KR20120067304A - Process for producing liquid crystal display device, the liquid crystal display device, and polymer composition - Google Patents

Abstract

PURPOSE: A method for manufacturing a liquid crystal display device, a liquid crystal display device, and a polymer composition are provided to obtain superior display features and high reliability. CONSTITUTION: A polymer composition is coated. A film is formed. The polymer composition includes polyorganosiloxane and polymerizable unsaturated compositions. A pair of substrates face the film. A liquid crystal cell is formed. Light is irradiated to the liquid crystal cell when a voltage is applied between conductive films. The conductive films have the substrates.

Description

The manufacturing method of a liquid crystal display element, a liquid crystal display element, and a polymer composition {PROCESS FOR PRODUCING LIQUID CRYSTAL DISPLAY DEVICE, THE LIQUID CRYSTAL DISPLAY DEVICE, AND POLYMER COMPOSITION}

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

Among the liquid crystal display elements, the MVA (Multi-Domain Vertical Alignment) 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 increasing the viewing angle. We are planning. However, according to this system, the lack of transmittance and contrast derived from the projections is inevitable, and there is a problem that the response speed of the liquid crystal molecules is further slow.

Recently, in order to solve the above problems of the MVA panel, a PSA (Polymer Sustained Alignment) mode has been proposed. PSA mode is a polymerizable compound in a gap between a pair of substrates formed of a substrate with a patterned conductive film and a substrate with a conductive film not having a pattern, or a gap of a pair of substrates formed of two substrates with a patterned conductive film. It is a technique which clamps the liquid crystal composition containing and polymerizes a polymeric compound by irradiating an ultraviolet-ray in the state which applied the voltage between electrically conductive films, expressing a pretilt angle characteristic by this, and suppressing the orientation direction of a liquid crystal. According to this technique, by setting the conductive film in a specific configuration, it is possible to increase the viewing angle and speed up the liquid crystal molecular response, thereby solving the problem of lack of transmittance and contrast which is inevitable in the MVA panel. However, for the polymerization of the polymerizable compound, irradiation of a large amount of ultraviolet light, such as 100,000 J / m 2, is required, which causes a problem that the liquid crystal molecules are decomposed. It is apparent that unreacted compounds which have not been left in the liquid crystal layer, which interact with each other, cause uneven display, adversely affect voltage preservation characteristics, or cause 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, in Non-Patent Document 1, there are no guidelines on what kind of reactive mesogen should be used in any amount, and the amount of ultraviolet irradiation required is still large, and concerns about display characteristics, in particular, voltage integrity characteristics, are not ignored. .

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)  T. J. Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)  F. Nakano et al., JPN. J. Appl. Phys. Vol. 19, p. 2013 (1980)

This invention is made | formed in view of the said situation, and an object of this invention is to provide the manufacturing method of the liquid crystal display element which has a wide viewing angle, the response speed of liquid crystal molecules is fast, and was excellent in display characteristics and long-term reliability.

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

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

(A) polyorganosiloxane and

(B) polymerizable unsaturated compound

A coating composition is formed by applying a polymer composition containing

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

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

The liquid crystal display device produced by the method of the present invention has a wide viewing angle, a fast response speed of liquid crystal molecules, a sufficient transmittance and contrast, excellent display characteristics, and no 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 contributes to the reduction of the manufacturing cost of a liquid crystal display element.

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

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

(B) polymerizable unsaturated compound

Lt; / RTI &gt;

[(A) Polyorganosiloxane]

It is preferable that the weight average molecular weight Mw of polystyrene conversion measured by the gel permeation chromatography about (A) polyorganosiloxane contained in the polymer composition used by this invention is 500-1,000,000, and it is 1,000-100,000. More preferably, it is preferable that it is 1,000-50,000.

(A) The polyorganosiloxane is a following formula (A-1):

(In formula (A-1), n1 is an integer of 0-2, n2 is 0 or 1, and when n1 + n2 is 2 or more, R is a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 fluoro. R is an alkyl group, and when n1 + n2 is 0 or 1, R is a group having a steroid structure, an alkyl group having 4 to 20 carbon atoms, or a fluoroalkyl group having 2 to 20 carbon atoms)

It is preferable to have group represented by.

As a group which has the steroid structure of R in said Formula (A-1), for example, 3-cholestanyl group, 3-cholesteryl group, 3-lanostanyl group, 3-collanyl group, 3-pregnal A group, 3-androstanyl group, 3-estranyl group, etc. are mentioned.

When carbon number which has the alkyl group and fluoroalkyl group of R in said Formula (A-1) is three or more, it is preferable that it is a linear group, respectively. As a fluoroalkyl group, following formula (F):

(In formula (F), a and b are integers of 0 to 19, respectively, when n1 + n2 in formula (A-1) is 2 or more, and a + b is an integer of 0 to 19, and n1 + n2 is 0 or 1; a + b is an integer of 3 to 19)

It is preferable that it is group represented by.

As a preferable example of group represented by said Formula (A-1), For example, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n- Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, following formula (A-1-1)? (A-1-3):

(R in Formula (A-1-1)? (A-1-3) has the same meaning as R in Formula (A-1), respectively.)

The group represented by these is mentioned. It is preferable that R in Formula (A-1-1)-(A-1-3) is a C1-C18 linear alkyl group or a fluoroalkyl group.

(A) As ratio of group represented by said formula (A-1) which occupies in polyorganosiloxane, it is preferable that it is 0.0002 mol / g or more, It is more preferable that it is 0.004-0.002 mol / g, Furthermore, 0.0005-0.0016 mol / It is preferable that it is g.

Such polyorganosiloxane (A) may be produced by any method as long as it has the above characteristics.

(A) The polyorganosiloxane is, for example, an alkoxysilane compound, preferably a silane compound having a group represented by the formula (A-1) and an alkoxyl group (hereinafter referred to as "silane compound (a1)"), Or a mixture of a silane compound (a1) and another alkoxysilane compound (hereinafter referred to as "silane compound (a2)"),

Reacting in the presence of dicarboxylic acid and alcohol (manufacturing method 1), or

Hydrolysis-condensation (manufacturing method 2), or

A silane compound having an epoxy group and an alkoxyl group (hereinafter referred to as "silane compound (a2-1)") or a silane compound (a2-1) and other alkoxysilane compound (hereinafter referred to as "silane compound (a2-2)" Mixture),

After reacting in the presence of dicarboxylic acid and alcohol, further reacting with a compound having a group represented by the formula (A-1) and a carboxyl group (hereinafter referred to as "specific carbonic acid") (Manufacturing Method 3), or

Method to further react with specific carboxylic acid after hydrolysis and condensation (manufacturing method 4)

It can manufacture by.

It is preferable that the said silane compounds (a2-1) and (a2-2) do not have group represented by said formula (A-1), respectively, In this case, a silane compound (a2-1) and (a2-2) The sum of the sums corresponds to the range of the silane compound (a2).

