryloyl group as a raw material used for the said method (5)

When manufacturing siloxane by the said method (1), the ratio of the compound (a1) which occupies for the whole hydrolyzable silane compound used for the hydrolysis condensation reaction for manufacturing the said raw material polyorganosiloxane shall be 30 mol% or more. It is preferable, and it is more preferable to set it as 50 mol% or more. In this case, when using other hydrolyzable silane compounds other than compound (a1), at least 1 sort (s) chosen from the group which consists of said compound (a2) and a compound (a3) can be used as another hydrolyzable silane compound.

When manufacturing the polyorganosiloxane which has a (meth) acryloyl group as a raw material used for the said method (5) by the said method (2), the said raw material polyorganosiloxane is removed.

It is preferable to make the ratio of the compound (a2) in the whole hydrolyzable silane compound used for the hydrolysis condensation reaction for preparation into 70 mol% or more, It is more preferable to set it as 80 mol% or more, 90 mol% or more It is more preferable to set it as. In this case, when using other hydrolyzable silane compounds in addition to the compound (a2), at least 1 type selected from the group which consists of said compound (a1) and a compound (a3) can be used as another hydrolyzable silane compound, It is preferable to use at least 1 sort (s) chosen from the group which consists of said compound (a3). When manufacturing the polyorganosiloxane which has a (meth) acryloyl group as a raw material used for the said method (5) by the said method (2), it is most preferable to use only compound (a2) as a hydrolyzable silane compound.

The use ratio of water used at the time of hydrolytic condensation reaction becomes like this. Preferably it is 0.5-100 mol with respect to 1 mol of total of a hydrolyzable silane compound, More preferably, it is 1-30 mol.

As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. can be used, for example.

As said alkali metal compound, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc. are mentioned, for example.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine;

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As a catalyst at the time of performing a hydrolysis condensation reaction, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or an organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis condensation rate without causing side reactions such as ring opening of an epoxy group, so that production stability is excellent and preferable. Do. Moreover, the polymer composition containing the 1st polymer which is a reaction product of the polyorganosiloxane which has the epoxy group synthesize | combined using the alkali metal compound or the organic base as a catalyst and carbonic acid is very suitable, since it is very excellent in storage stability. The reason is that when an alkali metal compound or an organic base is used as a catalyst in the hydrolytic condensation reaction, as indicated in Non-Patent Document 2 (Chemical Reviews, 95, p. 1409 (1995)), highly crosslinking It is guessed that the polyorganosiloxane with a small content rate of a silanol group is obtained by forming one three-dimensional structure. That is, since such polyorganosiloxane has a small content rate of silanol groups, condensation reaction of silanol groups is suppressed and condensation reaction with the 2nd polymer contained in the polymer composition in this invention is suppressed, and it is preserve | saved. It is estimated that stability will be an excellent result.

As the catalyst, an organic base is particularly preferable. Although the usage-amount of an organic base differs with reaction conditions, such as the kind of organic base, temperature, etc., and should be set suitably, For example, it is 0.01-3 mol with respect to 1 mol of total of a hydrolyzable silane compound, More Preferably it is 0.05-1 mol.

As an organic solvent which can be used when performing a hydrolysis condensation reaction, hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example.

As said hydrocarbon, For example, toluene, xylene, etc .;

As said ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc .;

Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like;

As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .;

Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. It is preferable that they are non-water-soluble among these, and 1 or more types chosen from the group which consists of such organic solvent can be used preferably.

The use ratio of the organic solvent at the time of performing a hydrolysis condensation reaction becomes like this. Preferably it is 10-10,000 weight part with respect to a total of 100 weight part of a hydrolyzable silane compound, More preferably, it is 50-1,000 weight part.

The hydrolytic condensation reaction is preferably carried out by dissolving the above hydrolyzable silane compound or a mixture thereof in an organic solvent, mixing the solution with an organic base and water, and heating it with, for example, an oil bath or the like. Do.

At the time of a hydrolysis condensation reaction, heating temperature becomes like this. Preferably it is 130 degrees C or less, More preferably, it is 40-100 degreeC, It is preferable to heat 0.5 to 12 hours, More preferably, it is 1 to 8 hours. During heating, the mixed liquid may be stirred or placed under reflux.

It is preferable to wash | clean the organic solvent layer fractionated from the reaction liquid after completion | finish of reaction with water. At the time of this washing | cleaning, it wash | cleans with water containing a small amount of salts, for example, about 0.2 weight% of ammonium nitrate aqueous solution, etc., and is preferable at the point which a washing operation becomes easy. The washing is carried out until the water layer after washing is neutral, and then the organic solvent layer is dried with a suitable drying agent such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed. Decomposition condensates can be obtained.

Here, when employ | adopting the said method (2) or the method (4) as a manufacturing method of (A) 1st polymer in this invention, what is marketed as a hydrolysis-condensation product which has an epoxy group can also be used. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso Corp. make) etc. are mentioned, for example.

[Carbon Mountain]

{Compound (b1)}

Compound (b1) is a carboxylic acid having a (meth) acryloyl group. As long as this compound (b1) has a (meth) acryloyl group and a carboxyl group, other structures are arbitrary, For example, following formula (b1-1):

(In formula (b1-1), R is a hydrogen atom or a methyl group, R <^1> is a methylene group, a C2-C10 alkylene group, a phenylene group, or a cyclohexylene group, a is an integer of 1-10, b And c are each 0 or 1, provided that b is 1 when c is 0.)

The compound represented by is mentioned. It is preferable that the phenylene group and cyclohexylene group of R <^1> are 1,2-phenylene group and 1,2-cyclohexylene group, respectively.

As a preferable specific example of such a compound (b1), acrylic acid, methacrylic acid, 2-acryloxyethyl-2-hydroxyethyl-phthalic acid, 4- (2-methyl- acryloyloxy) benzoic acid, 2-acryl Royloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-succinic acid, methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, phthalic acid monohydroxyethyl acrylate, and the like. And 1 or more types selected from these can be used. As these commercial items, acrylic acid, methacrylic acid (above, Tokyo Kasei Kogyo Co., Ltd.), light ester HO-MS, light ester HO-HH, HOA-MPL, HOA-MS, HOA-HH (above) , Kyoeisha Chemical Co., Ltd. make), and M-5400 (made by Toagosei Co., Ltd.).

{Compound (b2)}

Compound (b2) has the formula A, and other structures with (D ⁰⁾ is a carboxylic acid having a group represented by, a carboxyl group and a group represented by the above formula (D ⁰⁾ is arbitrary.

In the group represented by the formula (D ⁰ ) that the carboxylic acid has, R ^I in the formula (D ⁰ ) 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 It is preferable that it is a C1-C51 hydrocarbon group which has a steroid skeleton. As said C4-C40 alkyl group, it is preferable that it is a C6-C40 alkyl group;

As a C4-C40 fluoroalkyl group, it is preferable that it is a C4-C20 fluoroalkyl group. Preferred specific examples of such R ^I correspond to the above-mentioned preferred ranges in the description of R ^I in the group represented by the formula (D ⁰ ).

As a compound (b2), it is following formula (b2-1), for example:

D ⁰ -COOH (b2-1)

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

The compound etc. which are represented by are mentioned as a preferable thing.

