JP5874904B2 - Manufacturing method of liquid crystal display element - Google Patents

Description

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

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

  On the other hand, Non-Patent Document 1 proposes a method using a liquid crystal alignment film formed from a polyimide liquid crystal aligning agent containing a reactive mesogen. According to Non-Patent Document 1, a liquid crystal display element including a liquid crystal alignment film formed by such a method is said to respond quickly to liquid crystal molecules. However, Non-Patent Document 1 does not provide any guidance on what kind of reactive mesogen should be used, and the amount of necessary ultraviolet irradiation is still large, and there are concerns about display characteristics, particularly voltage holding characteristics. Not wiped out.

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

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

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element having a wide viewing angle, a high response speed of liquid crystal molecules, and excellent display characteristics and long-term reliability. To do.

According to the present invention, the above problem of the present invention is as follows.
On the conductive film of the pair of substrates having the conductive film,
Applying a polymer composition containing (A) a polyorganosiloxane and (B) a polymerizable unsaturated compound to form a coating film;
A pair of substrates on which the coating film is formed are arranged to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell,
This is achieved by a method for manufacturing a liquid crystal display element, which includes a step of irradiating light to the liquid crystal cell in a state where a voltage is applied between conductive films of the pair of substrates.

The liquid crystal display device manufactured by the method of the present invention has a wide viewing angle, a high response speed of liquid crystal molecules, sufficient transmittance and contrast, excellent display specification, and display characteristics even when driven continuously for a long time. Will not be damaged.
In addition, according to the method of the present invention, the amount of light required for irradiation can be reduced, which contributes to a reduction in manufacturing cost of the liquid crystal display element.
Therefore, the liquid crystal display device manufactured by the method of the present invention is superior to the conventionally known liquid crystal display device in both performance and cost, and can be suitably applied to various applications.

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

<Polymer composition>
The polymer composition used in the method of the present invention is:
(A) Polyorganosiloxane and (B) polymerizable unsaturated compound are contained.

[(A) Polyorganosiloxane]
Regarding the (A) polyorganosiloxane contained in the polymer composition used in the present invention, the polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography is 500 to 1,000,000. Preferably, it is 1,000 to 100,000, more preferably 1,000 to 50,000.
(A) The polyorganosiloxane has the following formula (A-1)

(In formula (A-1), n1 is an integer of 0 to 2,
n2 is 0 or 1,
when n1 + n2 is 2 or more, R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms;
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. However, when n1 + n2 is 0, R is not an octadecyl group. )
It has group represented by these.
Examples of the group having a steroid structure of R in the above formula (A-1) include a 3-cholestanyl group, 3-cholestenyl group, 3-lanostanyl group, 3-colanyl group, 3-pregnal group, 3-androstanyl group, A 3-estranyl group etc. can be mentioned.
When the carbon number of the alkyl group and fluoroalkyl group of R in the above formula (A-1) is 3 or more, each is preferably a linear group. As the fluoroalkyl group, the following formula (F)
_{CF 3 - (CF 2) a} - (CH 2) b - (F)
(In Formula (F), a and b are each an integer of 0 to 19, provided that when n1 + n2 in Formula (A-1) is 2 or more, a + b is an integer of 0 to 19,
When n1 + n2 is 0 or 1, a + b is an integer of 3-19. )
It is preferable that it is group represented by these.
Preferred examples of the group represented by the formula (A-1) include, for example, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, the following formulas (A-1-1) to (A-1-3)

(R in formulas (A-1-1) to (A-1-3) has the same meaning as R in formula (A-1)).
And a group represented by R in the formulas (A-1-1) to (A-1-3) is preferably a linear alkyl group having 1 to 18 carbon atoms or a fluoroalkyl group.
(A) The proportion of the group represented by the above formula (A-1) in the polyorganosiloxane is preferably 0.0002 mol / g or more, and is 0.004 to 0.002 mol / g. More preferably, it is preferably 0.0005 to 0.0016 mol / g.
Such (A) polyorganosiloxane 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 above formula (A-1) and an alkoxyl group (hereinafter referred to as “silane compound (a1)”), or silane. A mixture of the compound (a1) and another alkoxysilane compound (hereinafter referred to as “silane compound (a2)”)
A method of reacting in the presence of a dicarboxylic acid and an alcohol (production method 1), a method of hydrolysis / condensation (production method 2), or a silane compound having an epoxy group and an alkoxyl group (hereinafter referred to as “silane compound (a2-1)”. ) "Or a mixture of the silane compound (a2-1) and another alkoxysilane compound (hereinafter referred to as" silane compound (a2-2) "),
A method of reacting in the presence of a dicarboxylic acid and an alcohol and further reacting with a compound having a group represented by the above formula (A-1) and a carboxyl group (hereinafter referred to as “specific carboxylic acid”) (Production Method 3) ), Or a method of further reacting with a specific carboxylic acid after hydrolysis / condensation (production method 4)
Can be manufactured by.
The silane compounds (a2-1) and (a2-2) preferably each do not have a group represented by the formula (A-1). In this case, the silane compounds (a2-1) and (a2-1) The set obtained by combining (a2-2) matches 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) are respectively synonymous with n1, n2 and R in the formula (A-1), n is an integer of 1 to 3, and R ¹ is It is a phenyl group or an alkyl group having 1 to 12 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms.)
The compound represented by these can be mentioned. N in the formula (a1-1) is preferably 1.
Specific examples of such a silane compound (a1) include, for example, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-i-propoxysilane, n-butyltri -N-butoxy silane, n-butyl tri-sec-butoxy silane, n-butyl tri-n-pentoxy silane, n-butyl tri-sec-butoxy silane, n-butyl triphenoxy silane, n-butyl tri-p- Methylphenoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-pentyltri-n-propoxysilane, n-pentyltri-i-propoxysilane, n-pentyltri-n-butoxysilane, n-pentyltrisilane sec-butoxysilane, n-pentyl Ri-n-pentoxysilane, n-pentyltri-sec-butoxysilane, 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-propoxysilane, 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-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-propoxysilane, n-dodecyltri-i-propoxysilane, n- Examples include dodecyltri-n-butoxysilane and n-dodecyltri-sec-butoxysilane, and one or more selected from these can be used.

