TWI452067B - Silicon liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display components - Google Patents

Description

Lanthanide liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a fluorene-based liquid crystal alignment agent containing a polyoxyalkylene oxide obtained by polycondensation of alkoxysilane, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

A generally known liquid crystal display device is a substrate having a liquid crystal alignment film having a main component of polyamic acid and/or polyimine on a transparent electrode disposed in two opposite directions, and a liquid crystal filled in the gap The structure of matter. The most well-known method is TN (Twisted Nematic) type liquid crystal display element, but has developed a higher contrast STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type with reduced viewing angle dependence, and vertical alignment. (VA: Vertical Alignment) type.

In the use of the liquid crystal projector for business use and home theater, the light source used is a metal halide lamp having a high irradiation intensity, and therefore a liquid crystal alignment film material having high heat resistance and high light resistance is required.

In this case, an organic liquid crystal alignment film material such as polyimine which has been used in the past, and an inorganic liquid crystal alignment film material have been attracting attention.

For example, in the coated inorganic alignment film material which has been proposed, an alignment agent composition containing a tetraalkoxydecane, a trialkylnonane, an alcohol, and an oxalic acid reaction product can be formed on the electrode substrate of the liquid crystal display element to have excellent verticality. Report of a liquid crystal alignment film having an orientation, heat resistance, and uniformity (refer to Patent Document 1).

Further, a liquid crystal alignment agent composition containing a tetraalkoxynonane, a reaction product of a specific trialkoxysilane and water, and a specific glycol ether solvent can be formed to prevent display defects, and it is possible for a long time. After the driving, a good afterimage characteristic is obtained, and the liquid crystal alignment film having a reduced voltage holding ratio can be reduced with respect to light and heat without reducing the ability of liquid crystal alignment (refer to Patent Document 2).

In addition, in recent years, technological innovations of liquid crystal display elements including liquid crystal televisions have attracted attention, and in order to achieve this goal, in particular, increasing the long-term reliability of components has become an important issue. Therefore, it is required to obtain a homogeneous liquid crystal alignment film having good reproducibility and a film which is stable for a long period of time.

In particular, in the process of manufacturing a liquid crystal display element, it is not affected by the environment, and it is important to ensure the reliability of the element in a homogeneous liquid crystal alignment film having good reproducibility.

Further, it is also important to ensure the resistance to moisture and long-term reliability against intrusion from the outside of the liquid crystal display element.

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Publication No. 09-281502

Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-250244

In the inorganic liquid crystal alignment film described above, when a film is formed using a liquid crystal alignment agent, the remaining alkoxy group and stanol period are susceptible to moisture present in the air. Therefore, it has been difficult to obtain a homogeneous liquid crystal alignment film in the past, and as a result, the reliability of the liquid crystal display element has been reduced, which has become a major issue.

Further, moisture invaded from the outside of the liquid crystal display element, such as moisture invaded by the self-sealing member, also affects the liquid crystal alignment film, which may reduce the reliability of the liquid crystal display element.

Therefore, it is an important subject to improve the reliability of the liquid crystal display element by improving the resistance of the liquid crystal alignment film to moisture.

An object of the present invention is to provide a liquid crystal alignment film which is excellent in liquid crystal alignment and has high film stability, and can form a liquid crystal alignment film which is less susceptible to external moisture and has excellent electrical characteristics of a liquid crystal display element. A liquid crystal alignment agent, a liquid crystal alignment film obtained from the ruthenium liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

In order to achieve the above object, the gist of the present invention is as follows.

[1] A liquid crystal alignment agent characterized by having a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, and has 1 nitrogen atom and the nitrogen The above-mentioned hydrocarbon group and the latter may have one or two or more nitrogen atoms, and may have one or two or more polyoxyalkylene groups having 2 to 20 carbon atoms of an oxygen atom or a sulfur atom. The hydrocarbon groups may be bonded to the same polyoxyalkylene or each may be bonded to a different polyoxyalkylene.

[2] The liquid crystal alignment agent according to [1], which contains a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, and has a nitrogen atom An atom and a nitrogen atom having a nitrogen atom of a 1st, 2nd or 3rd order, and having an oxygen atom or a sulfur atom of 2 to 20 carbon atoms, or each having a hydrocarbon group of the former Two kinds of polyoxyalkylenes of the latter hydrocarbon group.

[3] The liquid crystal alignment agent according to [1], wherein the polycondensation contains an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (2). Polyoxyalkylene (AB) derived from oxoxane,

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group having 1 to 5 carbon atoms, and R ¹ is a carbon atom An alkyl group of 1 to 5, p is an integer from 0 to 2)

X ³ {Si(OR ² ) ₃ } _q (2)

(X ³ is a hydrocarbon group having 2 to 20 carbon atoms and having 1 or 2 or 3 nitrogen atoms in the nitrogen atom, and may have an oxygen atom or a sulfur atom, and 2 to 20 carbon atoms, and R ² is a carbon atom number 1 To an alkyl group of 5, q is an integer of 1 or 2.)