As a preferable example of such a compound (b2), a long-chain fatty acid, the benzoic acid derivative which has a long chain alkyl group, the benzoic acid derivative which has a long chain alkoxyl group, the benzoic acid derivative which has a steroid skeleton, the benzoic acid derivative which has a polycyclic structure, fluoro, for example Carbonic acid which has an alkyl group, etc. are mentioned. As these specific examples,

Examples of the long chain fatty acid include caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, and the like;

As the benzoic acid derivative having a long chain alkyl group, for example, 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4- Stearyl benzoic acid and the like;

As the benzoic acid derivative having a long chain alkoxyl group, for example, 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexa Decyloxybenzoic acid, 4-stearyloxybenzoic acid and the like;

As the benzoic acid derivative having a steroid skeleton, for example, cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, ranostanyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, ranostanyloxycarbon Nielbenzoic acid, succinic acid-5ξ-cholestan-3-yl, succinic acid-5ξ-cholester-3-yl, succinic acid-5ξ-lanostane-3-yl and the like;

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-bicyclohexyl-4-carboxylic acid, 4'-hexyl-bicyclohexyl-4-carboxylic acid, 4'-heptyl-bicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carbon Acid, 4'-hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4- Hexyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-heptyl-bicyclohexyl-4-yl) benzoic acid, 6- (4'-cyanobiphenyl-4-yloxy) hexanoic acid and the like;

As the carboxylic acid having a fluoroalkyl group, for example, the following formulas (b2-1-1) and (b2-1-2):

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

The compound etc. which are represented by each of these are mentioned, respectively.

{Other Carbonic Acid}

(A) In reaction of the hydrolysis-condensation product which has an epoxy group, and carbonic acid performed in order to manufacture a 1st polymer, it is a compound (b1) with the said compound (b1) or (b2) or a mixture thereof as carbonic acid. ) and (b2) other than carbonic acid (hereinafter also referred to as "compound (b3)") can also be used together. This compound (b3) is a carboxylic acid which does not have a (meth) acryloyl group and an epoxy group.

As such carbonic acid, formic acid, acetic acid, propionic acid, benzoic acid, methyl benzoic acid, etc. are mentioned, for example.

[Reaction of Hydrolyzed Condensate Having Epoxy Group with Carbonic Acid]

Reaction of the hydrolysis-condensate which has an epoxy group, and a carbonic acid is said method (2)-(4)

The hydrolysis-condensation product having the epoxy group obtained in the hydrolysis-condensation reaction of the carboxylic acid can be carried out by reacting preferably in the presence of a catalyst and an organic solvent.

When manufacturing a 1st polymer by the said method (2), it is a compound (b) as carboxylic acid

It is preferable to use only 1) or to use a mixture of compound (b1) and compound (b3). Here, it is preferable to set it as 75 mol% or more with respect to all the carboxylic acids, and, as for the usage ratio of a compound (b1), it is more preferable to set it as 90 mol% or more.

When the production of the first polymer is carried out by the method (3), the carboxylic acid is a compound (b)

It is preferable to use only 2) or to use a mixture of compound (b2) and compound (b3). Here, it is preferable to set it as 75 mol% or more with respect to all the carboxylic acids, and, as for the usage ratio of a compound (b2), it is more preferable to set it as 90 mol% or more.

When the production of the first polymer is carried out by the above method (4), as the carbonic acid, the compound (b

It is preferable to use a mixture of 1) and (b2) or a mixture of compounds (b1) to (b3). Here, it is preferable to set it as 30-60 mol% with respect to the whole carbonic acid, and, as for the usage ratio of a compound (b1), it is more preferable to set it as 35-50 mol%;

It is preferable to set it as 40-70 mol% with respect to all the carboxylic acids, and, as for the usage ratio of a compound (b2), it is more preferable to set it as 50-65 mol%.

As a use ratio of carbonic acid in reaction of the hydrolysis-condensation product which has an epoxy group, and carbonic acid as a mole ratio of the total carbonic acid with respect to the epoxy group which a hydrolysis-condensation product has,

In the said method (2), Preferably it is 5 mol% or more, More preferably, it is 10-80 mol%, More preferably, it is 15-60 mol%, Especially preferably, it is 20-40 mol%;

In the said method (3), Preferably it is 2 mol% or more, More preferably, it is 2-50 mol%, More preferably, it is 5-40 mol%, Especially preferably, it is 10-30 mol%;

In the said method (4), Preferably it is 7 mol% or more, More preferably, it is 10 mol% or more, More preferably, it is 20-80 mol%, Especially preferably, it is 30-60 mol%.

As a catalyst which can be used in the reaction of the hydrolysis-condensation product which has an epoxy group, and a carbonic acid, an organic base can be used and a well-known compound can be used as what is called a hardening accelerator which accelerates reaction of an epoxy compound.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;

Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;

And quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine;

Preference is given to quaternary organic amines, such as tetramethylammonium hydroxide.

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethylaminomethyl) phenol, cyclohexyl dimethylamine, and triethanolamine;

2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimeth

Thilimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecyl Midazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2-phenyl-4, 5-di (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4,5-di [(2'-sia Noethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl -s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 '-Methylimidazolyl- (1')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4- Amino-6 [2'-methylimidazole imidazolyl (1 ')] ethyl -s- isocyanuric acid addition imidazole compounds such as water-triazine;

Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium Iodine, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium-o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazoleate, tetra-n-butylphosphonium tetrafluoro Quaternary phosphonium salts such as loborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or organic acid salts thereof;

Organometallic compounds such as zinc octylate, octylate tin and aluminum acetylacetone complex;

Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride and triphenyl borate;

Metal halide compounds such as zinc chloride and tin tin;

High-melting-point dispersion | distribution type latent hardening accelerators, such as an amine addition type accelerator, such as a dicyandiamide, an amine, and an addition product of an epoxy resin;

Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;

Amine salt type latent curing accelerators;

Latent curing accelerators, such as high temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerators, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

Among these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferable.

The catalyst is preferably used in a proportion of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total carbonic acid to be used.

As an organic solvent which can be used in reaction of the hydrolysis-condensation product which has an epoxy group, and a carbonic acid, a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. are mentioned, for example. Of these, ether compounds, ester compounds, ketone compounds are preferable in view of solubility of raw materials and products, and ease of product purification, and specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, methyl isobutyl ketone and Butyl acetate is mentioned. It is preferable to use a solvent in the ratio which becomes solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies for the total weight of a solution) becomes 0.1 weight% or more, More preferably, 5-50 weight% It is a ratio.

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC.

The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

[Nucleophilic compound]

Next, the nucleophilic compound preferably used in the method (5) will be described.

As the nucleophilic compound preferably used in the method (5) of the present invention, at least one nucleophilic compound selected from the group consisting of amines and thiols, provided that the nucleophilic compound is represented by the formula (D ⁰ ) The thing which has group is mentioned.

Groups represented by the above formula (D ⁰⁾ which is a nucleophilic compound, it is preferred that the R ^I in the formula (D ⁰⁾ is a fluoroalkyl group of 2 to 12 carbon atoms or an alkyl group having a carbon number of 2 to 12. Preferred specific examples of such R ^I correspond to the above-mentioned preferred ranges in the description of R ^I in the group represented by the formula (D ⁰ ).

Examples of the formula (D ⁰⁾ (hereinafter referred to as "compound (c1)") having a group represented by the amine, it is preferred to use a primary amine or a secondary amine. Examples of the compound (c1) which is a primary amine include octylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, Pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, 4- (4-pentylcyclohexyl) -phenylamine, 4-octyloxyphenylamine and the like;

As a compound (c1) which is a secondary amine, it is diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, di Undecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, etc. are mentioned, respectively. Among these, it is preferable to use the compound (c1) which is a secondary amine from the point which is difficult to gelate when reacting with the polyorganosiloxane which has a (meth) acryloyl group, and the synthesis | combination is easy.