Examples of the silane compound (a2-1) include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylmethyldisilane. Ethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri An ethoxysilane etc. can be mentioned and 1 or more types selected from these can be used.
The silane compound (a2-2) is preferably an alkoxysilane compound other than the silane compound (a1) and the silane compound (a2-1), for example, preferably the following formula (a2-2-1)
(R ² ) _m Si (OR ³ ) _4-m (a2-2-1)
(In Formula (a2-2-1), R ² is an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a phenyl group, or has an alkyl group having 1 to 3 carbon atoms. An alkylphenyl group,
R ³ is a phenyl group or an alkyl group having 1 to 12 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 12 carbon atoms,
m is an integer of 0-3. )
The compound represented by these can be mentioned.

Specific examples of the compound represented by the above formula (a2-2-1) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, as a compound in which m is 0. Tetra-sec-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane and the like;
Examples of compounds in which m is 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri- n-pentoxysilane, methyltri-sec-butoxysilane, methyltriphenoxysilane, methyltri-p-methylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-i-propoxysilane Ethyl tri-n-butoxy silane, ethyl tri-sec-butoxy silane, ethyl tri-n-pentoxy silane, ethyl tri-sec-butoxy silane, ethyl triphenoxy silane, ethyl tri- -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-butoxysilane, n-propyltriphenoxysilane, n-propyltri-p-methylphenoxysilane 2- (trifluoromethyl) ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) 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-butoxysilane, phenyltri-sec-butoxysilane and the like;

Examples of compounds in which m is 2 include dimethyldimethoxysilane, diethyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, and di-n-propyldiethoxysilane. Di-i-propyldiethoxysilane, dimethyl-di-i-propoxysilane, diethyl-di-i-propoxysilane, di-n-propyl-di-i-propoxysilane, 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 compounds in which m is 3 include trimethylmethoxysilane, triethylmethoxysilane, tri-n-propylmethoxysilane, tri-i-propylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, 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-propi -sec- Butokishishishiran, tri -i- propyl -sec- Butokishishishiran, etc., can be exemplified respectively, may be used one or more selected from among these.
As the silane compound (a2-2), at least one selected from the group consisting of ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane and traethoxysilane is used. It is preferable to use at least one selected from the group consisting of tetramethoxysilane and tetraethoxysilane.

The ratio of each silane compound used as a raw material when producing (A) polyorganosiloxane in the present invention to all silane compounds is as follows according to the method for producing (A) polyorganosiloxane.
(1) (A) Production of polyorganosiloxane by production 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) Production of polyorganosiloxane by production method 3 or 4;
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, a method of reacting a silane compound in the presence of dicarboxylic acid and alcohol, which is performed in Production Methods 1 and 3, will be described.

Examples of the dicarboxylic acid used here include oxalic acid, malonic acid, a compound in which two carboxyl groups are bonded to an alkylene group having 2 to 4 carbon atoms, and benzene dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like, and it is preferable to use one or more selected from these. . Particularly preferred is oxalic acid.
The proportion of dicarboxylic acid used is preferably such that the amount of carboxyl groups relative to a total of 1 mol of alkoxyl groups in the silane compound used as a raw material is 0.2 to 2.0 mol, 0.5 to 1 More preferably, the amount is 5 mol.

As the alcohol, a primary alcohol can be preferably used. 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, heptanol-3, n-octanol, 2-ethylhexanol, n-nonyl alcohol, 2,6-dimethylheptanol -4, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc., and at least one selected from these Good to use Arbitrariness. The alcohol used here is preferably an aliphatic primary alcohol having 1 to 4 carbon atoms, from methanol, ethanol, i-propanol, n-propanol, i-butanol, sec-butanol and t-butanol. It is more preferable to use one or more selected from the group consisting of, and it is particularly preferable to use one or more selected from the group consisting of methanol and ethanol.
The proportion of alcohol used in production methods 1 and 3 is preferably such that the proportion of the silane compound and dicarboxylic acid in the total amount of the reaction solution is 3 to 80% by weight, and the proportion of 25 to 70% by weight. More preferably.
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 the reaction of the silane compound in Production Methods 1 and 3, it is preferable not to use any other solvent other than the alcohol as described above.
In the production method as described above, it is presumed that polyorganosiloxane, which is a (co) condensate of silane compound, is produced by the action of alcohol on the intermediate produced by the reaction of silane compound and dicarboxylic acid. .