As said silane compound (a1), following formula (a1-1):

N1, n2, and R in the (formula (a1-1), respectively, and the above formula (A-1) equal to the mean of n1, n2, and R, n is an integer of ^1? 3, R 1 is a phenyl or C1 Alkyl of 1 to 12 or an alkylphenyl group having an alkyl group of 1 to 12 carbon atoms)

The compound represented by is mentioned. It is preferable that n in Formula (a1-1) is 1.

As a specific example of such a silane compound (a1), for example, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane , n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-n-pentoxysilane, n-butyltri-sec-pentoxysilane, n-butyltriphenoxy Cysilane, n-butyltri-p-methylphenoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i -Propoxysilane, n-heptyltri-n-butoxysilane, n-pentyltri-sec-butoxysilane, n-pentyltri-n-pentoxysilane, n-pentyltri-sec-pen Methoxysilane, n-pentyltriphenoxysilane, n-pentyltri-p-methylphenoxysilane, 2- (perfluoro-n-hexyl) ethyltrimethoxysilane, 2- (perfluoro-n -Hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysil , 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n- Octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluoro Rho-n-octyl) ethyltri-i-propoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec -Butoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-dodecyltri-n-butoxysilane, n-dodecyltri-i-propoxysilane, n-dode Siltri-n-butoxysilane, n-dodecyl tri-sec-butoxysilane, etc. are mentioned, One or more types selected from these can be used.

As said silane compound (a2-1), for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3 -Glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. are mentioned, One or more types selected from these can be used.

The said silane compound (a2-2), Preferably it is an alkoxysilane compound other than the said silane compound (a1) and a silane compound (a2-1), For example, Preferably, it is a following formula (a2-2-1):

(In formula (a2-2-1), R <^2> is a C1-C3 alkyl group, a C1-C3 fluoroalkyl group, or a phenyl group, or is an alkylphenyl group which has a C1-C3 alkyl group, and R <^3> is a phenyl group. Or an alkyl group having 1 to 12 carbon atoms or an alkylphenyl group having 1 to 12 carbon atoms, and m is an integer of 0 to 3).

The compound represented by is mentioned.

As a specific example of the compound represented by said formula (a2-2-1), as a compound whose m is 0, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane Tetra-sec-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane and the like;

As the compound whose m is 1, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri -sec-butoxysilane, methyltri-n-pentoxysilane, methyltri-sec-pentoxysilane, methyltriphenoxysilane, methyltri-p-methylphenoxysilane, ethyltrimethoxysilane, ethyltrie Methoxysilane, ethyltri-n-propoxysilane, ethyltri-i-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-n-pentoxysilane, ethyltree -sec-pentoxysilane, ethyltriphenoxysilane, ethyltri-p-methylphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-i-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-n-pentoxysilane, n-propyltri-sec -Pentoxysilane, n-prop Philtriphenoxysilane, n-propyltri-p-methylphenoxysilane, 2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (tri Fluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (trifluoromethyl) ethyltri-n-butoxysilane, 2- ( Trifluoromethyl) ethyltri-sec-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-part Oxysilane, phenyltri-sec-butoxysilane, and the like;

As m is 2, for example, dimethyldimethoxysilane, diethyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, di -n-propyldiethoxysilane, di-i-propyldiethoxysilane, dimethyl-di-i-propoxysilane, diethyl-di-i-propoxysilane, di-n-propyl-di-i-propoxy Silane, di-i-propyl-di-i-propoxysilane, dimethyl-di-sec-butoxysilane, diethyl-di-sec-butoxysilane, di-n-propyl-di-sec-butoxysilane , Di-i-propyl-di-sec-butoxysilane and the like;

Examples of the compound in which m is 3 include trimethylmethoxysilane, triethylmethoxysilane, tri-n-propylmethoxysilane, tri-i-propylmethoxysilane, trimethylethoxysilane, triethylethoxysilane and tri -n-propylethoxysilane, tri-i-propylethoxysilane, trimethyl-n-propoxysilane, triethyl-n-propoxysilane, tri-n-propyl-n-propoxysilane, tri-i- Propyl-n-propoxysilane, trimethyl-i-propoxysilane, triethyl-i-propoxysilane, tri-n-propyl-i-propoxysilane, tri-i-propyl-i-propoxysilane, trimethyl -sec-butoxysilane, triethyl-sec-butoxysilane, tri-n-propyl-sec-butoxysilane, tri-i-propyl-sec-butoxysilane, etc. are mentioned, respectively, From these, One or more kinds selected may be used.

As the silane compound (a2-2), one kind selected from the group consisting of ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and tetraethoxysilane It is preferable to use the above, and it is especially preferable to use 1 or more types chosen from the group which consists of tetramethoxysilane and tetraethoxysilane.

The use ratio with respect to all the silane compounds of each silane compound used as a raw material in manufacturing (A) polyorganosiloxane in this invention is as follows according to the manufacturing method of (A) polyorganosiloxane. .

(1) The method of (A) preparation of polyorganosiloxane by manufacturing method 1 or 2;

Silane compound (a1): Preferably it is 1 mol% or more, More preferably, it is 2-40 mol%, More preferably, it is 5-20 mol%

Silane compound (a2): Preferably it is 99 mol% or less, More preferably, it is 60-98 mol%, More preferably, it is 80-95 mol%

(2) the process according to Preparation Method 3 or 4 for preparing the polyorganosiloxane;

Silane compound (a2-1): Preferably it is 50 mol% or more, More preferably, it is 60-100 mol%, More preferably, it is 80-100 mol%

Silane compound (a2-2): Preferably it is 50 mol% or less, More preferably, it is 0-40 mol%, More preferably, it is 0-20 mol%.

Hereinafter, the method of making the silane compound reacted in manufacture methods 1 and 3 in presence of dicarboxylic acid and alcohol is demonstrated.

Examples of the dicarboxylic acid used herein include oxalic acid, malonic acid, a compound in which two carboxyl groups are bonded to an alkylene group having 2 to 4 carbon atoms, benzenedicarboxylic acid, and the like. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. are mentioned, It is preferable to use 1 or more types selected from these. Particularly preferably oxalic acid.

It is preferable to make it the amount which the amount of a carboxyl group with respect to 1 mol of the alkoxyl groups which the silane compound used as a raw material uses is 0.2-2.0 mol, and the quantity of dicarboxylic acid used is made into 0.5-1.5 mol. desirable.

As said alcohol, primary alcohol can be used suitably. Specific examples thereof include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-ethylbutanol, 3-heptanol, n-octanol, 2-ethylhexanol, n-nonyl alcohol, 2, 6-dimethyl-4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, and the like. It is preferable to use one or more selected from. The alcohol used herein is preferably an aliphatic primary alcohol having 1 to 4 carbon atoms and is selected from the group consisting of methanol, ethanol, i-propanol, n-propanol, i-butanol, sec-butanol and t-butanol. It is more preferable to use 1 or more types, and it is especially preferable to use 1 or more types chosen from the group which consists of methanol and ethanol.