Examples of the thiol having a group represented by the formula (D ⁰ ) (hereinafter referred to as "compound (c2)") include methylthiol, ethylthiol, propylthiol, butylthiol, pentylthiol, hexylthiol, heptylthiol, and octyl. Thiol, nonylthiol, decylthiol, undecylthiol, dodecylthiol, tridecylthiol, tetradecylthiol, pentadecylthiol, hexadecylthiol, heptadecylthiol, octadecylthiol, nonadecylthiol, 4-butylphenylthiol, 4-pentylphenylthiol, 4-hexylphenylthiol, 4-heptylphenylthiol, 4-octylphenylthiol, 4-nonylphenylthiol, 4-decylphenylthiol, 4-undecylphenylthiol, 4-dodecylphenylthiol, 4-tridecylphenylthiol, 4-tetradecylphenylthiol, 4-pentadecylphenylthiol, 4-hexadecylphenylthiol, 4-heptadecylphenylthiol, 4-octadecylphenylthiol, 4-nonadecylphenylthiol, 4 -Butoxyphenylthiol, 4-pentyloxyphenylthiol, 4-hexyloxyphenylthiol, 4-heptyloxyphenylthiol, 4-octyloxyphenylthiol, 4-nonyloxype Nylthiol, 4-decyloxyphenylthiol, 4-undecyloxyphenylthiol, 4-dodecyloxyphenylthiol, 4- (4'-butylcyclohexyl) phenylthiol, 4- (4'-pentylcyclohexyl) phenyl Thiol, 4- (4'-hexylcyclohexyl) phenylthiol, 4- (4'-heptylcyclohexyl) phenylthiol, 4- (4'-octylcyclohexyl) phenylthiol, and the like.

[Reaction of Polyorganosiloxane with (meth) acryloyl Group and Nucleophilic Compound]

Next, reaction of the polyorganosiloxane which has a (meth) acryloyl group and a nucleophilic compound is divided into the case where a nucleophilic compound is a compound (c1) and the case of a compound (c2), and it demonstrates sequentially.

{When nucleophilic compound is compound (c1)}

Reaction of the nucleophilic compound is polyorganosiloxane having the formula (D ⁰⁾ in the case of an amine (compound (c1)) having a group shown in the (meth) acryloyl groups are, both, preferably, organic solvent, It can be performed by reacting in the presence of and optionally in the presence of a catalyst.

As a use ratio of the compound (c1) in reaction of the polyorganosiloxane which has a (meth) acryloyl group, and a compound (c1), the number-of-moles of the compound (c1) with respect to the (meth) acryloyl group which a polyorganosiloxane has As a ratio, Preferably it is 1 mol% or more and less than 100 mol%, More preferably, it is 3-50 mol%, More preferably, it is 5-30 mol%.

As an organic solvent which can be used in the reaction of the polyorganosiloxane which has a (meth) acryloyl group, and a compound (c1), a polar compound can be used preferably, For example, nitrile, sulfoxide, ether, ester, alcohol, etc. Can be mentioned. As these specific examples, As said nitrile, For example, acetonitrile etc .;

As said sulfoxide, For example, dimethyl sulfoxide etc .;

As said ether, For example, diethyl ether, dipropyl ether, etc .;

As said ester, For example, ethyl acetate, butyl acetate, etc .;

Examples of the alcohols include trifluoroethanol and hexafluoroethanol. Among them, it is preferable to use nitrile or sulfoxide from the viewpoint of the stability of the reaction. It is preferable to use a solvent in the ratio which solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution occupies for the total weight of a solution) becomes 40 weight% or more from a viewpoint of reaction rate, More preferably, it is 50 It is the ratio used as -90 weight%.

As a catalyst which can be used arbitrarily in reaction of the polyorganosiloxane which has a (meth) acryloyl group, and a compound (c1), aluminum chloride, formic acid, etc. are mentioned, for example.

Reaction temperature becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 60-100 degreeC. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

On the other hand, nucleophilic compound is reacted with the polyorganosiloxane having the formula (D ⁰⁾ in case of thiol (compound (c2)) having a group shown in the (meth) acryloyl groups are, both, preferably This can be done by reacting in the presence of an organic solvent and a catalyst.

The use ratio of the compound (c2) in the reaction between the polyorganosiloxane having a (meth) acryloyl group and the compound (c2) is a mole ratio of the compound (c2) to the (meth) acryloyl group of the polyorganosiloxane. As for 1 mol% or more, More preferably, it is 3-50 mol%, More preferably, it is 5-30 mol%.

As an organic solvent which can be used in reaction of the polyorganosiloxane which has a (meth) acryloyl group, and a compound (c2), a polar compound can be used preferably, for example, a nitrile, a sulfoxide, an ether, Ester etc. are mentioned. As these specific examples, As said nitrile, For example, acetonitrile etc .;

As said sulfoxide, For example, dimethyl sulfoxide etc .;

As said ether, For example, diethyl ether, dipropyl ether, etc .;

As said ester, ethyl acetate, butyl acetate, etc. are mentioned, respectively. It is preferable to use the solvent in the ratio which becomes 40 weight% or more of solid content concentration (the ratio which the total weight of components other than the solvent in a reaction solution accounts for the total weight of a solution), More preferably, 50-90 weight% It is a ratio.

As a catalyst used preferably in reaction of the polyorganosiloxane which has a (meth) acryloyl group, and a compound (c2), an organic salt base etc. are mentioned, for example, Tertiary amine, Specifically, Trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, tripropylamine and the like. The use ratio of a catalyst becomes like this. Preferably it is 50 weight part or less with respect to 100 weight part of compound (c2), More preferably, it is 10-30 weight part.

Reaction temperature becomes like this. Preferably it is 10-100 degreeC, More preferably, it is 40-80 degreeC. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

[(A) Recommended Method for Making the First Polymer]

In this invention, it is preferable that (A) manufacture of a 1st polymer is by the said method (3), the method (4), or the method (5). In the method (3) or the method (4), the first polymer is represented by a (meth) acryloyl group or the above formula (D ⁰ ) by using a carbonic acid in a ratio less than the epoxy group of the hydrolysis-condensation product. It is preferable to have all of a group and an epoxy group.

<(B) Second Polymer>

(B) 2nd polymer contained in the polymer composition used by this invention is at least 1 sort (s) chosen from the group which consists of a polyamic acid and a polyimide.

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

[Tetracarboxylic dianhydride]

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, butanetetracarboxylic dianhydride etc .;

As alicyclic tetracarboxylic dianhydride, For example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5- tricarboxy cyclopentyl acetic dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3- Oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3 Furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, 4 , 9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like;

As aromatic tetracarboxylic dianhydride, a pyromellitic dianhydride etc. can be mentioned, respectively, For example, tetracarboxylic dianhydride of patent document 2 (Unexamined-Japanese-Patent No. 2010-97188) can also be used.

As tetracarboxylic dianhydride used for synthesize | combining the said polyamic acid, it is preferable to use only alicyclic tetracarboxylic dianhydride among these, or to use the mixture of alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. Do. In the latter case, the ratio of the alicyclic tetracarboxylic dianhydride to the total tetracarboxylic dianhydride is preferably 20 mol% or more, more preferably 40 mol% or more.

[Diamine]

As a diamine used for synthesizing the polyamic acid, a diamine having a group represented by the formula (D ⁰ ) (hereinafter referred to as "specific diamine") and a diamine having no group represented by the formula (D ⁰ ) (hereinafter, ""Otherdiamine").

The above formula (D ⁰⁾ the membrane formed from a polymer composition containing a second polymer prepared by using a specific diamine having a group shown, will exhibit a satisfactory liquid crystal alignment capability.