Next, the hydrolysis / condensation reaction of the silane compound performed in the production methods 2 and 4 will be described.
This hydrolysis / condensation reaction can be carried out by reacting a silane compound and water, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
The ratio of the water used here is preferably 0.5 to 2.5 mol as an amount relative to a total of 1 mol of alkoxyl groups of the silane compound used as a raw material.
Examples of the catalyst include acids, bases, and metal compounds. Specific examples of such a catalyst include, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid and the like as the acid.
As the base, any of an inorganic base and an organic base can be used. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like. ;
Examples of the organic base include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; tetramethylammonium hydroxide, and the like.
Examples of the metal compound include a titanium compound and a zirconium compound.
The ratio of the catalyst used is preferably 10 parts by weight or less, more preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of the silane compounds used as raw materials. The amount is preferably 1 part by weight.

Examples of the organic solvent include alcohols, ketones, amides, esters, and other aprotic compounds. As the alcohol, any of an alcohol having one hydroxyl group, an alcohol having a plurality of hydroxyl groups, and a partial ester of an alcohol having a plurality of hydroxyl groups can be used. As said ketone, a monoketone and (beta) -diketone can be used preferably.
Specific examples of such an organic solvent include alcohols having one hydroxyl group such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, and n-pen. Tanol, i-pentanol, 2-methylbutanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol-3, n-octanol, 2-ethylhexanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like;
Examples of alcohols having a plurality of hydroxyl groups include ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptane Diol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

Examples of alcohol partial esters having a plurality of hydroxyl groups include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and ethylene glycol mono-2. -Ethyl butyl 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, B propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like;
Examples of monoketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di- -I-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, etc .;
Examples of the β-diketone include acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3 , 5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2 , 4-pentanedione, etc .;
Examples of amides include 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-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like;

Examples of esters include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, Sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, ethylene acetate monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene acetate Recall mono-n-butyl ether, 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, diacetic acid Glycol, 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, etc .;
Examples of other aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl- 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, etc. can be mentioned, and one or more selected from these can be used. can do.

The proportion of the organic solvent used is preferably such that the total weight of components other than the organic solvent in the reaction solution is 1 to 90% by weight as the proportion of the total amount of the reaction solution, and 10 to 70% by weight. It is more preferable to set it as a ratio.
The water added during the hydrolysis / condensation reaction of the silane compound can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent.
The catalyst may be added in advance to a raw material silane compound or a solution in which the silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in the added water.
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 means as described above, in the production methods 1 and 2, (A) polyorganosiloxane contained in the polymer composition in the present invention is directly obtained;
On the other hand, in production methods 3 and 4, (A) a polyorganosiloxane having an epoxy group, which is a precursor of polyorganosiloxane, is obtained. In production methods 3 and 4, the polyorganosiloxane having an epoxy group can be further reacted with a specific carboxylic acid to obtain (A) polyorganosiloxane contained in the polymer composition in the present invention.
The specific carboxylic acid used here is a compound having a group represented by the above formula (A-1) and a carboxyl group. As specific carboxylic acid, for example, the following formula (C-1)

(In the formula (C-1), n1, n2 and R are respectively synonymous with n1, n2 and R in the formula (A-1).)
The compound represented by these can be mentioned. Specific examples of the compound represented by the formula (C-1) include, 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. One or more selected from among them can be used.
The proportion of the specific carboxylic acid used for the reaction with the polyorganosiloxane having an epoxy group is preferably 5 to 50 mol with respect to 1 mol of the epoxy group possessed by the precursor of the polyorganosiloxane (A). 10 to 40 mol is more preferable.
The reaction between the polyorganosiloxane having an epoxy group and the specific carboxylic acid can be carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.
As the catalyst used here, an organic base can be used, and a known compound can be used as a so-called curing accelerator that accelerates the reaction between the epoxy compound and the 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;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide. Are preferable, and one or more selected from these can be used.

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

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium, o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, 4 such as tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Phosphonium salt;
1,8-diazabicyclo [5.4.0] undecene-7, a diazabicycloalkene such as its organic acid salt;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
In addition to metal halides such as zinc chloride and stannic chloride,
A latent curing accelerator can be mentioned. Examples of the latent curing accelerator include high melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide or an adduct of an amine and an epoxy resin;
A microcapsule-type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organic phosphorus compound, or quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing accelerator;
Examples thereof include high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride are preferred.
The catalyst is preferably used in an amount of 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane having an epoxy group. Is done.
Examples of the organic solvent used in the reaction between the polyorganosiloxane having an epoxy group and the specific carboxylic acid include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent is 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, more preferably 5 to 50% by weight. used.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
The (A) polyorganosiloxane obtained as described above by any one of production methods 1 to 4 is preferably purified by a known appropriate method and then used for the preparation of the polymer composition.

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

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

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

Specific examples thereof include di (meth) acrylate having a biphenyl structure, such as 4′-acryloyloxy-biphenyl-4-yl-acrylate,
4′-methacryloyloxy-biphenyl-4-yl-methacrylate,
2- [4 ′-(2-acryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl acrylate,
2- [4 ′-(2-methacryloyloxy-ethoxy) -biphenyl-4-yloxy] -ethyl methacrylate,
Bishydroxyethoxybiphenyl diacrylate,
Bishydroxyethoxybiphenyl dimethacrylate,
2- (2- {4 ′-[2- (2-acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl acrylate,
2- (2- {4 ′-[2- (2-methacryloyloxy-ethoxy) -ethoxy] -biphenyl-4-iroxy} -ethoxy) -ethyl methacrylate,
Diacrylate of biphenyl ethylene oxide adduct,
Dimethacrylate of biphenyl ethylene oxide adduct,
Diacrylate of biphenyl propylene oxide adduct,
Dimethacrylate of biphenyl propylene oxide adduct,
2- (4′-acryloyloxy-biphenyl-4-yloxy) -ethyl acrylate,
2- (4′-methacryloyloxy-biphenyl-4-yloxy) -ethyl methacrylate and the like;