It is preferable that the ratio of the silane compound and dicarboxylic acid which occupy the whole quantity of reaction solution to the use ratio of the alcohol in the manufacturing methods 1 and 3 shall be made into the ratio which becomes 3 to 80 weight%, and becomes 25 to 70 weight% It is more preferable to set it as a ratio.

The reaction temperature is preferably 1 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

In reaction of the silane compound of the manufacturing methods 1 and 3, it is preferable not to use other solvent other than the above alcohol.

In the above manufacturing method, it is inferred that the polyorganosiloxane which is the (co) polymer of a silane compound produces | generates by alcohol acting on the intermediate produced | generated by reaction of a silane compound and dicarboxylic acid.

Next, the hydrolysis-condensation reaction of the silane compound carried out in Production Methods 2 and 4 will be described.

This hydrolysis-condensation reaction can be performed by making a silane compound and water react in presence of a solvent, Preferably in a suitable organic solvent.

It is preferable that the ratio of the water used here is 0.5-2.5 mol as quantity with respect to the total of 1 mol of alkoxyl groups which the silane compound used as a raw material has.

As said catalyst, an acid, a base, a metal compound, etc. are mentioned. As an example of such a catalyst, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, etc. are mentioned, for example.

As the base, both an inorganic base and an organic base can be used, and examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide;

As the organic base, for example, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; Tetramethylammonium hydroxy etc. are mentioned, respectively.

As a metal compound, a titanium compound, a zirconium compound, etc. are mentioned, for example.

It is preferable to set it as 10 weight part or less with respect to a total of 100 weight part of the silane compound used as a raw material, It is more preferable to set it as 0.001-10 weight part, Furthermore, it is preferable to set it as 0.001-1 weight part Do.

As said organic solvent, alcohol, ketone, an amide, ester, and other aprotic compounds are mentioned, for example. As said alcohol, both the alcohol which has one hydroxyl group, the alcohol which has two or more hydroxyl groups, and the partial ester of the alcohol which has two or more hydroxyl groups can be used. As the ketone, monoketone and β-diketone can be preferably used.

Specific examples of such organic solvents include alcohols having one hydroxyl group, for example methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-ethylbutanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, di Acetone alcohol, etc .;

Examples of the alcohol having a plurality of hydroxyl groups include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, and 2,5-hexane Diol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

As partial ester of the alcohol which has two or more hydroxyl groups, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol Mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like;

Examples of the monoketone include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone and ethyl n-butyl ketone , Methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, phenchon, etc. ;

As said β-diketone, for example, acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4 Nonanodione, 3,5-nonandadione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5, 5-hexafluoro-2,4-pentanedione and the like;

As the amide, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N- Dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpi Lolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc .;

As ester, for example, diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-acetic acid Butyl, i-butyl acetate, see-butyl acetate, n-pentyl acetate, see-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cycloacetic acid Hexyl, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetic acid, ethyl acetoacetic acid, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, N-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. ;

As other aprotic solvents, for example, acetonitrile, dimethyl sulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethyl phosphate triamide, N-methylmorpholone, N-methylpyrrole, N -Ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-pi Peridone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone These etc. can be mentioned respectively, 1 or more types selected from these can be used.

As a usage ratio of an organic solvent, as a ratio which the total weight of components other than the organic solvent in a reaction solution occupies for the total amount of reaction solution, it is preferable to set it as the ratio which becomes 1 to 90 weight%, and becomes 10 to 70 weight% It is more preferable to set it as a ratio.

The water added in the hydrolysis-condensation reaction of the silane compound can be added intermittently or continuously in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent.

The catalyst may be added in advance in the silane compound as a raw material or in a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in water to be added.

The reaction temperature is preferably 1 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

By the above means, in Manufacturing method 1 and 2, (A) polyorganosiloxane contained in the polymer composition in this invention is obtained directly;

On the other hand, in manufacturing methods 3 and 4, the polyorganosiloxane which has an epoxy group which is a precursor of (A) polyorganosiloxane is obtained. In the manufacturing methods 3 and 4, (A) polyorganosiloxane contained in the polymer composition in this invention can be obtained by making the polyorganosiloxane which has this epoxy group react with specific carbonic acid further.

The specific carboxylic acid used herein is a compound having a group represented by the formula (A-1) and a carboxyl group. As a specific carbonic acid, it is following formula (C-1):

(N1, n2 and R in the formula (C-1) have the same meaning as n1, n2 and R in the formula (A-1), respectively.

The compound represented by is mentioned. As a specific example of a compound represented by said formula (C-1), for example, valeric acid, caproic acid, caprylic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, 4- (n-pentyl) benzoic acid, 4- (n -Hexyl) benzoic acid, 4- (n-heptyl) benzoic acid, 4- (n-octyl) benzoic acid, 4- (n-nonyl) benzoic acid, 4- (n-decyl) benzoic acid, 4- (n-dodecyl) benzoic acid , 4- (n-octadecyl) benzoic acid, 4- (4-pentyl-cyclohexyl) -benzoic acid, 4- (4-heptyl-cyclohexyl) -benzoic acid, and the like, and one or more selected from these. Can be used.

It is preferable that the use ratio of the specific carbon acid used for reaction with the polyorganosiloxane which has an epoxy group shall be 5-50 mol with respect to 1 mol of epoxy groups which the precursor of (A) polyorganosiloxane has, and it is 10-40. It is more preferable to make it into a mole.

The reaction between the polyorganosiloxane having an epoxy group and the specific carbonic acid can be carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.

As a catalyst used here, an organic base can be used and a well-known compound can be used as what is called a hardening accelerator which promotes reaction of an epoxy compound and a carboxylic acid.

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, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Same tertiary organic amine; And

Quaternary organic amines, such as tetramethylammonium hydroxide, are preferable, and one or more selected from these can be used.

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethyl aminomethyl) 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-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methyldi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s Triazine, 2,4-di Mino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, 2-phenylimidazole Imidazole compounds such as isocyanuric acid adducts of isocyanuric acid adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-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 bromide Nium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazoleate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate;

Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7, 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, tetraethyl ammonium chloride, tetra-n-butylammonium chloride;

Boron compounds such as boron trifluoride and triphenyl borate;

In addition to metal halide compounds such as zinc chloride and ditin,

Latent curing accelerators. As this latent hardening accelerator, For example, High melting-point dispersion type latent hardening accelerators, such as an amine addition type | mold accelerator, such as an adduct of dicyandiamide or an amine and an epoxy resin;

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

Amine salt type latent curing accelerators;

High temperature dissociation type | mold thermal cationic polymerization type latent hardening accelerator, such as a Lewis acid salt and Bronsted acid salt, etc. are mentioned.

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

The catalyst is preferably 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 polyorganosiloxane having an epoxy group.

As an organic solvent used at the time of reaction with the polyorganosiloxane which has an epoxy group, and a specific 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, and ketone compounds are preferred in view of solubility of raw materials and products and ease of purification of products. The solvent is used in an amount such that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, and more preferably 5-50% by weight. .