As the specific diamines of the present invention, the above formula (D ⁰⁾ is an aromatic diamine having a group represented by is preferable, for example, as its specific example dodecane oxy-2,4-diaminobenzene, pentadecane oxy -2 , 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, pentadecaneoxy-2,5 -Diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5 -Diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, and the like, and one or two of them It is preferable to use the above. Specific diamines in the present invention are, in particular, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene and cholesteryl It is preferable that it is at least 1 sort (s) chosen from the group which consists of oxy-3, 5- diamino benzene.

As said other diamine, what does not correspond to the said specific diamine as aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, etc. are mentioned, for example.

As these specific examples, As an aliphatic diamine, For example, 1, 1- metha xylylenediamine, 1, 3- propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc .;

As alicyclic diamine, For example, 1, 4- diamino cyclohexane, 4, 4'- methylenebis (cyclohexylamine), 1, 3-bis (aminomethyl) cyclohexane, etc .;

As aromatic diamine, for example, p-phenylenediamine, 4,4'- diaminodiphenylmethane, 4,4'- diaminodiphenyl sulfide, 1,5- diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy Phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m- Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3 , 6-diaminocarbazole, N-phenyl-3,6-di Benzidine and the like, N, N'- bis (4-aminophenyl) -N, N'- dimethyl benzidine-diamino carbazole, N, N'- bis (4-aminophenyl);

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

As a diamine used in order to synthesize | combine the (B) 2nd polymer in this invention, it is preferable that it is at least 1 sort (s) chosen from the above-mentioned specific diamine and other diamine. Diamine used more preferably and its use ratio differ slightly depending on the structure of said (A) 1st polymer.

In the case where the (A) first polymer does not have a group represented by the formula (D ⁰ ), in order to impart a liquid crystal alignment function to the (B) second polymer, a diamine containing the specific diamine is used as the diamine. It is preferable to contain, and it is more preferable to contain 2 mol% or more of such specific diamine with respect to all diamine, It is further more preferable to contain 2 to 60 mol%, It is preferable to contain 5-40 mol% especially, The Especially, it is preferable to contain 10-30 mol% especially.

On the other hand, when the (A) first polymer does not have a group represented by the formula (D ⁰ ), it is not necessary to use a specific diamine as the diamine, but the use of the specific diamine is not prohibited. In this case, specific diamine can be used in 90 mol% or less with respect to all diamine, It is preferable to use in 70 mol% or less, It is more preferable to use in 40 mol% or less.

[Molecular Weight Control Agent]

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

As said molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, etc. are mentioned, for example. As these specific examples, as an acid anhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back;

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

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

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

[Synthesis of Polyamic Acid]

The use ratio of tetracarboxylic dianhydride and diamine to be used for the polyamic acid synthesis reaction is preferably a ratio in which the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine, and more preferably. Is a ratio of 0.3 to 1.2 equivalents.

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

Here, as an organic solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Aprotic polar solvents such as hexamethylphosphotriamide;

Phenolic solvents, such as m-cresol, a xylenol, a phenol, and a halogenated phenol, are mentioned. It is preferable that the usage-amount (a) of an organic solvent is an amount so that the total amount (b) of tetracarboxylic dianhydride and diamine may be 0.1-30 weight% with respect to whole quantity (a + b) of a reaction solution.

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

This reaction solution may be used as it is in preparation of the polymer composition, or after isolation of the polyamic acid contained in the reaction solution, or in preparation of the polymer composition, or after purification of the isolated polyamic acid. It may be. When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be used as it is for dehydration ring closure reaction, or the polyamic acid contained in the reaction solution may be isolated before being used for dehydration ring closure reaction or the isolated polyamic acid. After purification, it may be used for a dehydration ring closure reaction. Isolation and purification of polyamic acid can be performed according to a well-known method.

Synthesis of Polyimide

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

The polyimide in the present invention is a complete imide compound in which all of the acid structures of polyamic acid, which is a precursor thereof, are dehydrated and ring-closed, or only a part of the acid structures are dehydrated and ring-closed, and the amic acid structure and the imide ring structure coexist. The partial imide may be sufficient. It is preferable that the imidation ratio of the polyimide in this invention is 40% or more.

This imidation ratio shows the ratio which the number of the imide ring structure to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage.

Dehydration ring closure of polyamic acid, Preferably it is performed by the method of heating a polyamic acid, or the method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst in this solution, and heating as needed. . Among these, it is preferable by the latter method.

In the method of adding a dehydrating agent and a dehydrating ring-closure catalyst in the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. As an organic solvent used for a dehydration ring-closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. The reaction temperature of the dehydration ring-closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing a polyimide is obtained. The reaction solution may be provided as it is to the preparation of the polymer composition as it is, or after removal of the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, to the preparation of the polymer composition, after isolation of the polyimide, or to the preparation of the polymer composition, Alternatively, the isolated polyimide may be purified and then used to prepare a polymer composition. These purification operations can be performed according to a well-known method.

<Use ratio of (A) 1st polymer and (B) 2nd polymer>

As a use ratio of the (A) 1st polymer and (B) 2nd polymer in the polymer composition used by the method of this invention, it is a use ratio of (A) 1st polymer with respect to 100 weight part of (B) 2nd polymers. It is preferable to set it as 1-90 weight part, It is more preferable to set it as 2-60 weight part, It is especially preferable to set it as 5-40 weight part.

<Other Ingredients>

Although the polymer composition used in the method of this invention contains the above-mentioned (A) 1st polymer and (B) 2nd polymer as an essential component, it may contain other components.

Other components that can be used herein include, for example, other polymers, radically polymerizable compounds, and compounds having at least one epoxy group in the molecule (except those corresponding to the first polymer (A). Compound ", and a functional silane compound.

[Other polymers]

Such other polymers can be used to improve the solution properties of the polymer composition and the electrical properties of the films formed from the polymer composition. Such other polymers are polymers other than the above-mentioned (A) 1st polymer and (B) 2nd polymer, For example, polyamic acid ester, polyester, polyamide, polysiloxane, a cellulose derivative, polyacetal, a polystyrene derivative, poly ( Styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.

As a usage ratio of another polymer, it is 40 weight part or less with respect to 100 weight part of (B) 2nd polymers, More preferably, it is 20 weight part or less. In this invention, it is preferable not to use another polymer.

[Radical polymerizable compound]

The radically polymerizable compound may be contained in the polymer composition of the present invention for the purpose of improving sensitivity to radiation.

As this radically polymerizable compound, it is a compound which has 1 or more, preferably 1-3, at least 1 group (henceforth a "radically polymerizable group") chosen from acryloyl group and methacryloyl group. It is preferable, and it is a compound which has 1 to 3 radically polymerizable group and a liquid crystal like structure together more preferably. More preferably as such a compound, the compound having one radically polymerizable group is represented by the following formula (d1):

(In formula (d1), R is a hydrogen atom or a methyl group,

R ^III is an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, a cyano group or a fluorine atom, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton;

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

R ^IV is a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms,

n5 is an integer of 1 to 3,

However, when n5 is 2 or 3, a plurality of R ^IV may be the same or different from each other,

n6 is 0 or 1)

The compound (henceforth "compound (d1)") represented by this is a compound which has two radically polymerizable groups, di (meth) acrylate which has a biphenyl structure, and di (meth) acryl which has a phenyl-cyclohexyl structure At least one selected from the group consisting of a di (meth) acrylate having a 2,2-diphenylpropane structure and a di (meth) acrylate having a diphenylmethane structure (hereinafter referred to as "compound (d2)"). As a compound which has three radically polymerizable groups, the tri (meth) acrylic acid ester of a trivalent or more polyhydric alcohol (henceforth "compound (d3)") is mentioned, respectively.