Examples of di (meth) acrylate having a phenyl-cyclohexyl structure include 4- (4-acryloyloxy-phenyl) -cyclohexyl acrylate,
4- (4-methacryloyloxy-phenyl) -cyclohexyl methacrylate,
2- {4- [4- (2-acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl acrylate,
2- {4- [4- (2-methacryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl methacrylate,
2- [2- (4- {4- [2- (2-acryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl acrylate,
2- [2- (4- {4- [2- (2-methacryloyloxy-ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl methacrylate and the like;

As di (meth) acrylate having a 2,2-diphenylpropane structure, for example, the following formula

(In the above formula, a plurality of R ⁴ are each independently a hydrogen atom or a methyl group,
A plurality of R ⁵ are each independently a hydrogen atom or a methyl group;
A plurality of n's are each independently an integer of 0 to 5. )
A compound represented by, for example, 4- [1- (4-acryloyloxy-phenyl) -1-methyl-ethyl] -phenyl acrylate,
4- [1- (4-methacryloyloxy-phenyl) -1-methyl-ethyl] -phenyl methacrylate,
2- (4- {1- [4- (2-acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl acrylate,
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 adduct of bisphenol A,
Diacrylate of propylene oxide adduct of bisphenol A,
Dimethacrylate of propylene oxide adduct of bisphenol A,

2- (4- {1- [4- (2-acryloyloxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethyl acrylate,
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-ethyl acrylate,
2- {2- [4- (1- {4- [2- (2-methacryloyloxy-propoxy) -propoxy] -phenyl} -1-methyl-1-ethyl) -phenoxy] -1-methyl-ethoxy } -1-methyl-ethyl methacrylate,
3- {4- [1- (3- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethylphenoxy-2 -Hydroxy-propyl acrylate,
3- {4- [1- (3- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethylphenoxy 2-hydroxy-propyl methacrylate,
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- {1- [4- (3-Methacryloyloxy-2-hydroxy-propoxy) -3-cyclohexyl-phenyl] -1-methyl-ethyl} -2-cyclohexyl-phenoxy) -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-yloxy) -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-propyl methacrylate,
3- (4- {1- [4- (3-acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propyl acrylate,
3- (4- {1- [4- (3-methacryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propyl methacrylate,
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-propyl acrylate,
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-propyl methacrylate,
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-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 methacrylate,
1- (2- {4- [1- (4- {2- [2-hydroxy-3- (1-methylene-allyloxy) -propoxy] -propoxy} -phenyl) -1-methyl-ethyl] -xy} -1-methyl-ethoxy) -3- (1-methylene-allyloxy) -propan-2-ol and the like;

Examples of di (meth) acrylates having a diphenylmethane structure include 4- (4-acryloyloxy-benzyl) -phenyl acrylate,
4- (4-methacryloyloxy-benzyl) -phenyl methacrylate,
2- {4- [4- (2-acryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl acrylate,
2- {4- [4- (2-methacryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl methacrylate,
Diacrylate of ethylene oxide adduct of bisphenol F,
Dimethacrylate of ethylene oxide adduct of bisphenol F,
Diacrylate of propylene oxide adduct of bisphenol F,
Dimethacrylate of propylene oxide adduct of bisphenol F,
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-ethyl acrylate,
2- {4- [4- (2-methacryloyloxy-propoxy) -benzyl-phenoxy} -1-methyl-ethyl methacrylate,
2- [2- (4- {4- [2- (2-acryloyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl-ethylethyl acrylate,
2- [2- (4- {4- [2- (2-methacryloyloxy-propoxy) -propoxy] -benzyl} -phenoxy) -1-methyl-ethoxy] -1-methyl-ethylethyl methacrylate and the like;
Examples of di-thio (meth) acrylates having a diphenylthioether structure include 4- (4-thioacryloylsulfanyl-phenylsulfanyl) -phenyldithioacrylate,
4- (4-thiomethacryloylsulfanyl-phenylsulfanyl) -phenyldithiomethacrylate,
Bis (4-methacryloylthiophenyl) sulfide and the like;
Examples of the other compound (B-1) include 2,5-bis {4- (3-acryloyloxy-propoxy) -benzoic acid} toluene and the like.

Such a compound (B-1) can be synthesized by appropriately combining organic chemistry methods, or can be obtained as a commercial product. Examples of commercially available compounds (B-1) include bishydroxyethoxy BP diacrylate and bishydroxyethoxy Bis-A diacrylate (manufactured by Honshu Chemical Industry Co., Ltd.);
Aronix M-208, M-210 (manufactured by Toagosei Co., Ltd.);
SR-349, SR-601, SR-602 (manufactured by Sartomer);
KAYARAD R-712, R-551 (manufactured by Nippon Kayaku Co., Ltd.);
NK ester BPE-100, NK ester BPE-200, NK ester BPE-500, NK ester BPE-1300, NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Actilane 420 (manufactured by Nippon Shibel Hegner Co., Ltd.) ):
Light ester BP-2EM, light acrylate BP-4EA, light acrylate BP-4PA, epoxy ester 3000M, epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.);
V # 540, V # 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.);
FA-321M (manufactured by Hitachi Chemical Co., Ltd.);
MPSMA (manufactured by Sumitomo Seika);
Lipoxy VR-77 (manufactured by Showa Polymer Co., Ltd.) can be exemplified.