[4] The liquid crystal alignment agent according to [1] or [2], which comprises the following polyoxyalkylene (A) and polyoxyalkylene (B), polyoxyalkylene (A): polycondensation-containing formula (1) A polyoxyalkylene obtained by alkoxydecane of alkoxydecane, X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1) (X ¹ may be substituted by a fluorine atom And may have an oxygen atom, a phosphorus atom or a sulfur atom of a hydrocarbon group having 8 to 30 carbon atoms, X ² is an alkyl group having 1 to 5 carbon atoms, and R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is An integer of 0 to 2) polyoxyalkylene (B): a polyoxyalkylene obtained by polycondensing an alkoxydecane containing an alkoxydecane represented by the formula (2), X ³ {Si(OR ² ) ₃ } _q (2) (X ³ is a hydrocarbon group having 2 to 20 carbon atoms and having a nitrogen atom as a 1, 2 or 3 nitrogen atom, and having an oxygen atom or a sulfur atom, 2 to 20, R ² It is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 to 2.

[5] The liquid crystal alignment agent according to the above [3], wherein the polyfluorene oxide (AB) is a polyfluorene obtained by further condensing an alkoxysilane having an alkoxydecane represented by the formula (3). Oxane, (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom, or may be a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, The isocyanate group or the acryloxy group is substituted, and may have a hydrocarbon atom having 1 to 6 carbon atoms of a hetero atom, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

[6] The liquid crystal alignment agent according to the above [4], wherein the polyfluorene oxide (A) contains a polyoxyalkylene represented by the formula (1) and an alkoxy group represented by the formula (3). a polyoxyalkylene derived from alkoxy alkane, (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom, or may be a halogen atom, a vinyl group, a propylene group An oxy group, a decyl group, a methacryloxy group, an isocyanate group or an acryloxy group, and may have a hydrocarbon atom having 1 to 6 carbon atoms of a hetero atom, and R ³ is an alkyl group having 1 to 5 carbon atoms, n It is an integer from 0 to 3.)

[7] The liquid crystal alignment agent according to [4], wherein the polyoxyalkylene (B) is a polycondensation containing the alkoxydecane represented by the formula (2) and represented by the formula (3) Polyoxazane derived from alkoxy decane of alkoxydecane, (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom, or may be a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate group or an acryloxy group, and may have a hydrocarbon atom having 1 to 6 carbon atoms of a hetero atom, and R ³ is an alkyl group having 1 to 5 carbon atoms. Base, n is an integer from 0 to 3.)

[8] The liquid crystal alignment agent according to any one of [1] to [7] which has one nitrogen atom and the nitrogen atom is a nitrogen atom of a first, second or third order, and may have an oxygen atom or a hydrocarbon group having 2 to 20 carbon atoms of a sulfur atom, an alkyl group having 1 nitrogen atom and having 1 or 2 or 3 nitrogen atoms, and having 2 to 20 carbon atoms of an oxygen atom or Alkyl.

[9] The liquid crystal alignment agent according to [8], which has one nitrogen atom and the nitrogen atom is a nitrogen atom of a first, second or third order, and may have an oxygen atom or a sulfur atom of 2 to The alkyl group or alkylene group of 20 is a group represented by the formula (S1).

─P ¹ ─N─P ² P ³ (S1)

(wherein P ¹ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, and P ² is an alkyl group having 1 to 5 carbon atoms which may have a hydrogen atom, an oxygen atom or a sulfur atom, P ³ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, or an alkyl group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom.

[10] The liquid crystal alignment agent according to any one of [1] to [9] wherein the content of the polyoxyalkylene is 0.5 to 15% by mass in terms of SiO ₂ .

[11] The liquid crystal alignment agent according to any one of [5], wherein the alkoxydecane represented by the above formula (3) is a tetraalkoxy group in which n is 0 in the formula (3). Decane.

[12] A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of [1] to [11] above.

[13] A liquid crystal display element comprising the liquid crystal alignment film according to [12] above.

[14] The liquid crystal alignment agent according to [5], wherein the polyoxyalkylene (AB) is contained in an organic solvent to hydrolyze, condense the alkoxydecane represented by the formula (1) and the formula (3) The alkoxydecane shown is produced by adding a step of hydrolyzing and condensing the alkoxydecane represented by the formula (2).

[15] The liquid crystal alignment agent according to [6], wherein the polyoxyalkylene (A) is hydrolyzed and condensed in an organic solvent to form an alkoxydecane represented by the formula (3), and then added to the formula ( 1) A process for the step of rehydrolysis and condensation of the alkoxydecane shown.

[16] The liquid crystal alignment agent according to the above [7], wherein the polyoxyalkylene (B) is obtained by hydrolyzing and condensing the alkoxysilane represented by the formula (3) in an organic solvent. (2) A method of the step of rehydrolysis and condensation of the alkoxydecane shown.

According to the present invention, it is possible to form a liquid crystal alignment film having a good liquid crystal alignment property and having high film stability, and a ruthenium liquid crystal alignment agent which obtains a liquid crystal display element having excellent electrical characteristics. Further, since the liquid crystal alignment film of the present invention is less susceptible to moisture from the outside, a liquid crystal display element having high reliability can be obtained, and in particular, a liquid crystal display element having high stability and high reliability can be obtained.