As a specific example of the said compound (d1), 4- (4-octadecylcyclohexyl) phenyl acrylate, 4- (4-butylcyclohexyl) phenyl methacrylate, 4- (4-pentylcyclohexyl) phenyl, for example Methacrylate, 4- (4-hexylcyclohexyl) phenyl methacrylate, 4- (4-octylcyclohexyl) phenyl methacrylate, 4- (4-decylcyclohexyl) phenyl methacrylate, 4- (4 -Dodecylcyclohexyl) phenyl methacrylate, 4- (4-hexadecylcyclohexyl) phenyl methacrylate, 4- (4-octadecylcyclohexyl) phenyl methacrylate, 4- (4-butylcyclohexyl) Cyclohexyl acrylate, 4- (4-pentylcyclohexyl) cyclohexyl acrylate, 4- (4-hexylcyclohexyl) cyclohexyl acrylate, 4- (4-octylcyclohexyl) cyclohexyl acrylate, 4- ( 4-decylcyclohexyl) cyclohexyl acrylate, 4- (4-dodecylcyclohexyl) cyclohexyl Acrylate, 4- (4-hexadecylcyclohexyl) cyclohexyl acrylate, 4- (4-octadecylcyclohexyl) cyclohexyl acrylate, 4- (4-butyl cyclohexyl) cyclohexyl methacrylate, 4- (4-pentylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexylcyclohexyl) cyclohexyl methacrylate, 4- (4-octylcyclohexyl) cyclohexyl methacrylate, 4- (4-decylcyclo Hexyl) cyclohexyl methacrylate, 4- (4-dodecylcyclohexyl) cyclohexyl methacrylate, 4- (4-hexadecyl cyclohexyl) cyclohexyl methacrylate, 4- (4-octadecylcyclohexyl) Cyclohexyl methacrylate, (meth) acrylic acid-5ξ-cholestan-3-yl, (meth) acrylic acid-5ξ-cholester-3-yl, (meth) acrylic acid 4- (4'-pentylbicyclohexyl-4 -Yl) phenyl ester etc. are mentioned.

As a specific example of the said compound (d2), it is di (meth) acrylate which has a biphenyl structure, for example, 4 '-(meth) acryloyloxy-biphenyl-4-yl-acrylate and 2- [4. '-(2- (meth) acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl (meth) acrylate, 2- (2- {4'-[2- (2- (meta ) Acryloyloxyethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl acrylate, bishydroxyethoxy biphenyl di (meth) acrylate, etc .;

As di (meth) acrylate having a phenyl-cyclohexyl structure, for example, 4- (4- (meth) acryloyloxy-phenyl) -cyclohexyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl (meth) acrylate, etc .;

As di (meth) acrylate which has a 2, 2- diphenyl propane structure, for example, 4- [1- (4- (meth) acryloyloxy-phenyl) -1-methyl-ethyl] -phenyl (meth ) Acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl (meth) acrylate , Ethoxy bisphenol A di (meth) acrylate, and the like;

As di (meth) acrylate having a diphenylmethane structure, for example, 4- (4- (meth) acryloyloxy-benzyl) -phenyl (meth) acrylate, 2- {4- [4- (2 -(Meth) acryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl (meth) acrylate, the di (meth) acrylate of the ethylene oxide adduct of bisphenol F, etc. are mentioned, respectively.

As a specific example of the said compound (d3), for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, penta Erythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl Phosphate, tri (2-methacryloyloxyethyl) phosphate, and the like.

As a radically polymerizable compound used by this invention, a compound (d1) or a compound (d2) is preferable, Especially the compound (d1) whose n5 in the said Formula (d1) is 2 or 3, and n6 is 1, it is a compound (d2) di (meth) acrylate having the formula (d1) the R ^III hydrocarbons resulting compound (d1) or biphenyl structure having a carbon number of 17-51 with a steroid skeleton in the preferred.

The use ratio of a radically polymerizable compound is 50 weight part or less with respect to 100 weight part of (B) 2nd polymers, More preferably, it is 1-50 weight part, More preferably, it is 3-30 weight part It is preferable that it is 5-15 weight part especially. By setting it as such a use ratio, the effect scavenged to the said compound can be effectively expressed, without causing the problem of the voltage retention reduced of the liquid crystal display element manufactured.

[Epoxy Compound]

It is preferable that it is a compound which has at least 2 epoxy group in a molecule | numerator as said epoxy group compound, For example, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid) Dilaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-di Glycidyl-aminomethylcyclohexane, N, N- diglycidyl-cyclohexylamine, etc. are mentioned as a preferable thing. All.

The compounding ratio of these epoxy compounds becomes like this. Preferably it is 10 weight part or less with respect to 100 weight part of (B) 2nd polymers, More preferably, it is 5 weight part or less.

[Functional silane compound]

As said functional silane compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimeth Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3 , 6-Diazonayl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, 9-trimethoxysilyl-3,6-methyl diazanoanoate, 9-triethoxy Methyl 3,6-diazananoic acid, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltrie A methoxysilane, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, etc. are mentioned.

The compounding ratio of these functional silane containing compounds becomes like this. Preferably it is 2 weight part or less with respect to 100 weight part of (B) 2nd polymers, More preferably, it is 0.2 weight part or less.

<Polymer composition>

It is preferable that the polymer composition used in this invention is prepared as a solution which melt | dissolved the above-mentioned (A) 1st polymer and (B) 2nd polymer, and other components used arbitrarily in a suitable organic solvent.

As an organic solvent which can be used here, for example, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, (gamma) -butyrolactam, N, N- dimethylformamide, N, N- dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutylke Tones, isoamyl propionate, isoamyl isobutylate, diisopentyl ether and the like.

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

<< manufacturing method of liquid crystal display element >>

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

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

The coating film of a pair of board | substrates which formed the said coating film forms the liquid crystal cell of the structure which opposingly arranged through the layer of liquid crystal molecules,

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

Here, as a board | substrate, For example, glass, such as a float glass and a soda glass;

A transparent substrate made of polyethylene such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used.

Preferable to use a transparent conductive film as the conductive film, and for example may be used NESA film, ITO film or the like made of In ₂ O ₃ -SnO ₂ made of SnO _2. It is preferable that this conductive film is a pattern-shaped conductive film partitioned in several area | regions, respectively. With such a conductive film configuration, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region when a voltage is applied between the conductive films (to be described later), thereby changing the viewing angle characteristics. It becomes possible to make it wider.

In order to apply | coat a polymer composition on the said electrically conductive film of such a board | substrate, it can be based on suitable coating methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, for example. After application | coating, the said coating surface is preheated (prebaked) and then baked (postbaking), and a coating film is formed. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the postbaking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and preferably 5 to 200. Minutes, More preferably, it is 10 to 100 minutes. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

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

Next, the said coating film of the pair of board | substrates in which the said coating film was formed forms the liquid crystal cell of the structure which opposingly arranged through the layer of liquid crystal molecules.

As a liquid crystal molecule used here, the nematic liquid crystal which has negative dielectric anisotropy is preferable, for example, dicyano benzene liquid crystal, a pyridazine liquid crystal, a siphon base liquid crystal, a cyanide liquid crystal, a biphenyl liquid crystal, a phenylcyclo Hexane type liquid crystal etc. can be used. It is preferable that the layer thickness of liquid crystal molecule shall be 1-5 micrometers.

For forming a liquid crystal cell using such a liquid crystal, the following two methods are mentioned, for example.

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

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

The voltage applied here can be, for example, 5 to 50 V DC or alternating current.

As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used, for example. Ultraviolet rays in the above preferred wavelength region can be obtained by means of using the light source together with a filter, a diffraction grating, or the like, for example.

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

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

<< liquid crystal display element >>

The liquid crystal display device manufactured as described above according to the method of the present invention has a wide viewing angle, a very fast response speed of liquid crystal molecules, excellent display properties and long-term reliability, and a low production cost. Therefore, the present invention can be suitably applied to various applications including liquid crystal televisions of two-dimensional display and three-dimensional display.