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

[Other ingredients]
The polymer composition used in the present invention comprises the (A) polymer and the (B) polymerizable unsaturated compound as essential components as described above, but other than these, other effects may be used as long as the effects of the present invention are not diminished. It may contain components. Examples of other components that can be used here include polymers other than (A) polymers (hereinafter referred to as “other polymers”), epoxy compounds, photopolymerization initiators, radical scavengers, and light stabilizers. An agent etc. can be mentioned.
The above-mentioned other polymers can be used for further improving the solution characteristics of the obtained polymer composition and the electrical characteristics of the formed coating film, and the response speed of the resulting liquid crystal display element. Such other polymers are polymers other than the polymer (A) as described above, for example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, Examples thereof include poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylates, and one or more selected from these can be used. The other polymer is preferably at least one selected from the group consisting of polyamic acid and polyimide.

The polyamic acid can be produced, for example, by using tetracarboxylic dianhydride and diamine described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188) and reacting them by a known method. .
In order to synthesize the polyamic acid, an alicyclic tetracarboxylic dianhydride as a tetracarboxylic dianhydride, specifically 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3 , 5-Tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2, 5-Dioxotetrahydro-3- Ranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4 , 6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane It is preferable to use -3,5,8,10-tetraone, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride and the like.

As the diamine used to synthesize the polyamic acid, it is preferable to use a diamine having a group having the property of aligning liquid crystal molecules (hereinafter referred to as “liquid crystal alignment diamine”), more preferably. It is to use a mixture of a liquid crystal alignment diamine and other diamines.
Examples of the liquid crystal alignment diamine include cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4- Diaminobenzene, 3,5-diaminobenzoate cholestanyl, 3,5-diaminobenzoate cholestenyl, 3,5-diaminobenzoate lanostannyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis ( 4-aminophenoxy) cholestane, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diamino Benzene, dodecanoxy 2,5-diaminobenzene, Tetoradekanokishi 2,5-diaminobenzene, Pentadekanokishi 2,5-diaminobenzene, Hekisadekanokishi 2,5-diaminobenzene, Okutadekanokishi 2,5-diaminobenzene, the following formula

The compound etc. which are represented by each of these can be mentioned, One or more types selected from these can be used.
Examples of the other diamine include p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, and 2,2′-dimethyl-4,4′-diamino. Biphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diaminodiphenylamine, 4,4 ′-(m-phenylenediisopropylidene) dianiline , One or more selected from these can be used.
The diamine used for synthesizing the polyamic acid preferably contains 3 mol% or more of the liquid crystal aligning diamine, more preferably 4 to 80 mol%, based on the total diamine. More preferably, it is contained in an amount of 5 to 50%, particularly preferably 10 to 40%.
The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0-100 ° C, preferably 0.1-24 hours, more preferably 0.5-12 hours. Done.
Here, examples of the organic solvent include an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, and hydrocarbon.

The polyimide can be obtained by dehydrating and ring-closing the polyamic acid produced as described above to imidize.
The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating if necessary. . Of these, the latter method is preferred.
In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  When the polymer composition used in the present invention contains other polymer, the use ratio of the other polymer is the total amount of the polymer ((A) the sum of the polymer and the other polymer). The same shall apply hereinafter), preferably 99% by weight or less, more preferably 70 to 98% by weight, and even more preferably 80 to 95% by weight.

When the polymer composition in the present invention contains an epoxy compound, adhesion of the formed coating film to the substrate and heat resistance can be further improved, and the response speed of the obtained liquid crystal display element is further improved. This is preferable.
As such an epoxy compound, an epoxy compound having two or more epoxy groups in the molecule is preferable. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N , N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexa N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, etc. Can be mentioned as preferred. A particularly preferable epoxy compound is an epoxy compound having two or more N-glycidyl groups in the molecule.
The blending ratio of the epoxy compound in the polymer composition in the present invention is preferably 50 parts by weight or less, more preferably 1 to 40 parts by weight, particularly 5 parts per 100 parts by weight of the total polymer. It is preferable to set it as -30 weight part.

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

Examples of commercially available photopolymerization initiators include IRGACURE-124, -149, -184, -369, -500, -651, -819, -907, -1000, and -1700. -1800, -1850, -1959, Darocur-1116, -1173, -1664, -2959, -4093 (above, manufactured by Ciba Specialty Chemicals);
KAYACURE-BMS, same-DETX, same-MBP, same-DMBI, same-EPA, same-OA (above, manufactured by Nippon Kayaku Co., Ltd.);
LUCIRIN TPO (BASF);
VICURE-10, -55 (above, manufactured by STAUFER);
TRIGONALP1 (manufactured by AKZO);
SANDORAY 1000 (manufactured by SANDOZ);
DEAP (manufactured by APJOHN);
QUANTACURE-PDO, the same -ITX, the same -EPD (manufactured by WARD BLEKINSSOP) and the like.
As the photopolymerization initiator, a benzophenone compound is preferably used from the viewpoint of high thermal stability.
The use ratio of the photopolymerization initiator is preferably 30 parts by weight or less, more preferably 0.1 to 30 parts by weight, and particularly preferably 0 to 100 parts by weight of the (B) polymerizable unsaturated compound. It is preferable to set it as 5-20 weight part.