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.

It is preferable to provide for the adjustment of a polymer composition, after refine | purifying by the appropriate suitable method of well-known (A) polyorganosiloxane obtained by the method in any one of manufacturing methods 1-4.

[(B) Polymerizable Unsaturated Compound]

The polymerizable unsaturated compound (B) used in the present invention is a group having a polymerizable carbon-carbon double bond, and preferably in the molecule, the following formula (B-II):

(In formula (B-II), R is a hydrogen atom or a methyl group, and Y ² and Y ³ are each independently an oxygen atom or a sulfur atom.)

It includes compound (B-1) which has at least two of l-valent groups represented by these.

It is preferable that the number of monovalent groups represented by said formula (B-II) in a compound (B-1) is two. As Y <^2> in the said Formula (B-II), it is preferable that it is an oxygen atom.

Compound (B-1) is a following formula (B-I) in a molecule | numerator:

(In formula (BI), X <^1> and X <^2> are respectively independently a 1, 4- phenylene group or l, 4- cyclohexylene group, Y <^1> is a single bond and C1-C4 bivalent hydrocarbon. Group, an oxygen atom, a sulfur atom or? COO ?, provided that X ¹ and X ² are substituted with one or a plurality of C 1-4 alkyl groups, C 1-4 alkoxyl groups, fluorine atoms or cyano groups good)

It is preferable to further contain at least one of the divalent groups represented by.

As a C1-C4 bivalent hydrocarbon group in said Formula (B-I), a methylene group, a dimethyl methylene group, etc. are mentioned, for example. As a bivalent group represented by said Formula (B-I), it is following formula (B-I-1)? (B-I-6):

The group etc. which are represented by each of these are mentioned. The benzene ring and the cyclohexane ring in the formulas (BI-1) to (BI-6) may each be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a fluorine atom or a cyano group, respectively. .

As the compound (B-1) used in the present invention, a di (meth) acrylate having a biphenyl structure (the divalent group represented by the formula (BI) is a group represented by the formula (BI-1), Y ² and Y ³ in (B-II) are each an oxygen atom, and a di (meth) acrylate having a phenyl-cyclohexyl structure (divalent group represented by the formula (BI) is represented by the above formula (BI). -2), Y ² and Y ^{3 in} the formula (B-II) are each an oxygen atom, and a di (meth) acrylate having a 2,2-diphenylpropane structure (the above The divalent group represented by Formula (BI) is a group represented by Formula (BI-3), Y ² and Y ^{3 in} Formula (B-II) are each an oxygen atom), and a diphenylmethane structure Di (meth) acrylate which has (Divalent group represented by said formula (BI) is group represented by said formula (BI-4), Y <^2> and Y <^{3> in} said Formula (B-II) are oxygen, respectively. Atoms), Phenylthio dithio (meth) a group represented by the acrylate (the formula (BI), 2-valent group the formula (BI-5) represented by, Y ² is oxygen in the formula (B-Ⅱ) having an ether structure An atom, and Y ³ is a sulfur atom) and other compounds (B-1).

As these specific examples, it is di (meth) acrylate which has a biphenyl structure, for example, 4'-acryloyloxy-biphenyl-4-yl-acrylate and 4'-methacryloyloxy-biphenyl 4-yl-methacrylate, 2- [4 '-(2-acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethylacrylate, 2- [4'-(2-meta Chryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl methacrylate, bishydroxyethoxybiphenyldiacrylate, bishydroxyethoxybiphenyldimethacrylate, 2- (2 -{4 '-[2- (2-Acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethylacrylate, 2- (2- {4'- Diacrylate, ratio of ethylene oxide adduct of [2- (2-methacryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethylmethacrylate, biphenyl Dimethacrylate of ethylene oxide adducts of phenyl, propylene oxide adducts of biphenyl Methacrylate, dimethacrylate of propylene oxide adducts of biphenyl, 2- (4'-acryloyloxy-biphenyl-4-yloxy) -ethylacrylate, 2- (4'-methacryloyloxy -Biphenyl-4-yloxy) -ethyl methacrylate and the like;

As the di (meth) acrylate having a phenyl-cyclohexyl structure, for example, 4- (4-acryloyloxy-phenyl) -cyclohexyl acrylate, 4- (4-methacryloyloxy-phenyl)- Cyclohexyl methacrylate, 2- {4- [4- (2-acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethylacrylate, 2- {4- [4- (2- Methacryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl methacrylate, 2- [2- (4- {4- [2- (2-acryloyl-ethoxy) -e Methoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethylacrylate, 2- [2- (4- {4- [2- (2-methacryloyloxy-ethoxy) -ethoxy] -Phenyl} -cyclohexyloxy) -ethoxy] -ethyl methacrylate and the like;

As di (meth) acrylate which has a 2, 2- diphenyl propane structure, it is following formula, for example:

(In formula, two or more R <^4> is respectively independently a hydrogen atom or a methyl group, Two or more R <^5> is each independently a hydrogen atom or a methyl group, Two or more n exists each independently, 0 Is an integer of? 5)

Compounds represented by, for example, 4- [1- (4-acryloyloxy-phenyl) -1-methyl-ethyl] -phenylacrylate,

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

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

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

Bishydroxyethoxy-bisphenol A diacrylate,

Bishydroxyethoxy-bisphenol A dimethacrylate,

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

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

Diacrylate of ethylene oxide adduct of bisphenol A,

Dimethacrylate of ethylene oxide adducts of bisphenol A,

Diacrylate of propylene oxide adduct of bisphenol A,

Dimethacrylate of propylene oxide adducts of bisphenol A,

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Diacrylates of ethylene oxide adducts of bisphenol F,

Dimethacrylate of ethylene oxide adducts of bisphenol F,

Diacrylates of propylene oxide adducts of bisphenol F,

Dimethacrylate of propylene oxide adducts of bisphenol F,

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

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

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

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

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

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

As dithio (meth) acrylate which has a diphenyl thioether structure, For example, 4- (4-thioacryloylsulfanyl- phenylsulfanyl) -phenyldithioacrylate,

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

Bis (4-methacryloylthiophenyl) sulfide and the like;

As other compound (B-1), 2, 5-bis {4- (3-acryloyloxy-propoxy)-benzoic acid} toluene etc. are mentioned, for example.

Such a compound (B-1) can be synthesize | combined by combining suitably the organic chemical method, and can obtain it as a commercial item. As a commercial item of a compound (B-1), For example, Bishydroxyethoxy BP diacrylate and Bishydroxyethoxy Bis-A dia acrylate (Honshu Chemical Co., Ltd. make);

ARONIX M-208 and M-210 (made by Toagosei Co., Ltd.);

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

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

NK ester BPE-100, NK ester BPE-200, NK ester BPE-500, NK ester BPE-1300, NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Actilane420 (Nihon Sieber Hegna) KK)

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

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

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

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

RIPOXY VR-77 (made by Showa Kobunshi Co., Ltd.) etc. is mentioned.