Why is it possible to obtain a liquid crystal alignment film having a good liquid crystal alignment property by using the liquid crystal alignment agent of the present invention, and particularly a liquid crystal alignment film which is less susceptible to external moisture, although it is not clearly known, but an embodiment of the present invention will be described later. It is inferred from the comparative examples that, in the examples of the present invention, even if the water is treated under specific conditions, the liquid crystal cell having the same electrical characteristics superior to that of the water-resistant high water resistance can be obtained. The polysiloxane of the liquid crystal alignment agent of the present invention has a hydrocarbon group having a specific number of carbon atoms, and has a nitrogen atom and the nitrogen atom is a 1, 2 or 3 nitrogen atom and may have an oxygen atom or a sulfur atom. a hydrocarbon group of a specific carbon number.

Form of implementing the invention

The liquid crystal aligning agent of the present invention has a hydrocarbon group having 8 to 30 carbon atoms (hereinafter also referred to as a first specific organic group) which may be substituted by a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, and has a nitrogen The atom and the nitrogen atom are a nitrogen atom of the first, second or third order and may have an oxygen atom or a sulfur atom and a hydrocarbon group having 2 to 20 carbon atoms (hereinafter also referred to as a second specific organic group).

The liquid crystal alignment agent of the present invention contains one or more polyoxoxanes having the first specific organic group and the second specific organic group, and the first specific organic group and the second specific organic group may be bonded. They are formed in the same polyoxane or each is bonded to a different polyoxyalkylene. Wherein the liquid crystal alignment agent of the present invention preferably contains one polyoxoxane having both a first specific organic group and a second specific organic group, or two polyfluorene oxides each having a hydrocarbon group of the former or a hydrocarbon group of the latter. alkyl.

The first specific organic group is preferably a hydrocarbon group which may be substituted by a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, preferably has 8 to 22 carbon atoms, more preferably 8 to 18 carbon atoms.

The first specific organic group mainly has an effect of aligning the liquid crystal in one direction, and is, for example, an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a vinylphenylalkyl group, a naphthyl group, a fluorophenylalkyl group. Wait. The first specific organic group Among the oxygen atom, phosphorus atom or sulfur atom, an oxygen atom is preferred, and examples thereof include an acryloxyalkyl group, a benzomethoxyalkyl group, an alkoxyphenoxyalkyl group, an epoxycycloalkyl group and the like. It is particularly preferred that the first specific organic group which is lower in price and which is commercially available is an alkyl or fluoroalkyl alkoxydecane.

Further, the second specific organic group preferably has a nitrogen atom and the nitrogen atom is a hydrocarbyl group having a number of 1, 2 or 3 nitrogen atoms of 2 to 12, more preferably 2 to 10.

The second specific organic group, the nitrogen atom is a nitrogen atom refers to a level, such as -NH ₂ nitrogen atom bonded to two hydrogen atoms, a nitrogen atom is at Level 2 means a nitrogen atom, a nitrogen atom such as -NHR Bonded to a hydrogen atom and R. When the nitrogen atom is a nitrogen atom of a third order, it means that a nitrogen atom such as -NRR' is bonded to R and R'. In this case, R and R' are monovalent hydrocarbon groups which may have an oxygen atom or a sulfur atom.

The second specific organic group is preferably a group represented by the following formula (S1).

-P ¹ -NP ² P ³ (S1)

In the formula, P ¹ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, and P ² is an alkyl group having 1 to 5 carbon atoms which may have a hydrogen atom or an oxygen atom or a sulfur atom, P ³ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, or an alkyl group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom.

Specific examples of the group represented by the formula (S1) are as follows.

Aminopropyl, 2-aminoethylthioethyl, N,N-diethyl-3-aminopropyl, 3-(N,N-dimethylaminopropyl), diethylamine Methyl, N-methylaminopropyl, N-ethylaminoisobutyl, n-butylaminopropyl, t-butylaminopropyl, bis(2-hydroxyethyl)- 3-aminopropyl, 3-(N-allylamino)propyl, 3-(t-butoxycarbonylamino)propyl, 3-(ethoxy)carbonylamino)propyl, 3-(4-Hydroxybutane decylamine)propyl, N-phenylaminopropyl, 3-cyclohexylaminopropyl, N-(3-methylpropenyloxy-2-hydroxypropyl) 3-aminopropyl, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyl, 3-((2-methylpropenyloxy)ethoxy)carbonyl Amino)propyl, 3-((vinyloxymethoxy)carbonylamino)propyl, (E)-3-(3-carboxypropenylamine)propyl, -CH ₂ -CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -N(CH ₃ )-CH ₂ -CH ₂ -CH ₂ -, and the like.

The first aspect and the second aspect of the preferred embodiment of the liquid crystal alignment agent of the present invention will be explained below.

[First aspect of the invention]

A liquid crystal alignment agent containing a polyoxane (AB) obtained by polycondensing an alkoxydecane represented by the following formula (1) and an alkoxydecane represented by the following formula (2).

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

In the formula (1), X ¹ is the first specific organic group, and the preferred aspects thereof are as defined above.

In the formula (1), X ² is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, it is a methyl group or an ethyl group.

In the formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. In the formula (1), p is from 0 to 2, preferably from 0 to 1.