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

As these commercial products, ADEKA Corporation ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO -330;
Sumilizer GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd .;
IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1326, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX3456, IRGANOX3114, IRGANOX3114, IRGANOX3114, manufactured by Ciba Japan
Examples include Yoshinox BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314, and the like manufactured by API Corporation.
The use ratio of the radical scavenger in the polymer composition in the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the (B) polymerizable unsaturated compound. .

[Polymer composition]
The polymer composition used in the present invention is a solution in which the above-mentioned (A) polymer and (B) polymerizable unsaturated compound and other optional additives are dissolved in a suitable organic solvent. It is preferable to be prepared.
Examples of the organic solvent that can be used here include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, and 4-hydroxy-4-methyl. -2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol -I-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether Ter, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether and the like.
As the use ratio of the organic solvent, the solid content concentration of the polymer composition (the ratio of the total weight of components other than the organic solvent in the polymer composition to the total weight of the polymer composition) is 1 to 15% by weight. It is preferable to set it as the ratio which becomes 1.5 to 8 weight%.

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

In order to apply the polymer composition onto the conductive film of the substrate, for example, an appropriate application method such as a roll coater method, a spinner method, a printing method, or an ink jet method can be used. After coating, the coated surface is preheated (prebaked) and then baked (postbaked) to form a coating film. The pre-bake conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C., and the post-bake conditions are preferably 120 to 300 ° C., more preferably 150 to 250 ° C., preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
The coating film thus formed may be used as it is for the production of a liquid crystal cell in the next step, or may be subjected to a rubbing treatment on the coating surface as necessary prior to the production of the liquid crystal cell. The rubbing treatment can be performed by rubbing the coating film surface in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Here, as described in Patent Document 1 (Japanese Patent Laid-Open No. 5-107544), a resist film is formed on a part of the coating surface after once rubbing, and is different from the previous rubbing. By performing a process of removing the resist film after performing the rubbing process in the direction and setting the rubbing direction to be different for each region, it is possible to further improve the visual field characteristics of the obtained liquid crystal display element.
Next, a pair of substrates on which the coating film has been formed are arranged to face each other with the coating film facing each other through a layer of liquid crystal molecules to form a liquid crystal cell.
The liquid crystal molecules used here are preferably nematic liquid crystals having negative dielectric anisotropy, such as dicyanobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals. Etc. can be used. The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.

In order to produce a liquid crystal cell using such a liquid crystal, for example, the following two methods can be mentioned.
As a first method, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap defined by the substrate surface and the sealing agent and then sealing the injection hole. Alternatively, as a second method, for example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and then a predetermined position on the liquid crystal alignment film surface is applied. After dropping the liquid crystal in several places, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant Thus, a liquid crystal cell can be manufactured.

Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
The voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
The amount of light irradiation is preferably 1,000 J / m ² or more and less than 100,000 J / m ² , more preferably 1,000 to 50,000 J / m ² . In the manufacture of a conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In} the method of the present invention, the amount of light irradiation was set to 50,000 J / M ² or less, and even if it is 10,000 J / m ² or less, a desired liquid crystal display element can be obtained, which contributes to a reduction in manufacturing cost of the liquid crystal display element and is caused by irradiation with strong light. It is possible to avoid deterioration of electrical characteristics and long-term reliability.
And a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after performing the above-mentioned treatment. As a polarizing plate used here, a polarizing plate formed by sandwiching a polarizing film called an “H film” in which iodine is absorbed while stretching and orientation of polyvinyl alcohol is sandwiched between cellulose acetate protective films, or a polarizing plate made of the H film itself, etc. Can be mentioned.

<Synthesis example of (A) polyorganosiloxane>
The weight average molecular weight Mw in the following synthesis examples is a polystyrene conversion value measured by gel permeation chromatography (GPC).
Synthesis Example A-1 (Synthesis Example by Production Method 1)
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 11.3 g of oxalic acid and 24.2 g of ethanol, and stirred to prepare an ethanol solution of oxalic acid. Next, this solution was heated to 70 ° C. in a nitrogen atmosphere, and then a mixture of 12.3 g of tetraethoxysilane and 2.2 g of dodecyltriethoxysilane was added dropwise thereto as a silane compound. After completion of the dropwise addition, the temperature of 70 ° C. was maintained for 6 hours, then cooled to 25 ° C., and then 40.0 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (A-1).
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)
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 45.2 g of propylene glycol monomethyl ether, 18.8 g of tetraethoxysilane, and 3.3 g of dodecyltriethoxysilane. A mixed solution of silane compounds was prepared. Subsequently, after heating this solution to 60 degreeC, the oxalic acid solution which consists of 8.8g of water and oxalic acid 0.1g was dripped here. After completion of dropping, the solution was heated at a solution temperature of 90 ° C. for 3 hours and then cooled to room temperature. Next, a solution containing polyorganosiloxane (A-2) was prepared by adding 76.2 g of butyl cellosolve thereto.
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 / condensation reaction of silane compounds]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) 246.4 as a silane compound, methyl isobutyl ketone 1, as a solvent, 000 g and 10.0 g of triethylamine as a catalyst were charged and mixed at room temperature. Next, 200 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure, whereby a polyorgano having an epoxy group is obtained. Siloxane was obtained as a viscous transparent liquid.
As a result of ¹ H-NMR analysis of this polyorganosiloxane, a peak based on epoxy groups was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and side reactions of epoxy groups occurred during the reaction. Not confirmed.
[Reaction of polyorganosiloxane having epoxy group with specific carboxylic 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, 82.3 g of 4- (4-pentyl-cyclohexyl) -benzoic acid as a specific carboxylic acid (the above polyorgano 0.10 g of UCAT 18X (trade name, manufactured by San Apro Co., Ltd., an epoxy compound curing accelerator) as a catalyst, and 100 ° C. The reaction was carried out with stirring for 48 hours. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried using magnesium sulfate, and then the solvent was distilled off to obtain (A) the first polymer, which is a polymer. 261.2g of organosiloxane (A-3) was obtained. The weight average molecular weight Mw of this polyorganosiloxane (A-3) was 6,500.