(Example)

<(A) Synthesis of First Polymer>

Synthesis Example S-1

Hydrolytic 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) ethyltrimethoxysilane (ECETS) and γ-methacryloxypropyl as hydrolyzable silane compounds 24.8 g of trimethoxysilane (GMPTS) (ECETS: GMPTS = 75: 25 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous ammonium nitrate solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a hydrolyzed condensate having an epoxy group. (Iii) obtained as a transparent liquid.

As a result of performing ¹ H-NMR analysis on this hydrolysis-condensation product, a peak based on the epoxy group is obtained according to the theoretical strength near the chemical shift (б) = 3.2 ppm, and side reactions of the epoxy group occur during the reaction. Was confirmed.

[Reaction of Hydrolyzed Condensate Having Epoxy Group with Carbonic 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 carbonic acid in the hydrolysis-condensation product having the epoxy group obtained above (the epoxy group of the hydrolysis-condensation product 0.10 g of UCAT 18X (trade name, which is an epoxy compound curing accelerator manufactured by San Afro Co., Ltd.) was added as a catalyst and a catalyst, and the reaction was carried out at 100 ° C. for 48 hours with stirring. After the completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed three times with water, dried using magnesium sulfate, and then the solvent was distilled off to remove (A) polyorganosiloxane (PS-1) as the first polymer. 100.2 g was obtained. About this polyorganosiloxane (PS-1), the weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) was 7,100.

Synthesis Examples S-2 to S-6, S-10, S-11 and S-16

[Hydrolytic Condensation Reaction] and [Reaction of Hydrolyzed Condensate Having Epoxy Group with Carbonic Acid]

In the above Synthesis Example S-1, the hydrolytic condensation reaction and the hydrolysis condensate were carried out in the same manner as in Synthesis Example S-1 except that the hydrolyzable silane compound and the carbonic acid of the kind and amount shown in the first table were used, respectively. By reacting with carbonic acid, (A) polyorganosiloxanes (PS-2) to (PS-6), (PS-10), (PS-11) and (PS-16), which are the first polymers, were obtained, respectively. . The yield and Mw of these polyorganosiloxanes were also shown in the 1st table | surface. In the synthesis examples S-3 to S-5 and S-16, two types of carboxylic acids were used, respectively. Synthesis Example S-6 is a comparative synthesis example.

Synthesis Example S-7-S-9

Hydrolytic Condensation Reaction

In the said synthesis example S-1, except having used the hydrolyzable silane compound of the kind and quantity shown in the 1st table | surface, it carries out a hydrolytic condensation reaction similarly to the synthesis example S-1, and (A) 1st polymer Phosphorus polyorganosiloxane (PS-7)-(PS-9) were obtained, respectively. The quantity and Mw of these polyorganosiloxane were combined with the 1st table | surface.

Synthesis Example S-12

Hydrolytic Condensation Reaction

In the said Synthesis Example S-1, except for using the hydrolyzable silane compound of the kind and quantity shown in the 1st table | surface, the hydrolysis-condensation reaction was performed similarly to the Synthesis Example S-1, and the valence which has an acryloyl group The decomposition condensate was obtained as a viscous transparent liquid.

[Reaction of Hydrolysis Condensate Having Acryloyl Group with Nucleophilic Compound (Thiol)]

In a 500 mL three-necked flask equipped with a stirrer and a thermometer, 165.3 g of the above hydrolysis condensate, 60.7 g of n-dodecyl-1-thiol (DT) as a nucleophilic compound, 160 mL of acetonitrile as a solvent and triethylamine as a catalyst 22.3g was put, it heated up at 50 degreeC, stirred for 90 minutes, and reacted. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and catalyst were distilled off under reduced pressure, thereby (A) polyorganosiloxane as the first polymer. 225.3 g of (PS-12) was obtained as a viscous transparent liquid. About this polyorganosiloxane (PS-12), the weight average molecular weight (Mw) of polystyrene conversion measured by GPC was 7,400.

Synthesis Example S-13

Hydrolytic Condensation Reaction

In the said Synthesis Example S-1, except for using the hydrolyzable silane compound of the kind and quantity shown in the 1st table | surface, the hydrolysis-condensation reaction was performed similarly to the Synthesis Example S-1, and the valence which has an acryloyl group The decomposition condensate was obtained as a viscous transparent liquid.

[Reaction of Hydrolyzed Condensate Having Acryloyl Group with Nucleophilic Compound (Amine)]

Into a 500 mL three-necked flask equipped with a stirrer and a thermometer, 165.3 g of the hydrolysis condensate obtained above, 48.3 g of di-n-octylamine (DOA) as a nucleophilic compound (amine) and 160 mL of acetonitrile as a solvent were added thereto. It heated up at 50 degreeC, stirred for 6 hours, and reacted. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent was distilled off under reduced pressure to obtain the (A) first polymer having a dioctylamino group. 212.2 g of polyorganosiloxane (PS-13) was obtained as a viscous transparent liquid. About this polyorganosiloxane (PS-13), the weight average molecular weight (Mw) of polystyrene conversion measured by GPC was 7,200.

Synthesis Example S-14 and S-15

[Hydrolytic Condensation Reaction] and [Reaction of Hydrolyzed Condensate Having Acryloyl Group with Nucleophilic Compound (Thiol)]

In the Synthesis Example S-12, the hydrolytic condensation reaction and the hydrolysis were carried out in the same manner as in Synthesis Example S-12 except that the hydrolyzable silane compound and the nucleophilic compound (thiol) of the kind and amount shown in the first table were used, respectively. By reacting the decomposition condensate with the nucleophilic compound, (A) polyorganosiloxane (PS-14) and (PS-15) as the first polymers were obtained, respectively. The quantity and Mw of these polyorganosiloxane were combined with the 1st table | surface.

Synthesis Example S-17

[Reaction of silsesquioxane having acryloyl group with nucleophilic compound (thiol)]

In the said synthesis example S-12, 165.0 g of AC-SQ TA-100 (made by Toagosei Co., Ltd.) which is a silsesquioxane which has acryloyl group instead of the synthesized hydrolysis-condensate was used, and a nucleophilic compound Except having made phosphorus n-dodecyl-1-thiol (DT) into 40.5 g, it carried out similarly to reaction of the hydrolysis-condensation product and nucleophilic compound in Synthesis Example S-12, and (A) Polyorganosiloxane (PS-17) which is a 1st polymer was obtained. The quantity and Mw of this polyorganosiloxane were combined with the 1st table | surface.

The abbreviation of each compound in a 1st table | surface has the following meanings, respectively.

{Hydrolyzable silane compound}

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

GMPTS: γ-methacryloxypropyltrimethoxysilane

GAPTS: γ-acryloxypropyltrimethoxysilane

{Silsesquioxane having acryloyl group}

ACSQ: product name `` AC-SQ TA-100 '', manufactured by Toagosei Co., Ltd.

{Carbonic acid}

OCTBA: 4-octyloxybenzoic acid

ACRYA: Acrylic Acid

AEHEP: 2-acryloxyethyl-2-hydroxyethyl-phthalic acid

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

In addition, the usage-amount of carbonic acid is mol% with respect to the epoxy group which a hydrolysis-condensation product has. In synthesis examples S-3 to S-5 and S-16, two types of carboxylic acids were used, respectively.

{Nucleophilic compound}

Thiol

DT: n-dodecyl-1-thiol

PCBT: 4- (4'-pentylcyclohexyl) phenylthiol

BT: n-butyl-1-thiol

Amine

DOA: Di-n-octylamine

The notation of "-" in the first table indicates that the compound corresponding to the corresponding column was not used.