The alkoxydecane represented by the formula (1) is preferably an alkoxydecane represented by the following formula (1-1).

R ⁴ Si(OR ⁵ ) ₃ (1-1) (R ⁴ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom, and R ⁵ is an alkyl group having 1 to 5 carbon atoms).

Specific examples of the alkoxydecane represented by the above formula (1) are as follows, but are not limited thereto.

For example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane,dodecyltrimethoxydecane,dodecyltriethoxydecane , cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxynonane, heptadecyltriethoxydecane,octadecyltrimethoxydecane,18 Alkyl triethoxy decane, nonadecyl trimethoxy decane, nonadecyl triethoxy decane, undecyl triethoxy decane, undecyl trimethoxy decane, 21- twenty Dienyl triethoxy decane, tridecafluorooctyl trimethoxy decane, tridecafluorooctyl triethoxy decane, heptadecafluorodecyl trimethoxy decane, heptadecafluorodecyl triethoxy decane , isooctyltriethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, m-vinylphenylethyltrimethoxydecane, p-vinylphenyl Trimethoxy decane, (1-naphthyl) triethoxy decane, (1-naphthyl) trimethoxy decane, allyloxy undecyl triethoxy decane, benzoquinone Propyltrimethoxydecane, 3-(4-methoxyphenoxy)propyltrimethoxydecane, 1-[(2-triethoxydecyl)ethyl]cyclohexane-3,4- Epoxide, 2-(diphenylphosphino)ethyltriethoxydecane, diethoxymethyloctadecyldecane, dimethoxymethyloctadecyldecane, diethoxy-10- Dialkylmethyl decane, dimethoxy dodecylmethyl decane, diethoxy decyl methyl decane, dimethoxy decyl methyl decane, diethoxy octyl methyl decane, two Methoxyoctylmethyl decane, ethoxy dimethyl octadecyl decane, methoxy dimethyl octadecyl decane, and the like. Of these, preferred are octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane,dodecyltrimethoxydecane,dodecyltriethoxy Baseline, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, Octadecyltriethoxydecane, nonadecyltrimethoxynonane, nonadecyltriethoxydecane, undecyltriethoxydecane, or undecanetrimethoxydecane,diethyl Oxymethylmethyloctadecyldecane, or diethoxydodecylmethylnonane.

When the alkoxydecane represented by the formula (1) having the first specific organic group is used in an amount of less than 0.1 mol% based on the total alkoxydecane used in the production of the polyoxyalkylene (AB), Since a good liquid crystal alignment property cannot be obtained, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or less. When the amount exceeds 30 mol%, the formed liquid crystal alignment film may not be sufficiently cured. Therefore, it is preferably 30 mol% or less, more preferably 22 mol% or less, still more preferably 15 mol% or less.

X ³ {Si(OR ² ) ₃ } _q (2)

In the above formula (2), X ³ is a second specific organic group, and its definition and preferred embodiment are the same as described above. In the formula (2), R ^{2 is} as defined above, but is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

In the alkoxydecane represented by the formula (2), when q is 1, the alkoxydecane represented by the formula (2-1).

X ³ Si(OR ² ) ₃ (2-1)

Further, when q is 2, it is an alkoxydecane represented by the formula (2-2).

(R ² O) ₃ Si-X ³ -Si(OR ² ) ₃ (2-2)

Specific examples of the alkoxydecane represented by the above formula (2-1) and formula (2-2) are as follows, but are not limited thereto.

Specific examples when X ³ is a grade 1 amine: 2-aminoethyltrimethoxydecane, 2-aminoethyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyl Triethoxy decane, 3-aminopropyl dimethoxy decane, 3-aminopropyl diethoxy decane, 3-aminopropyl dimethyl ethoxy decane, 3-aminopropyl Dimethyl methoxy decane, 2-(2-aminoethyl thioethyl) triethoxy decane, 2-(2-aminoethyl thioethyl) trimethoxy decane, 2-amino group Ethylaminomethyltrimethoxydecane, 2-aminoethylaminoethyltriethoxydecane, 2-aminoethylaminoethyltrimethoxydecane, 2-aminoethylamine Ethyltriethoxydecane, γ-ureidopropyltriethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 3-(2-aminoethylamine Propyl)dimethoxydecane, 3-(2-aminoethylaminopropyl)dimethoxydecane, 3-[2-(2-aminoethylaminoethylamino)propyl Specific examples of trimethoxydecane, 3-[2-(2-aminoethylaminoethylamino)propyl]triethoxydecane, and X ³ are a 2- or 3-amine group: N,N-diethyl-3-aminopropyl) Triethoxy decane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, 3-(N,N-dimethylaminopropyl)triethoxydecane, 3- (N,N-Dimethylaminopropyl)trimethoxydecane, diethylaminomethyltriethoxydecane, diethylaminomethyltrimethoxydecane, N-methylaminopropyl Triethoxy decane, N-methylaminopropyltrimethoxydecane, N-ethylaminoisobutyltriethoxydecane, N-ethylaminoisobutyltrimethoxydecane, n -butylaminopropyltriethoxydecane, n-butylaminopropyltrimethoxydecane, t-butylaminopropyltriethoxydecane, t-butylaminopropyltrimethoxy Baseline, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltrimethoxydecane, 3-(N-ene Propylamino)propyltriethoxydecane, 3-(N-allylamino)propyltrimethoxydecane, (3-triethoxydecylpropyl)-t-butylamino Formate, (3-trimethoxydecylpropyl)-t-butylcarbamate, triethoxydecylpropylethylcarbamate, trimethoxydecylpropyl B Amine Formate, N-(3-triethoxydecylpropyl)-4-hydroxybutylguanamine, N-(3-trimethoxydecylpropyl)-4-hydroxybutylguanamine, N -Phenylaminopropyltriethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-cyclohexylaminopropyltriethoxydecane, 3-cyclohexylaminopropyltrimethoxy Baseline, bis(triethoxydecylpropyl)amine, bis(trimethoxydecylpropyl)amine, bis(triethoxydecylpropyl)-N-methylamine, bis(trimethoxy) Base propyl propyl)-N-methylamine, bis(methyldiethoxydecylpropyl)amine, bis(methyldimethoxydecylpropyl)amine, N-(3-methyl Propylene oxime-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-(3-methylpropenyloxy-2-hydroxypropyl)-3-aminopropyltrimethyl Oxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)- 3-aminopropyltrimethoxydecane, O-(methacryloxyethyl)-N-(triethoxydecylpropyl)carbamate, O-(methacryloxyl) Base ethyl)-N-(trimethoxydecylpropyl) Urethane, O-(vinyloxyethyl)-N-(triethoxydecylpropyl)carbamate, O-(vinyloxyethyl)-N-(trimethoxy Amidyl propyl) urethane, triethoxy decyl maleamic acid, trimethoxy decyl maleamic acid, and the like.