<Synthesis examples of other polymers>
Synthesis example PI-1
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine as diamine and 3 (3,5-diaminobenzoyl) 52 g (0.10 mol) of oxy) cholestane was dissolved in 830 g of N-methylpyrrolidone (NMP) and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP (removing pyridine and acetic anhydride used in the imidization reaction out of the system in this operation), so that the imidation ratio was about 50%. A solution containing about 15% by weight of polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 47 mPa · s.

Example 1
<Preparation of polymer composition>
(A) To the solution containing the polyorganosiloxane (A-1) obtained in Synthesis Example A-1 as a polyorganosiloxane, butyl cellosolve is added as a solvent, and (B) a polymerizable unsaturated compound is added to the formula described below. 15 parts by weight of the compound represented by (B-1-1) was added to 100 parts by weight of the polyorganosiloxane (A) to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
<Manufacture of liquid crystal cells>
Using the polymer composition prepared above, a total of nine liquid crystal cells were produced by changing the transparent electrode pattern (three types) and the ultraviolet irradiation amount (three levels), and evaluated as follows.

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

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

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (1)]
The polymer composition prepared above is patterned into a slit shape as shown in FIG. 1, and a liquid crystal alignment film is printed on each electrode surface of glass substrates A and B each having an ITO electrode partitioned into a plurality of regions. Apply using a machine (Nissha Printing Co., Ltd.), heat on a hot plate at 80 ° C for 1 minute (pre-bake) to remove the solvent, then heat on a hot plate at 150 ° C for 10 minutes (post-bake) ) To form a coating film having an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.
Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edge of the surface having one liquid crystal alignment film of the pair of substrates, the liquid crystal alignment film surfaces of the pair of substrates are relative to each other. The adhesive was cured by overlapping and pressing. Next, after filling nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) between a pair of substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. did.
The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of response speed as described later. For the remaining two liquid crystal cells, 10,000 J / m ² or 100,000 J / m in a state where a voltage is applied between the conductive films by the same method as in the production of the liquid crystal cell having the transparent electrode without pattern. After irradiating with light at an irradiation amount of m ² , the response speed was evaluated.
The electrode pattern used here is the same type as the electrode pattern in the PSA mode.

[Evaluation of response speed]
For each of the liquid crystal cells produced above, first, the luminance of light transmitted through the liquid crystal cell by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was defined as a relative transmittance of 0%. . Next, the transmittance when AC 60 V was applied between the electrodes of the liquid crystal cell for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%.
At this time, when 60 V AC was applied to each liquid crystal cell, the time until the relative transmittance shifted from 10% to 90% was measured, and this time was defined as the response speed and evaluated.
The liquid crystal cell of not irradiated with light, each of the response speed of the liquid crystal cell and the liquid crystal cells of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} are shown in Table 1.

[Production of Liquid Crystal Cell Having Patterned Transparent Electrode (2)]
A liquid crystal having the patterned transparent electrode except that glass substrates A and B each having ITO electrodes patterned in a fishbone shape as shown in FIG. 2 were used using the polymer composition prepared above. in the same manner as in preparation of the cell (1), a liquid crystal cell of not irradiated with light, a liquid crystal cell and a liquid crystal cell of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} was produced, respectively in the same manner as described above The response speed was evaluated. The evaluation results are shown in Table 1.

Examples 2-7 and 9 and Comparative Examples 1 and 2
In Example 1 above, the polymer composition was the same as Example 1 except that the types and amounts of (A) polyorganosiloxane and (B) polymerizable unsaturated compound were as shown in Table 1. A product was prepared, and various liquid crystal cells were produced and evaluated using the product.
In the preparation of the polymer composition, in Examples 5 and 6, two (B) polymerizable unsaturated compounds were used,
In Example 7, in addition to (A) polyorganosiloxane and (B) polymerizable unsaturated compound, the types and amounts of photopolymerization initiators shown in Table 1 were used.
In Comparative Example 2, a large amount of coating repellency was generated when the polymer composition was applied, and an evaluable liquid crystal cell could not be produced.
The evaluation results are shown in Table 1.