It is preferable to use at least 1 sort (s) chosen from the group which consists of a compound illustrated above as compound (B-1) used in this invention.

As the polymerizable unsaturated compound (B), only the compound (B-1) may be used, or the compound (B-1) and other unsaturated compounds may be used in combination.

The said other unsaturated compound can be contained in the polymer composition in this invention in order to make the pretilt angle closer to 90 degrees, and to express the effect which this application aims at more effectively by this. Such other unsaturated compounds are preferably compounds having one carbon-carbon double bond, and more preferably have one group of carbon-carbon double bonds and the group represented by the formula (A-1). As a specific example of such other unsaturated compounds, methacrylic acid-5ξ-cholestan-3-yl, methacrylic acid 4- (4'-phenyl-bicyclohexyl-4-yl) phenyl ester, etc. are mentioned, for example. have.

As a usage ratio of the (B) polymerizable unsaturated compound in the polymer composition used in this invention, 1 with respect to 100 weight part of (A) polyorganosiloxane (henceforth "(A) polymer"), It is preferable to set it as 100 weight part, and it is more preferable to set it as 5-50 weight part.

(B) When using other unsaturated compound with compound (B-1) as a polymerizable unsaturated compound, as the use ratio, it shall be 80 weight% or less with respect to the total amount of (B) polymerizable unsaturated compound. It is preferable to set it as 50 weight% or less. The other unsaturated compound can express the desired effect by using this 2 weight% or more with respect to the total amount of (B) polymerizable unsaturated compound.

[Other Ingredients]

The polymer composition used in the present invention contains the above-mentioned (A) polymer and (B) polymerizable unsaturated compound as essential components, but contains other components within a range that does not attenuate the effects of the present invention. You may be. As other components which can be used here, polymers other than (A) polymer (henceforth "other polymer"), an epoxy compound, a photoinitiator, a radical trapping agent, a light stabilizer, etc. are mentioned, for example.

The said other polymer can be used for the further improvement of the solution characteristic of the polymer composition obtained, the electrical characteristic of the coating film formed, and the response speed of the liquid crystal display element obtained. Such other polymers are polymers other than the above-mentioned (A) polymer, for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene -Phenyl maleimide) derivative, poly (meth) acrylate, etc. can be mentioned, One or more types selected from these can be used. It is preferable that it is at least 1 sort (s) chosen from the group which consists of polyamic acid and polyimide among these as another polymer.

The polyamic acid can be produced by, for example, using tetracarboxylic acid dianhydride and diamine described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188) and reacting these by a known method.

In order to synthesize the polyamic acid, an alicyclic tetracarboxylic dianhydride, specifically, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2, 3,5-tricarboxylic acid, is used as tetracarboxylic dianhydride. Pentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbor I-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatri Cyclo [5.3.1,0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [2.2.1] heptane- It is preferable to use 2,3,5, 6-tetracarboxylic acid dianhydride and the like.

As the diamine used for synthesizing the polyamic acid, it is preferable to use a diamine (hereinafter referred to as "liquid crystal aligning diamine") having a group having a property of orienting liquid crystal molecules, and more preferably a liquid crystal aligning diamine and its It is to use a mixture with other diamine.

As said liquid crystal aligning diamine, for example, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholester Nyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis ( 4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, decanoxy-2,4-diaminobenzene, tetradecaneoxy-2,4-diaminobenzene, pentadecaneoxy -2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecaneoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecaneoxy-2 , 5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, the following formula:

The compound etc. which are represented by each of these are mentioned, l or more types selected from these can be used.

As said other diamine, p-phenylenediamine, 3, 5- diamino benzoic acid, 4,4'- diamino diphenyl ether, 4,4'- diamino diphenylmethane, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenylamine, 4,4 ' -(m-phenylenediisopropylidene) dianiline etc. can be mentioned, One or more types selected from these can be used.

It is preferable that the diamine used for synthesize | combining the said polyamic acid contains 3 mol% or more of liquid crystal aligning diamine with respect to all the diamine, It is more preferable that it contains 4 to 80 mol%, It is 5-50% It is more preferable to contain, Especially preferably, it contains 10 to 40%.

The use ratio of tetracarboxylic dianhydride and diamine to be used for the polyamic acid synthesis reaction is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group of the diamine. Preferably it is the ratio used as 0.3-1.2 equivalent.

The 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, examples of the organic solvent include aprotic polar solvents, phenols and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

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

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

In the method of adding the dehydrating agent and the dehydrating ring-closure catalyst to the solution of the polyamic acid, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the dark acid structure of polyamic acid. As the dehydration ring 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.

When the polymer composition used in this invention contains another polymer, as a use ratio of the said other polymer, it is 99 with respect to the total amount of a polymer (to say the sum total of (A) polymer and another polymer, the same below). It is preferable to set it as weight% or less, It is more preferable to set it as 70-98 weight%, It is further more preferable to set it as 80-95 weight%.

When the polymer composition in the present invention contains an epoxy compound, the adhesion of the coating film formed to the substrate, heat resistance and the like can be further improved, and the response speed of the resulting liquid crystal display element is further improved, which is preferable. .

As such an epoxy compound, the epoxy compound which has two or more epoxy groups in a molecule | numerator is preferable, 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. The. Particularly preferred epoxy compounds are epoxy compounds having two or more N-glycidyl groups in the molecule.

It is preferable to set it as 50 weight part or less with respect to a total of 100 weight part of polymers, and, as for the compounding ratio of the epoxy compound in the polymer composition in this invention, it is more preferable to set it as 1-40 weight part, especially 5? It is preferable to set it as 30 weight part.

As said photoinitiator, (alpha)-diketone, acyloin, an acyloin ether, a benzophenone compound, an acetophenone compound, a quinone compound, a halogen compound, an acylphosphine oxide, an organic peroxide etc. are mentioned, for example. As these specific examples, For example, benzyl, diacetyl, etc. as (alpha)-diketone;

As acyloin, For example, benzoin etc .;

As acyloin ether, For example, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc .;

As the benzophenone compound, for example, thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (di Ethylamino) benzophenone, phenyl- (4-p-tolylsulfanyl-phenyl) -methanone and the like;

Examples of the acetophenone compound include acetophenone, p-dimethylaminoacetophenone, 4- (α, α'-dimethoxyacetoxy) benzophenone, 2,2'-dimethoxy-2-phenylacetophenone and p-meth Methoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one and the like;

Examples of the quinone compound include anthraquinone, 1,4-naphthoquinone, and the like;

Examples of the halogen compound include phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine and the like;

As the acyl phosphine oxide, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide and the like;

Examples of the organic peroxides include di-t-butyl peroxide and the like, and one or more selected from these can be used.