The polyoxyalkylene (AB) used in the present invention can be obtained by using one alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (2), or a plurality of them.

When the alkoxydecane represented by the formula (2) having the second specific organic group is used in an amount of less than 0.5 mol% based on the total alkoxydecane used in the production of the polyoxyalkylene (AB), Will not get good compared to water The reliability is preferably 0.5 mol% or more, more preferably 1 mol% or more. When the amount exceeds 50 mol%, the stability of the polyoxyalkylene solution is deteriorated, so it is preferably 50 mol% or less, more preferably 40 mol% or less.

In the polyoxane (AB), the alkoxydecane represented by the formula (1) in the alkoxydecane used is preferably from 0.1 to 30 mol%, particularly preferably from 0.5 to 22 mol%, and The alkoxydecane content represented by the formula (2) in all the alkoxydecane used is preferably from 0.5 to 50 mol%, particularly preferably from 1.0 to 30 mol%.

In the polyoxane (AB) of the present invention, in addition to the alkoxydecane represented by the formula (1) and the formula (2), an alkoxydecane represented by the following formula (3) is preferably used. Got it. Since the alkoxydecane represented by the formula (3) can impart various properties to the polyoxane (AB), one or more kinds can be selected depending on the necessary properties.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

Wherein X ⁴ is a hydrogen atom or may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate group or an acryloxy group, and may have a carbon atom of a hetero atom A hydrocarbon group of 1 to 6 (hereinafter also referred to as a third specific organic group), R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3.

When X ⁴ is a third specific organic group, the third specific organic group may have an aliphatic hydrocarbon, an aliphatic ring, an aromatic ring, a heterocyclic alicyclic structure or a branched structure, and may contain an unsaturated bond or an oxygen atom. a hetero atom such as a sulfur atom or a phosphorus atom. Further, the third specific organic group may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate group, an acryloxy group or the like as described above.

In the formula (3), R ^{3 is} as defined above, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. In the formula (3), n is the same as defined above, and is preferably an integer of 0 to 2.

Specific examples of the alkoxydecane represented by the above formula (3) are as follows, but are not limited thereto.

In the alkoxydecane of the formula (3), specific examples of the alkoxydecane in the case where X ⁴ is a hydrogen atom are, for example, trimethoxydecane, triethoxydecane, tripropoxydecane, tributoxydecane, and the like.

Further, in the alkoxydecane of the formula (3), specific examples of the alkoxydecane in the case where X ⁴ is the third specific organic group are, for example, methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxy. Base decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, methyl tripropoxy decane, 3-mercaptopropyl triethoxy decane, decyl methyl trimethoxy Base decane, vinyl triethoxy decane, vinyl trimethoxy decane, allyl triethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl propylene decyloxy Propyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3. Isocyanatepropyltriethoxydecane, Trifluoropropyl Trimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, dimethyldiethoxydecane, dimethyldimethoxydecane , diethyldiethoxydecane, diethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, m-vinyl Trimethoxy Silane, p-vinylphenyl trimethoxy Silane, trimethyl ethoxy Silane, trimethyl methoxy silane-like.

The polydecane oxide (AB) used in the present invention may have one or a plurality of the above-mentioned third specific organic groups in order to improve the adhesion to the substrate, the affinity to the liquid crystal molecules, and the like without departing from the effects of the present invention. .