Example 8
(A) As a polyorganosiloxane, the polyorganosiloxane (A-3) obtained in Synthesis Example A-3 is added to the solution containing the polyorganosiloxane (A-1) obtained in Synthesis Example A-1. After adding 10 parts by weight with respect to 90 parts by weight of the polyorganosiloxane (A-1), butyrocellosolve is added thereto as a solvent, and (B) a polymerizable unsaturated compound is represented by the formula (B-1- In 2), 8 parts by weight of the mixture of compounds in which n is 2 to 4 is added to 100 parts by weight of the total of (A) polyorganosiloxane to obtain a solution having a solid content concentration of 5.0% by weight. A polymer composition was prepared by filtering this solution using a filter having a pore size of 1 μm.
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
A solution containing the polyimide (PI-1) obtained in Synthesis Example PI-1 as another polymer was taken in an amount corresponding to 90 parts by weight in terms of polyimide and diluted with NMP, and then (A) As polyorganosiloxane, 10 parts by weight of polyorganosiloxane (A-3) obtained in Synthesis Example A-3 was added, and (B) a polymerizable unsaturated compound was represented by the formula (B-1-4) described later. The compound to be added was added in an amount of 30 parts by weight to a total of 100 parts by weight of the polymer to obtain a solution having a solid content concentration of 5.0% by weight. The solution was filtered using a filter having a pore size of 1 μm to prepare a polymer composition, and various liquid crystal cells were produced and evaluated using the polymer composition.
The evaluation results are shown in Table 1.

Example 11
In Example 10 above, the amounts of other polymers and (A) polyorganosiloxane used were as shown in Table 1, respectively, except that the types and amounts of epoxy compounds shown in Table 1 were further used. A polymer composition was prepared in the same manner as in Example 10, and various liquid crystal cells were produced and evaluated using the polymer composition.
The evaluation results are shown in Table 1.

In the above Table 1, the abbreviations of each component in the polymer composition have the following meanings.
[(B) polymerizable unsaturated compound]
Compound (B-1)
B-1-1: Compound represented by the following formula (B-1-1) B-1-2-1: Mixture of compounds in which n is 2 to 4 in the following formula (B-1-2) B -1-2-2: In the following formula (B-1-2), a mixture in which the average of the total value of two n is 2.6 B-1-3: represented by the following formula (B-1-3) Compound B-1-4-1: n = 3 in the following formula (B-1-4) B-1-4-2: n = 5 in the following formula (B-1-4) Is a compound

Other unsaturated compounds B-2-1: Methacrylic acid 4- (4′-phenyl-bicyclohexyl-4-yl) phenyl ester B-2-2: Methacrylic acid-5ξ-cholestan-3-yl [photopolymerization initiation Agent]
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: Light shielding film

Claims (10)

On the conductive film of the pair of substrates having the conductive film,
(A) The following formula (A-1)
(In formula (A-1), n1 is an integer of 0 to 2,
n2 is 0 or 1,
when n1 + n2 is 2 or more, R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms;
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. However, when n1 + n2 is 0, R is not an octadecyl group. )
A coating film is formed by applying a polymer composition containing a polyorganosiloxane having a group represented by formula (B) and a polymerizable unsaturated compound (B),
A pair of substrates on which the coating film is formed are arranged to face each other so that the coating film faces through a layer of liquid crystal molecules to form a liquid crystal cell,
A method for producing a liquid crystal display element, comprising a step of irradiating the liquid crystal cell with light while applying a voltage between conductive films of the pair of substrates. The polymerizable unsaturated compound (B) has the following formula (B-II) in the molecule:
(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 of Claim 1 which contains the compound (B-1) which has at least 2 of monovalent group represented by these. The compound (B-1) has the following formula (BI) in the molecule:
^{-X 1 -Y 1 -X 2 - (} B-I)
(In Formula (BI), X ¹ and X ² are each independently a 1,4-phenylene group or a 1,4-cyclohexylene group, and Y ¹ is a single bond having 1 to 4 carbon atoms. A divalent hydrocarbon group, an oxygen atom, a sulfur atom or —COO—, wherein X ¹ and X ² are one or more alkyl groups having 1 to 4 carbon atoms and alkoxyl groups having 1 to 4 carbon atoms. , May be substituted with a fluorine atom or a cyano group.)
The manufacturing method of the liquid crystal display element of Claim 2 which further contains at least 1 of the bivalent group represented by these.   The compound (B-1) is a di (meth) acrylate having a biphenyl structure, a di (meth) acrylate having a phenyl-cyclohexyl structure, a di (meth) acrylate having a 2,2-diphenylpropane structure, and a di (meth) acrylate having a diphenylmethane structure. The manufacturing method of the liquid crystal display element of Claim 3 which is at least 1 type of compound selected from the group which consists of (meth) acrylate and di-thio (meth) acrylate which has a diphenyl thioether structure.   The liquid crystal display according to claim 1, wherein the (A) polyorganosiloxane is obtained by reacting a silane compound having an alkoxyl group or a halogen atom or a mixture thereof in the presence of a dicarboxylic acid and an alcohol. Device manufacturing method. The method for producing a liquid crystal display element according to claim 1, wherein the (A) polyorganosiloxane is obtained by hydrolysis and condensation of a silane compound having an alkoxyl group or a halogen atom or a mixture thereof.   The method for producing a liquid crystal display element according to claim 1, wherein the polymer composition further contains at least one selected from the group consisting of polyamic acid and polyimide.   The method for producing a liquid crystal display element according to claim 1, wherein the polymer composition further contains an epoxy compound.   The method for manufacturing a liquid crystal display element according to claim 1, wherein each of the conductive films is a patterned conductive film partitioned into a plurality of regions. (A) The following formula (A-1)
(In formula (A-1), n1 is an integer of 0 to 2,
n2 is 0 or 1,
when n1 + n2 is 2 or more, R is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms;
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. However, when n1 + n2 is 0, R is not an octadecyl group. )
A polymer composition comprising a polyorganosiloxane having a group represented by formula (B) and a polymerizable unsaturated compound (B) and used in the method for producing a liquid crystal display device according to claim 1. .