As a commercial item of a photoinitiator, for example, IRGACURE-124, copper-149, copper-184, copper-369, copper-500, copper-651, copper-819, copper-907, copper-1000, copper- 1700, East-1800, East-1850, East-2959, Darocur-1116, East-1173, East-1664, East-2959, East-4043 (above, manufactured by Chiba-Specialty Chemicals Co., Ltd.);

KAYACURE-BMS, Copper-DETX, Copper-MBP, Copper-DMBI, Copper-EPA, Copper-OA (above, manufactured by Nippon Kayaku Co., Ltd.);

LUCIRIN TPO (made by BASF Corporation);

VICURE-10, copper-55 (above, manufactured by STAUFFER Co., Ltd.);

TRIGONALP1 (manufactured by AKZ0);

SANDORAY 1000 (manufactured by SANDOZ);

DEAP (made by APJOHN);

QUANTACURE-PDO, copper-ITX, copper-EPD (above, WARD BLEKINSOP company), etc. are mentioned.

As a photoinitiator, it is preferable to use a benzophenone compound from a viewpoint of high thermal stability.

The use ratio of the photopolymerization initiator is preferably 30 parts by weight or less, more preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 20 parts by weight based on 100 parts by weight of the (B) polymerizable unsaturated compound. Do.

In order to avoid that (B) polymerizable unsaturated compound produces undesirable reaction by the heating which is preferably performed when the polymer composition in this invention is apply | coated and made into a coating film on the board | substrate, It may be contained in the liquid crystal aligning agent of this invention.

As a specific example of such a radical trapping agent, for example, pentaerythritol tetrakis

[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) prop Cypionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3 ', 3 ", 5', 5" -hexa-tert-butyl-α, α ', α "-(mesitylene-2, 4,6-triyl) tri-p-cresol, 4,6 -Bis (octylthiomethyl) -ο-cresol, 4,6-bis (dodecylthiomethyl) -ο-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy- m-tolyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di- tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (lH, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl 3-hydroxy-2,6-xylene) ] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio)- 1,3,5-triazin-2-ylamine) phenol etc. are mentioned, One or more types selected from these can be used.

As these commercial items, the ADEKA ASTKA AADE-20, ADEKAASTA AO-30, the ADEKA STAB AO-40, the ADEKA STAB AO-50, the ADEKA STAB AO-60, adeka Decas staff AO-70, adecas staff AO-80, adecas staff AO-330; SumilizerGM, sumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizerGA-80 manufactured by Sumitomo Kagaku Co., Ltd .;

IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX2565, IRGANOX2114;

Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 Etc. can be mentioned.

The use ratio of the radical trapping agent in the polymer composition in this invention becomes like this. Preferably it is 10 mass parts or less with respect to 100 mass parts of (B) polymerizable unsaturated compounds, More preferably, it is 5 mass parts 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) polymer, (B) polymerizable unsaturated compound, and the other additive 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, diisobutyl Tone, and the like can be mentioned isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether.

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

<Method of Manufacturing Liquid Crystal Display Element>

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

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

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

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.

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

As the conductive film, it is preferable to use a transparent conductive film, and, for example, may be used NESA (registered trademark) film, ITO film or the like made of In ₂ 0 ₃ -Sn0 ₂ made of Sn0 _2. It is preferable that this conductive film is a patterned conductive film partitioned into a plurality of regions, respectively. With such a conductive film configuration, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage for each region when a voltage is applied between the conductive films (to be described later). It becomes possible to widen.

In order to apply | coat a polymer composition on the said electrically conductive film of such a board | substrate, it can be based on appropriate coating methods, such as a roll coater method, a spinner method, the printing method, the inkjet method, for example. After application | coating, the coating surface is formed by preheating (prebaking) and then baking (postbaking). Prebaking conditions are 0.1-5 minutes, for example at 40-120 degreeC, Post-baking conditions are preferably 120-300 degreeC, More preferably, it is 150-250 degreeC, Preferably it is 5-200 minutes, More Preferably it is 10-100 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 manufacture of the liquid crystal cell of a next process, or you may perform a rubbing process with respect to a coating film surface as needed before manufacture of a liquid crystal cell. This rubbing 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. After performing a rubbing process, the process of removing a resist film is performed, and it is possible to further improve the viewing characteristic of the liquid crystal display element obtained by making it into the rubbing direction different for every area | region.

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

As a liquid crystal molecule used here, the nematic liquid crystal which has negative dielectric anisotropy is preferable, For example, a dicyano benzene system liquid crystal, a pyridazine system liquid crystal, a siphon base system liquid crystal, a cyan clock liquid crystal, a biphenyl system A liquid crystal, a phenyl cyclohexane type liquid crystal, etc. can be used. It is preferable that the thickness of the layer of liquid crystal molecules shall be 1-5 micrometers.

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

As a 1st method, two board | substrates are opposingly arranged through gap | gap (cell gap) so that each liquid crystal aligning film may oppose, the peripheral part of two board | substrates is joined using a sealing agent, and a surface of a board | substrate and a sealing compound are carried out. A liquid crystal cell can be manufactured by injecting and filling a liquid crystal in the cell gap partitioned by sealing, and sealing an injection hole. Or as a 2nd method, an ultraviolet-ray curable sealing compound is apply | coated to predetermined | prescribed place on one board | substrate among two board | substrates with which the liquid crystal aligning film was formed, and liquid crystal is further made to predetermined several places on the liquid crystal aligning film surface. After dripping, the other board | substrate is bonded together so that a liquid crystal aligning film may oppose, a liquid crystal may be pushed out to the whole surface of a board | substrate, and then ultraviolet light is irradiated to the whole surface of a board | substrate, and a sealing compound will be hardened, and a liquid crystal cell can be manufactured. Can be.

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, although it was necessary to irradiate about 100,000 J / m <2> light, in the method of this invention, the light irradiation amount is 50,000 J / m <2> or less, Furthermore, 10,000 J / m <2> or less Even if it is set as desired, a desired liquid crystal display element can be obtained, and it can contribute to the reduction of the manufacturing cost of a liquid crystal display element, and can lower the electrical characteristic resulting from strong light irradiation, and the fall of long-term reliability.

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

(Example)

<Synthesis example of (A) polyorganosiloxane>

The weight average molecular weight Mw in the following synthesis examples is polystyrene conversion value measured by the gel permeation chromatography (GPC).

Synthesis Example A-1 (Synthesis Example by Production Method 1)

Oxalic acid 11.3g and ethanol 24.2g were put into the reaction container provided with the stirrer, the thermometer, the dropping funnel, and the reflux cooling tube, and it stirred and prepared the ethanol solution of oxalic acid. Subsequently, after heating this solution to 70 degreeC under nitrogen atmosphere, the mixture which consists of 12.3 g of tetraethoxysilane and 2.2 g of dodecyl triethoxysilane was dripped here as a silane compound. After completion | finish of dripping, the temperature of 70 degreeC was hold | maintained for 6 hours, It cooled to 25 degreeC after that, Then, the solution containing polyorganosiloxane (A-1) was prepared by adding 40.0 g of butyl cellosolves.

The weight average molecular weight Mw of the polyorganosiloxane (A-1) contained in this solution was 12, 000.