Among the alkoxydecanes represented by the formula (3), the alkoxydecane wherein n is 0 is more preferably tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane. It is preferred that the tetramethoxy decane or the tetraethoxy decane or the tetraalkoxy decane are condensed with the alkoxy decane represented by the formula (1) and the formula (2), and the polyoxy siloxane of the present invention is preferably used. .

When the alkoxydecane represented by the formula (3) is used in combination, the alkoxydecane represented by the formula (3) is preferably used in an amount relative to all alkoxydecane used in the production of the polyoxyalkylene (AB). 20 to 99.4% by mole, and preferably 45 to 99.4% by mole. More preferably, the alkoxydecane represented by the formula (3) is from 50 to 99.8 mol%.

[Second aspect of the invention]

The second aspect of the present invention is a liquid crystal alignment agent containing the following polyoxyalkylene oxide (A) and the following polyoxyalkylene oxide (B).

Polyoxane (A): a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (1).

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ , and p are each as defined above).

Polyoxane (B): a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (2).

X ³ {Si(OR ² ) ₃ } _q (2)

(X ³ , R ² , and q are each as defined above).

[polyoxane (A)]

The polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the following formula (1).

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

In the formula (1), X ¹ (first specific organic group), X ² , R ¹ and p are as defined above, and preferred ones are also as described above.

The description and preferred embodiment of the alkoxydecane represented by the above formula (1) are the same as those of the alkoxydecane represented by the formula (1) described in the above polyoxyalkylene (AB). Further, the polyoxyalkylene (A) used in the present invention may have a plurality of first specific organic groups.

The alkoxydecane represented by the formula (1) having the first specific organic group is used in an amount of less than 0.2 mol% based on the total alkoxydecane used in the production of the polyoxyalkylene (A). The liquid crystal alignment property is not obtained, so it is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or more. When the amount exceeds 30 mol%, the formed liquid crystal alignment film may not be sufficiently cured. Therefore, it is preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less.

The polyoxyalkylene (A) used in the present invention preferably contains at least one alkoxy group of the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the following formula (3). A polyoxyalkylene obtained by polycondensation of a decane. The alkoxydecane represented by the formula (3) can impart various properties to the polyoxyalkylene, and if necessary, one or more of the alkoxydecanes represented by the formula (3) can be used.

(X ⁴ ) _n si(OR ³ ) _4-n (3)

X ⁴ and R ³ in the formula (3), and preferred embodiments thereof are the same as those described in the formula (3) of the polyoxyalkylene (AB), and the alkoxydecane represented by the formula (3) is also the same. It is described in the polyoxyalkylene (AB) term.

The polyoxyalkylene (A) of the present invention may have one or a plurality of third specific organic groups in order to improve the adhesion to the substrate, the affinity to the liquid crystal molecules, and the like without departing from the effects of the present invention.

When a polyoxyalkylene (A) is used in combination with the alkoxydecane represented by the formula (3), the alkane represented by the formula (3) is used with respect to all alkoxydecane used in the production of the polyoxyalkylene (A). The oxydecane is preferably from 70 to 99.8 mol%, more preferably from 75 to 99.8 mol%, still more preferably from 80 to 99.8 mol%.

In the present invention, the polyoxyalkylene oxide (A) is preferably polycondensed from at least one compound selected from the group consisting of the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (3). The polyoxyalkylene obtained.

[polyoxane (B)]

The polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the formula (2).

X ³ [Si(OR ² ) ₃ } _q (2)

In the formula (2), X ³ (second specific organic group), R ² and q are as defined above, and preferred ones are also as described above.

Further, the description of the alkoxydecane represented by the formula (2) is the same as the description of the alkoxydecane represented by the formula (2) described in the above polyoxyalkylene (AB), and preferred embodiments thereof are preferred. The full description is also applicable. Further, the polyoxyalkylene (B) used in the present invention may have a plurality of second specific organic groups.

The polyoxyalkylene (B) used in the present invention may have a plurality of alkoxydecanes represented by the formula (2).

When the alkoxydecane represented by the formula (2) having the second specific organic group is used in an amount of less than 1 mol% relative to all alkoxydecane used in the production of the polyoxyalkylene (B), Water will not be able to obtain good reliability characteristics. Therefore, it is preferably 1 mol% or more, more preferably 2 mol% or more. When the amount is 60 mol% or more, the stability of the polyoxyalkylene solution is deteriorated, so it is preferably 60 mol% or less, more preferably 50 mol% or less.

In addition, the polyoxyalkylene (B) used in the present invention may contain at least one alkoxy group of the alkoxydecane represented by the formula (2) and the polyoxyalkylene represented by the following formula (3). The base decane is obtained by polycondensation.

(X ⁴ ) _n Si(OR ₃ ) _4-n (3)

In the formula (3), X ⁴ , R ³ and n, and preferred embodiments thereof are as described in the polyoxyalkylene (AB) term, and the specific examples of the alkoxydecane represented by the formula (3) are also homopolymerized. It is described in the oxime (AB) term.

The polysiloxane (B) used in the present invention may have one or a plurality of third specific organic groups in order to improve the adhesion to the substrate, the affinity for liquid crystal molecules, and the like without departing from the effects of the present invention. .