<B Synthesis of Second Polymer>

Synthesis Example P-1

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

Subsequently, 1,900 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring closure reaction, the solvent in the system was solvent-substituted with fresh N-methyl-2-pyrrolidone (pyridine and acetic anhydride used in the dehydration ring closure reaction in this operation were removed from the system), thereby (B) a second polymer, A solution containing about 15% by weight of polyimide (PI-1) having an imidation ratio of about 50% was obtained. A small amount of the obtained polyimide solution was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding N-methyl-2-pyrrolidone was 47 mPa · s.

Synthesis Example P-2

200 g (1.0 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 210 g (1.0 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine Was dissolved in 3670 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours to obtain a solution containing 10% by weight of polyamic acid (PA-1) as the second polymer (B). The solution viscosity of this polyamic acid solution was 160 mPa * s.

Synthesis Example P-3

1,2,3,4-cyclobutanetetracarboxylic dianhydride 98 g (0.50 mol) as tetracarboxylic acid dianhydride and 110 g (0.50 mol) pyromellitic dianhydride, and 4,4'-diaminodiphenyl as diamine After dissolving 200 g (1.0 mol) of methane in 2,330 g of N-methyl-2-pyrrolidone and reacting for 3 hours at 40 ° C., 1,350 g of N-methyl-2-pyrrolidone was added to the obtained reaction mixture. And (B) The solution containing 10 weight% of polyamic acid (PA-2) which is a 2nd polymer was obtained. The solution viscosity of this polyamic acid solution was 125 mPa * s.

Example 1

<Preparation of a polymer composition>

(B) N-methyl-2-pyrrolidone (NMP) and butyl cellosolve as a organic solvent in a solution containing 100 parts by weight of the polyimide (PI-1) obtained in Synthesis Example P-1 as the second polymer. (BC) was added, and (A) 5 parts by weight of the polyorganosiloxane (PS-1) obtained in Synthesis Example S-1 was added as a first polymer, and the solvent composition was NMP: BC = 50: 50 (weight ratio). It was set as the solution of 6.0 weight% of solid content concentration. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

Preparation and Evaluation of Liquid Crystal Cells

Using the polymer composition prepared above, the pattern (two types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed as follows, and six liquid crystal display elements in total were manufactured and evaluated.

[Production of Liquid Crystal Cell Having Patternless Transparent Electrode]

The polymer composition prepared above was apply | coated on the transparent electrode surface of the glass substrate which has a transparent electrode which consists of an ITO film | membrane using a liquid crystal aligning film printing machine (made by Nippon Shashin Inc.), and for 1 minute on an 80 degreeC hotplate After heating (prebaking) to remove the solvent, it was heated (postbaking) for 10 minutes on a 150 ° C hot plate to form a coating film having an average film thickness of 600 kPa.

About this coating film, the rubbing process was performed by the rubbing machine which has the roll which rolled up the rayon cloth at roll rotation speed 400rpm, stage movement speed 3cm / sec, and hairpin indentation length 0.1mm. Then, the board | substrate which has a liquid crystal aligning film was obtained by performing ultrasonic cleaning for 1 minute in ultrapure water, and then drying for 10 minutes in a clean oven at 100 degreeC. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after applying the 5.5-micrometer-diameter aluminum oxide sphere containing epoxy resin adhesive agent to each outer edge which has the liquid crystal aligning film of the said pair of board | substrates, it overlaps with each other so that a liquid crystal aligning film surface may face and hardens an adhesive agent. I was. Next, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was produced by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

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

To two of the liquid crystal cells obtained above, an alternating current of 10 Hz at a frequency of 60 Hz was applied between the electrodes, respectively, and ultraviolet light was 10,000 J / m 2 using an ultraviolet irradiation device using a metal halide lamp as the light source while the liquid crystal was being driven. Or it investigated with the irradiation amount of 100,000 J / m <2>. In addition, this irradiation amount is the value measured using the photometer measured by the wavelength 365nm reference.

[Evaluation of Pretilt Angle]

For each liquid crystal cell prepared above, Non-Patent Document 3 (TJ Scheffer et. Et al., J. Appl. Phys. Vo. 48, p. 1783 (1977)) and Non-Patent Document 4 (F. Nakano) Inclination angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using He-Ne laser light according to the method described in JPN. J. Appl. Phys. Vo. 19, p. 2013 (1980)). The value was made into the pretilt angle.

Each pretilt angle of the liquid crystal cell of tailings irradiation, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2> was shown to the 3rd table | surface.

[Evaluation of Voltage Integrity]

About each liquid crystal cell produced above, after applying the voltage of 5V in 60 microsecond application time and 167 millisecond span in 23 degreeC, the voltage retention rate after 167 milliseconds after application | release cancellation was measured. As a measuring apparatus, VHR-1 by Toyo Technica Co., Ltd. was used.

Voltage retention rates of the liquid crystal cell having an irradiation amount of 10,000 J / m 2 and the liquid crystal cell having an irradiation amount of 100,000 J / m 2 are shown in the third table.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode (1)]

The polymer composition prepared above is patterned in a slit shape as shown in FIG. 1 and has a liquid crystal aligning film printer (Nihonshashin Inc.) on each electrode surface of glass substrates A and B each having ITO electrodes partitioned into a plurality of regions. After application | coating using, the heating is carried out for 1 minute on a 80 degreeC hotplate (prebaking), and a solvent is removed, it heats on a 150 degreeC hotplate for 10 minutes (postbaking), and the average film thickness of 600 kPa is carried out. A coating film was formed. About this coating film, after performing ultrasonic cleaning in ultrapure water for 1 minute, it dried in a 100 degreeC clean oven for 10 minutes, and the board | substrate which has a liquid crystal aligning film was obtained. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

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

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it is. About the remaining two liquid crystal cells, the irradiation amount of 10,000 J / m <2> or 100,000 J / m <2> in the state which applied the voltage between electrically conductive films in the same way as the manufacture of the liquid crystal cell which has the said transparent electrode without a pattern is applied. After light irradiation, the response speed was used for evaluation.

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

[Evaluation of response speed]

About each liquid crystal cell manufactured above, the brightness of the light which permeate | transmitted the liquid crystal cell was irradiated by irradiating a visible light lamp first without applying a voltage, and this value was made into 0% of the relative transmittance. Next, the transmittance | permeability when AC 60V was applied for 5 second between the electrodes of a liquid crystal cell was measured similarly to the above, and this value was made into 100% of the relative transmittance | permeability.

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

The response speed of the liquid crystal cell of tailings irradiation, the liquid crystal cell of irradiation amount 10,000J / m <2>, and the liquid crystal cell of irradiation amount 100,000J / m <2> was shown to the 3rd table | surface.

[Production of Liquid Crystal Cell with Patterned Transparent Electrode (2)]

Using the polymer composition prepared above, a liquid crystal cell having the patterned transparent electrode, except that glass substrates A and B each having an ITO electrode patterned in a fishbone shape as shown in FIG. 2 were used. In the same manner as in Preparation (1), a liquid crystal cell of tailings irradiation, 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 prepared, respectively, and were subjected to evaluation of the response speed in the same manner as described above. . The evaluation result was shown to the 3rd table | surface.

Examples 2-23 and 27-29

In Example 1, a polymer composition is prepared in the same manner as in Example 1, except that the types and amounts of the (A) first polymer and (B) the second polymer are each as described in the second table. Various liquid crystal cells were produced and evaluated using this. In addition, in Example 11, 12, 15-17, 22, 28, and 29, (B) 2nd polymer was used 2 types, respectively.