Synthesis Example A-2 (Synthesis Example by Production Method 2)

45.2 g of propylene glycol monomethyl ether, 18.8 g of tetraethoxysilane, and 3.3 g of dodecyl triethoxysilane were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, and the mixture was stirred to obtain a silane compound. The mixed solution was prepared. Subsequently, after heating this solution to 60 degreeC, the oxalic acid solution which consists of 8.8 g of water and 0.1 g of oxalic acid was dripped here. After completion of the dropwise addition, the solution was heated to 90 ° C for 3 hours, and then cooled to room temperature. Next, the solution containing polyorganosiloxane (A-2) was prepared by adding 76.2 g of butyl cellosolves here.

The weight average molecular weight Mw of the polyorganosiloxane (A-2) contained in this solution was 11, 000.

Synthesis Example A-3 (Synthesis Example by Production Method 4)

[Hydrolysis and Condensation Reaction of Silane Compounds]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) 246.4 as a silane compound, 1,000 g of methyl isobutyl ketone as a solvent, and 10.0 g of triethylamine was put as a catalyst, and it mixed at room temperature. Subsequently, 200 g of deionized water was added dropwise thereto over 30 minutes from the dropping funnel, followed by reaction at 80 ° C. for 6 hours while stirring under reflux. 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 and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an epoxy group. Obtained as a clear liquid.

It is confirmed that the poly turned with respect to the organosiloxane, obtained ^l H-NMR performing the analysis results, the chemical shifts (δ) = a peak based on the epoxy group in the vicinity of 3.2ppm as theoretical strength, a side reaction of the epoxy group is not up in the reaction It became.

[Reaction of Polyorganosiloxane with Epoxy Group with Specific Carbonic Acid]

In a 500 mL three-necked flask, polyorganosiloxane having an epoxy group obtained above, 60.0 g of methyl isobutyl ketone as a solvent, and 82.3 g of 4- (4-pentyl-cyclohexyl) -benzoic acid as the specific carbonic acid (the above polyorgano) Equivalent to 30 mol% with respect to the epoxy group of the siloxane) and 0.10 g of UCAT 18X (trade name, which is a curing accelerator of an epoxy compound manufactured by San Afro Co., Ltd.), were reacted under stirring at 100 ° C. for 48 hours. After 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) the polyorganosiloxane (A-3). ) 261.2 g. The weight average molecular weight Mw of this polyorganosiloxane (A-3) was 6,500.

<Synthesis example of other polymer>

Synthesis Example PI-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 and 3- (3,5-diaminobenzoyloxy) as diamine 52 g (0.10 mol) of cholestan were dissolved in 830 g of N-methylpyrrolidone (NMP), and the mixture was reacted at 60 ° C for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was aliquoted, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP was 60 mPa? S.

Subsequently, NMP1,900g was added to the obtained polyamic acid solution, pyridine 40g and acetic anhydride 51g were added, and the dehydration ring-closure reaction was performed at 110 degreeC for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was substituted with fresh NMP (the pyridine and acetic anhydride used in the imidization reaction were removed to the outside of the system by this operation) to thereby remove the polyimide (PI-1) having an imidization rate of about 50%. The solution containing 15 weight% was obtained. The obtained polyimide solution was fractionated and the solution viscosity measured as a solution of 10 weight% of polyimide concentration by adding NMP was 47 mPa * s.

Example 1

<Preparation of a polymer composition>

(A) To a solution containing the polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as polyorganosiloxane, butyl cellosolve is added as a solvent, and further (B) as a polymerizable unsaturated compound. The compound represented by Formula (B-1-1) described later was added to 15 parts by weight based on 100 parts by weight of the polyorganosiloxane (A), to obtain a solution having a solid content concentration of 5.0% by weight. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

<Production of Liquid Crystal Cells>

Using the polymer composition prepared above, the pattern (three types) and ultraviolet irradiation amount (three levels) of the transparent electrode were changed, nine liquid crystal cells in total were manufactured, and the following evaluation was performed.

[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 Sashing Co., Ltd.), 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 a mother-foot indentation length 0.1mm. Thereafter, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

Next, after apply | coating the aluminum oxide sphere containing epoxy resin adhesive of diameter 5.5micrometer to the outer edge of the surface which has one liquid crystal aligning film among the said pair of board | substrates, a liquid crystal aligning film surface may be The adhesive was cured by overlapping each other so as to face each other. Subsequently, after filling a nematic liquid crystal (MLC-6608 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal injection port, the liquid crystal cell was manufactured by sealing a liquid crystal injection port with an acryl-type photocuring adhesive.

The above operation was repeated to produce three liquid crystal cells having a transparent electrode without a pattern.

One of them was used for evaluation of the pretilt angle mentioned later as it was. Each of the remaining two liquid crystal cells was subjected to light irradiation in the state where a voltage was applied between the conductive films by the following method, and then used for evaluation of the pretilt angle and the voltage holding ratio.

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

[Evaluation of Pretilt Angle]

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

Table 1 shows 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>.

[Evaluation of Voltage Integrity]

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

Table 1 shows the voltage holding ratios 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 10,000 J / m 2.

[Production of Liquid Crystal Cell Having 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 printing machine (Nihon Sashingsatsu Co., Ltd.) on each electrode surface of glass substrates A and B each having an ITO electrode partitioned into a plurality of regions. Co., Ltd.) was applied, and the solvent was removed by heating (prebaking) on a hot plate at 80 ° C. for 1 minute, and then heating (postbaking) on a hot plate at 150 ° C. for 10 minutes to obtain an average film thickness of 600 mm 3. A coating film was formed. After performing ultrasonic cleaning for 1 minute in ultrapure water about this coating film, the board | substrate which has a liquid crystal aligning film was obtained by drying for 10 minutes in 100 degreeC clean oven. This operation was repeated and the pair (2 sheets) of the board | substrate which has a liquid crystal aligning film was obtained.

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

The above operation was repeated to produce three liquid crystal cells having a patterned transparent electrode. One of them was used for evaluation of the response speed mentioned later as it was. For the remaining two liquid crystal cells, light is emitted at a dose of 10,000 J / m 2 or 100,000 J / m 2 in a state where a voltage is applied between the conductive films by the same method as in the production of the liquid crystal cell having the transparent electrode without the pattern. After the investigation, the response speed was evaluated.

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 by irradiating a visible light lamp first without applying a voltage was measured with the photomultimeter, and this value was made into 0% of the relative transmittance. Next, the transmittance | permeability when AC 60V was applied for 5 second between 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 speeds 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>, respectively are shown in Table 1.

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

Preparation of the liquid crystal cell which has the said patterned transparent electrode except having used the glass substrates A and B which respectively have the ITO electrode patterned to the fishbone shape as shown in FIG. 2 using the polymer composition prepared above (1) In the same manner as in the above, 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 produced, respectively, and were subjected to evaluation of the response speed in the same manner as described above. The evaluation results are shown in Table 1.