When the alkoxydecane represented by the formula (3) is used in the polyoxyalkylene (B), the alkoxy group represented by the formula (3) is used with respect to all the alkoxydecane used in the production of the polyoxyalkylene (B). The decane is preferably from 40 to 99 mol%, more preferably from 50 to 99 mol%.

In the present invention, the polyoxyalkylene (B) is preferably a polycondensation obtained by polycondensation of an alkoxydecane represented by the formula (2) with an alkoxydecane of an alkoxydecane represented by the formula (3). Oxane.

[Manufacturing method of polyoxyalkylene (AB)]

The method for producing the polyoxyalkylene (AB) used in the present invention is not particularly limited. The present invention is obtained by condensing an essential component of the above formula (1) and the alkoxy decane of the formula (2) in an organic solvent. The polysiloxane (AB) generally obtained is a solution obtained by polycondensing the above alkoxysilane and uniformly dissolving in an organic solvent.

A method of polycondensing an alkoxy decane, for example, a method of hydrolyzing and condensing an alkoxy decane in a solvent such as an alcohol or a glycol.

The hydrolysis and condensation reaction at this time may be any of partial hydrolysis and complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is generally preferred to add water in an amount of more than 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is generally preferably 0.5 to 2.5 times moles of all alkoxy groups in the alkoxydecane.

Further, in general, in order to promote hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; an alkali such as ammonia, methylamine, ethylamine, ethanolamine or triethanolamine may be used. a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, a solution in which alkoxysilane is dissolved is heated to further promote hydrolysis and condensation reaction. The heating temperature and heating time at this time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C for 24 hours, or heating under reflux, stirring for 1 hour, or the like.

Further, another method is a method in which a mixture of alkoxydecane, a solvent and oxalic acid is heated to carry out polycondensation. Specifically, a method in which oxalic acid is first added to an alcohol to form an alcohol solution of oxalic acid, and then the alkoxy decane is mixed while heating the solution. The amount of oxalic acid used at this time is preferably 0.2 to 2 moles based on 1 mole of all alkoxy groups contained in the alkoxydecane. In this method, heating can be carried out at a liquid temperature of 50 to 180 °C. It is preferably a method of heating under reflux for several tens of minutes to several ten hours without causing evaporation or volatilization of the liquid.

When the polyoxyalkylene oxide (AB) of the present invention is used, when a plurality of alkoxysilanes are used, the alkoxysilane may be mixed first to obtain a mixture, or may be mixed, or a plurality of alkoxydecane may be sequentially mixed.

The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxysilane may be one which can dissolve the alkoxysilane, and is not particularly limited. Further, even if the alkoxydecane cannot be dissolved, it may be a substance which can be dissolved when the alkoxysilane is subjected to a polycondensation reaction. Generally, since an alcohol is formed by a polycondensation reaction of an alkoxydecane, an alcohol, a glycol, a glycol ether, or an organic solvent having a good solubility to an alcohol is used.

Specific examples of the polyoxyalkylene oxide include alcohols such as methanol, ethanol, propanol, butanol, and diacetone; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3-propanediol; 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1, Diols such as 4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, B Diol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl Glycol ethers such as propyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; N-methyl-2- Pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethylphosphoric acid , m-cresol and the like.

In the present invention, a plurality of the above polymerization solvents may be used in combination.

Further, another method for producing the polyoxyalkylene oxide (AB) of the present invention includes, for example, hydrolyzing, condensing an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3) in an organic solvent. Thereafter, a method for producing a polyoxyalkylene (AB) in which alkoxysilane represented by the formula (2) is subjected to hydrolysis and condensation is added.

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ , and p are each as defined above).

X ₃ {Si(OR ₂ ) ₃ } _q (2)

(X ³ , R ² and q are each as defined above).

(X ₄ )nSi(OR ₃ ) _4-n (3)

(X ⁴ , R ³ and n, each of which is as defined above).

The hydrolysis and condensation reaction of the alkoxydecane represented by the formula (1) and the formula (3) at this time may be any of partial hydrolysis and complete hydrolysis. In the case of complete hydrolysis, water of 0.5 times moles of all alkoxy groups in the alkoxydecane may theoretically be added, but it is generally preferred to add water in an amount of more than 0.5 times.

In the present invention, the amount of water used in the above reaction may be appropriately selected, but it is generally preferably 0.5 to 2.5 times moles of all alkoxy groups in the alkoxydecane.

Further, in general, in order to promote hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid may be used; ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. A base; a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, a solution obtained by dissolving and dissolving an alkoxysilane can further promote hydrolysis and condensation reaction. The heating temperature and heating time at this time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C for 24 hours, or heating under reflux, stirring for 1 hour, or the like.

The alkoxy decane represented by the formula (2) is added to the solution obtained by hydrolyzing and condensing the alkoxy decane represented by the formula (1) and the alkoxy decane represented by the formula (3), and continues. Stirring gives a solution of polyoxane (AB). Heating the solution at this time further promotes hydrolysis and condensation reaction. The heating temperature and heating time at this time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C for 24 hours, or heating under reflux, stirring for 1 hour, or the like.

The solvent used in the polycondensation of the alkoxysilane (hereinafter also referred to as a polymerization solvent) is the same as the polymerization solvent described in the above [Production method of polyoxyalkylene (AB)], and the same applies to the specific example, and a plurality of these may be used. Solvent.