The evaluation result was shown to the 3rd table | surface.

Example 24

<Preparation of a polymer composition>

(B) N-methyl-2-pyrrolidone (NMP) and butyl cellosolve as a organic solvent in a solution containing 100 parts by weight of the polyimide (PI-1) obtained in Synthesis Example P-1 as the second polymer. (BC) was added thereto, and (A) 6 parts by weight of the polyorganosiloxane (PS-1) obtained in Synthesis Example S-1 as the first polymer and methacrylic acid-5ξ-cholestane-3 as a radical polymerizable compound. -5 weight part of days (MACY) were added, and the solvent composition was made into the solution of NMP: BC = 50: 50 (weight ratio), and solid content concentration 6.0weight%. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

Preparation and Evaluation of Liquid Crystal Cells

Except having used the polymeric compound prepared above, it carried out similarly to Example 1, and produced and evaluated various liquid crystal cells.

The evaluation result was shown to the 3rd table | surface.

Examples 25 and 26

In Example 24, the polymer composition was prepared in the same manner as in Example 24, except that the type and amount of radically polymerizable compound were used as shown in the second table, respectively, to prepare various liquid crystal cells using the same. Evaluated. In addition, in Example 25, two types of radically polymerizable compounds were used.

The evaluation result was shown to the 3rd table | surface.

Comparative Example 1

In the said Example 1, except having not used (A) 1st polymer, it carried out similarly to Example 1, prepared the polymer composition, and produced and evaluated various liquid crystal cells using this.

The evaluation result was shown to the 3rd table | surface.

Comparative Examples 2-4

In Example 1, the polymer composition was prepared in the same manner as in Example 1, except that (A) other polymers or compounds shown in the second table were used instead of the first polymer, respectively, in the amounts shown in the second table. Various liquid crystal cells were produced and evaluated using this.

The evaluation result was shown to the 3rd table | surface.

The abbreviated-name in a 2nd table | surface has the following meanings, respectively.

[Other Compounds]

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

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

[Radical polymerizable compound]

MACY: Methacrylic acid-5ξ-cholestan-3-yl

PBCHPM: Methacrylic acid 4- (4'-pentylbicyclohexyl-4-yl) phenyl ester

HEIXA: dipentaerythritol hexaacrylate

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

The notation of "-" in the first table indicates that the compound corresponding to the corresponding column was not used.

From the results of the third table, in the method of the present invention, when the ultraviolet irradiation amount is set to 100,000 J / m 2 (the value conventionally employed in the PSA mode), the degree of pretilt angle obtained is excessive, and 10,000 J / m 2 or less. It turns out that it becomes an appropriate pretilt angle in the irradiation amount of. Moreover, even if the irradiation amount is small, a sufficiently fast response speed is obtained, and the voltage holding ratio is also excellent.

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

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

Claims (15)

On the said conductive film of a pair of board | substrates which have a conductive film, respectively
(A) the first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and also
(B) at least one second polymer selected from the group consisting of polyamic acid and polyimide
A coating film is formed by applying a polymer composition containing
The said coating film of the pair of board | substrates which provided the said coating film forms the liquid crystal cell of the structure which opposingly arranged through the liquid crystal layer,
And a step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates. The method of claim 1,
The (A) of claim 1 to a polymer, adding formula (D ^0):

(In 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 hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton;
Z ^I is a single bond, ^* -O-, ^* -COO- or ^* -OCO- (wherein the bond to which "*" is attached is the R ^I side),
R ^II is a cyclohexylene group or a phenylene group, provided that the cyclohexylene group or phenylene group may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms,
n1 is 1 or 2,
Provided that when n1 is 2, the 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 bond to which "*" is attached is the R ^I side),
n3 is an integer of 0 to 2,
n4 is 0 or 1)
The manufacturing method of the liquid crystal display element which has group represented by the. The method of claim 1,
The manufacturing method of the liquid crystal display element whose said (A) 1st polymer is a hydrolyzable condensate of a hydrolyzable silane compound (However, this hydrolyzable silane compound contains the hydrolyzable silane compound which has a (meth) acryloyl group.). The method of claim 1,
The first polymer (A) is a hydrolyzable condensate of a hydrolyzable silane compound (wherein the hydrolyzable silane compound contains a hydrolyzable silane compound having an epoxy group) and a carboxylic acid (wherein the carboxylic acid is (meth) And a carbonic acid having an acryloyl group). The method of claim 2,
The said (A) 1st polymer is a polyorganosiloxane which has a (meth) acryloyl group, and
Liquid crystal which is a reaction product with at least one nucleophile compound selected from the group consisting of amines and thiols, wherein the nucleophile compound contains a nucleophilic compound having a group represented by the above formula (D ⁰ ) The manufacturing method of a display element. The method of claim 5,
The liquid crystal display in which the polyorganosiloxane which has the said (meth) acryloyl group is a hydrolysis-condensation product of a hydrolyzable silane compound (However, this hydrolyzable silane compound contains the hydrolyzable silane compound which has a (meth) acryloyl group.) Method of manufacturing the device. The method of claim 5,
The polyorganosiloxane which has the said (meth) acryloyl group is a hydrolyzable condensate of a hydrolyzable silane compound (However, this hydrolyzable silane compound contains the hydrolyzable silane compound which has an epoxy group.)
The manufacturing method of the liquid crystal display element which is a reaction product with carbonic acid (However, this carbonic acid contains the carbonic acid which has a (meth) acryloyl group.). 8. The method according to any one of claims 5 to 7,
And the nucleophilic amine compound of Formula (D ⁰⁾ in the carbon number of R ^I is an alkyl group or a fluoroalkyl group having a carbon number of 2 to 12 of 2 to 12, n2 and n4 is zero The method of liquid crystal display elements, respectively. 8. The method according to any one of claims 5 to 7,
The nucleophilic property and the thiol compound of Formula (D ⁰⁾ of R ^I the method for manufacturing a liquid crystal display element is a fluoroalkyl group of 2 to 12 carbon atoms or an alkyl group having a carbon number of 2 to 12. The method of claim 2,
Hydrolysis-condensation of the said (A) 1st polymer with a hydrolyzable silane compound (However, this hydrolyzable silane compound contains the hydrolyzable silane compound which has a (meth) acryloyl group, and the hydrolyzable silane compound which has an epoxy group.) Water and
Carboxylic acid process for producing a liquid crystal display device of (provided the carbon acid is the formula (D ⁰⁾ as comprising a carboxylic acid having a group represented) reaction of the product. The method of claim 2,
The first polymer (A) is a hydrolyzable condensate of a hydrolyzable silane compound, provided that the hydrolyzable silane compound contains a hydrolyzable silane compound having an epoxy group.
Carboxylic acid process for producing a liquid crystal display device of (provided the carbon acid is (meth) acryloyl group having a carboxylic acid and the above formula (D ⁰⁾ as comprising a carboxylic acid having a group represented) reaction of the product. The method according to claim 10 or 11, wherein
The expression (D ⁰⁾ of carbon atoms, or R ^I is an alkyl group or a fluoroalkyl group with a carbon number of 4-40 4-40, or process for producing a hydrocarbon group of a carbon number of liquid crystal display elements 17-51 having a steroid skeleton. The method according to any one of claims 1 to 7, 10, 11,
A method for producing a liquid crystal display element, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions. As a polymer composition used for manufacturing the liquid crystal display element of Claim 1,
(A) the first polymer which is a polyorganosiloxane having a (meth) acryloyl group, and also
(B) at least one second polymer selected from the group consisting of polyamic acid and polyimide
A polymer composition, comprising: The liquid crystal display element manufactured by the manufacturing method of the liquid crystal display element in any one of Claims 1-7, 10, and 11.

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