Examples 2-7 and 9 and Comparative Examples l and 2

In Example 1, a polymer composition was prepared in the same manner as in Example 1, except that the types and amounts of the polyorganosiloxanes (B) and the polymerizable unsaturated compounds (B) were used as shown in Table 1, respectively. Using this, various liquid crystal cells were produced and evaluated.

In the preparation of the polymer composition, in Examples 5 and 6, two types of (B) polymerizable unsaturated compounds are used, respectively, and in Example 7, in addition to (A) polyorganosiloxane and (B) polymerizable unsaturated compounds, , Photopolymerization initiators of the kind and amount shown in Table 1 were used.

In the comparative example 2, when apply | coating a polymer composition, many application | coating splashes generate | occur | produced and the evaluable liquid crystal cell was not able to be manufactured.

The evaluation results are shown in Table 1.

Example 8

(A) Polyorganosiloxane (A-3) obtained in Synthesis Example A-3 was added to a solution containing polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as polyorganosiloxane. After adding 10 weight part with respect to 90 weight part of polyorganosiloxane (A-1), a butyl cellosolve is added to this as a solvent, and also as (B) polymerizable unsaturated compound, Formula (B-1) mentioned later In -2), the mixture of the compound whose n is 2-4 was added 8 weight part with respect to a total of 100 weight part of (A) polyorganosiloxane, and it was set as the solution of 5.0 weight% of solid content concentration. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters.

Various liquid crystal cells were produced and evaluated in the same manner as in Example 1 except that the polymer composition prepared above was used.

The evaluation results are shown in Table 1.

Example 10

The solution containing the polyimide (PI-1) obtained in Synthesis Example PI-1 as the other polymer, in an amount equivalent to 90 parts by weight in terms of polyimide, was diluted with NMP, followed by (A) polyorgano. As a siloxane, 10 weight part of polyorganosiloxanes (A-3) obtained by the said synthesis example A-3 are added, and also as a (B) polymerizable unsaturated compound, the compound represented by Formula (B-1-4) mentioned later, 30 weight part was added with respect to a total of 100 weight part of a polymer, and it was set as the solution of 5.0 weight% of solid content concentration. The polymer composition was prepared by filtering this solution using the filter of 1 micrometer of pore diameters, and produced and evaluated various liquid crystal cells using this.

The evaluation results are shown in Table 1.

Example 11

In Example 10, the amount of the other polymer and (A) polyorganosiloxane was used as described in Table 1, except that the epoxy compounds of the kind and amount shown in Table 1 were further used. In the same manner as described above, a polymer composition was prepared, and various liquid crystal cells were produced and evaluated using this.

The evaluation results are shown in Table 1.

In said Table 1, abbreviated-name of each component in a polymer composition is the following meanings, respectively.

[(B) Polymerizable Unsaturated Compound]

Compound (B-1)

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

B-1-2-1: Mixture of compounds whose n is 2-4 in following formula (B-1-2).

B-1-2-2: Mixture whose average of the sum total of two n is 2.6 in following formula (B-1-2)

B-1-3: compound represented by the following formula (B-1-3)

B-1-4-1: a compound in which n = 3 in following formula (B-1-4).

B-1-4-2: a compound in which n = 5 in the following formula (B-1-4).

Other unsaturated compounds

B-2-1: Methacrylic acid 4- (4'-phenyl-bicyclohexyl-4-yl) phenyl ester

B-2-2: Methacrylic acid-5ξ-cholestan-3-yl

[Photopolymerization initiator]

C-1: Phenyl- (4-p-tolylsulfanyl-phenyl) -methanone

[Epoxy Compound]

E-1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

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

Claims (12)

On the said conductive film of a pair of board | substrates which have a conductive film, respectively,
(A) polyorganosiloxane and
(B) polymerizable unsaturated compound
A coating composition is formed by applying a polymer composition containing
A pair of substrates on which the coating film is formed are disposed to face each other such that the coating film is opposed to each other via a layer of liquid crystal molecules to form a liquid crystal cell,
And a step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films having the pair of substrates. The method of claim 1,
The said (B) polymerizable unsaturated compound is a following formula (B-II) in a molecule | numerator:

(In formula (B-II), R is a hydrogen atom or a methyl group, and Y ² and Y ³ are each independently an oxygen atom or a sulfur atom.)
The manufacturing method of the liquid crystal display element which contains the compound (B-1) which has at least 2 of the monovalent group shown by these. The method of claim 2,
The said compound (B-1) is a following formula (BI) in a molecule | numerator:

(In formula (BI), X <^1> and X <^2> are respectively independently a 1, 4- phenylene group or l, 4- cyclohexylene group, Y <^1> is a single bond and C1-C4 bivalent hydrocarbon. Group, an oxygen atom, a sulfur atom or? COO ?, provided that X ¹ and X ² are substituted with one or a plurality of C 1-4 alkyl groups, C 1-4 alkoxyl groups, fluorine atoms or cyano groups good)
The manufacturing method of the liquid crystal display element which further contains at least 1 of the bivalent group shown by these. 4. The method according to any one of claims 1 to 3,
Said (A) polyorganosiloxane is following formula (A-1):

(In formula (A-1), n1 is an integer of 0-2, n2 is 0 or 1, and when n1 + n2 is 2 or more, R is a hydrogen atom, a C1-C20 alkyl group, or a C1-C20 fluoro. R is an alkyl group, and when n1 + n2 is 0 or 1, R is a group having a steroid structure, an alkyl group having 4 to 20 carbon atoms, or a fluoroalkyl group having 2 to 20 carbon atoms)
The manufacturing method of the liquid crystal display element which has group represented by. The method of claim 3,
The compound (B-1) has a di (meth) acrylate having a biphenyl structure, a di (meth) acrylate having a phenyl-cyclohexyl structure, and a di (meth) acrylate having a 2,2-diphenylpropane structure And at least one compound selected from the group consisting of di (meth) acrylate having a diphenylmethane structure and di-thio (meth) acrylate having a diphenylthioether structure. The method of claim 1,
The said (A) polyorganosiloxane is a manufacturing method of the liquid crystal display element obtained by reacting the silane compound which has an alkoxyl group or a halogen atom, or its mixture in presence of dicarboxylic acid and alcohol. The method of claim 1,
The said (A) polyorganosiloxane is a manufacturing method of the liquid crystal display element obtained by hydrolyzing and condensing the silane compound which has an alkoxyl group or a halogen atom, or its mixture. The method of claim 1,
The said polymer composition is a manufacturing method of the liquid crystal display element which further contains at least 1 sort (s) chosen from the group which consists of a polyamic acid and a polyimide. The method of claim 1,
The said polymer composition is a manufacturing method of the liquid crystal display element which further contains an epoxy compound. 4. The method according to any one of claims 1 to 3,
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. It was manufactured by the manufacturing method of the liquid crystal display element in any one of Claims 1-3, The liquid crystal display element characterized by the above-mentioned. A polymer composition containing (A) a polyorganosiloxane and (B) a polymerizable unsaturated compound and used in the method for producing a liquid crystal display device according to claim 1.

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