The polymerization solution of the polyoxyalkylene obtained by the above method (hereinafter also referred to as a polymerization solution) is preferably a concentration in which cerium atoms of all alkoxysilanes added as a raw material are converted in terms of SiO ₂ (hereinafter referred to as SiO ₂ conversion). The concentration) is 20% by mass or less, more preferably 5 to 15% by mass. Within this concentration range, gel formation can be inhibited by selecting any concentration to obtain a homogeneous solution.

[Manufacturing method of polyoxyalkylene (A)]

The method for producing the polyoxyalkylene (A) used in the present invention is not particularly limited, but the present invention is obtained by condensing an alkoxydecane having an alkoxydecane of the above formula (1) as an essential component in an organic solvent. . The polysiloxane (A) which is generally obtained is a solution obtained by uniformly condensing the above alkoxysilane and uniformly dissolving it in an organic solvent.

The polycondensation method of the present invention is a method of hydrolyzing and condensing the above alkoxysilane in a solvent such as an alcohol or a glycol. The hydrolysis and condensation reaction at this time may be either a partially hydrolyzed or a completely hydrolyzed towel. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of all alkoxy groups in the alkoxydecane, but it is generally preferred to add water in an amount of more than 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is generally preferably 0.5 to 2.5 times moles of all alkoxy groups in the alkoxydecane.

Further, when a polyoxyalkylene oxide (A) is produced, when a plurality of alkoxysilanes are used, the alkoxydecane may be mixed first to obtain a mixture, followed by mixing, or a plurality of alkoxydecane may be sequentially mixed.

The polycondensation method, the polymerization solvent, and the like used in the production of the polyoxyalkylene (A) are as described in the section of the production method of the polyoxyalkylene (AB), and the preferred ranges thereof are also the same.

Another method for producing a polyoxyalkylene (A) is to hydrolyze and condense the alkoxydecane represented by the formula (3) in an organic solvent, and then hydrolyze the alkoxysilane represented by the formula (1). A method for producing a polyoxyalkylene (A) in the condensation step.

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ , and p are each as defined above).

(X ⁴ ) _n Si(OR ₃ ) _4-n (3)

(X ⁴ , R ³ and n, each of which is as defined above).

The hydrolysis and condensation reaction of the alkoxydecane represented by the formula (3) at this time may be any of partial hydrolysis and complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of all alkoxy groups in the alkoxydecane, but it is generally preferred to add water in an amount of more than 0.5 times mole, more preferably 0.5 to 2.5 times moles. .

Further, in general, a catalyst used for promoting hydrolysis or a condensation reaction, a heating method, or the like, a catalyst described in [Production Method of Polyoxane (AB), or a heating method.

The alkoxydecane represented by the formula (1) is added to a solution obtained by hydrolyzing and condensing the alkoxydecane represented by the formula (3) obtained by the above method, and the solution of the polyoxane (A) can be produced by continuously stirring. . Heating the solution at this time further promotes the hydrolysis and condensation reaction. The heating temperature and heating time at this time can be appropriately selected as desired. For example, heating at 50 ° C, stirring for 24 hours, or heating under reflux, stirring for 1 hour, etc.

The polymerization solution of the polyoxane (A) obtained by the above method (hereinafter also referred to as a polymerization solution) is generally converted into a concentration of SiO _{2 in terms} of a ruthenium atom of all the alkoxysilanes to which the raw material is added (hereinafter referred to as SiO ₂ conversion). The concentration) is 20% by mass or less, more preferably 5 to 15% by mass. Within this concentration range, gel formation can be inhibited by selecting any concentration to obtain a homogeneous solution.

[Method for producing alkoxydecane (B)]

The method for producing the polyoxyalkylene (B) of the present invention is not particularly limited, and may be the same as the above [the method for producing polyoxyalkylene (A)] in the present invention.

In the case of producing polyoxyalkylene (B), when a plurality of alkoxydecanes are used, the alkoxydecane may be mixed first to obtain a mixture, followed by mixing, or a plurality of alkoxydecanes may be sequentially mixed.

In another method, for example, a polyoxane which is subjected to a step of hydrolysis and condensation by adding an alkoxydecane represented by the formula (2) after hydrolyzing and condensing the alkoxydecane represented by the formula (3) in an organic solvent. B) Manufacturing method.

X ³ {Si(OR ² ) ₃ } _q (2)

(X ³ , R ² and q are each as defined above).

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

(X ⁴ , R ³ and n are each as defined above).

The hydrolysis and condensation reaction of the alkoxydecane represented by the formula (3) at this time may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of all alkoxy groups in the alkoxydecane, but it is generally preferred to add water in an amount of more than 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is generally preferably 0.5 to 2.5 times moles of all alkoxy groups in the alkoxydecane.

Further, in general, a catalyst or a heating method described in [Production Method of Polyoxane (AB)] is used to promote hydrolysis or condensation reaction, or a heating method.

The alkoxydecane represented by the formula (2) is added to a solution obtained by hydrolyzing and condensing the alkoxydecane represented by the formula (3) obtained by the above method, and the solution of the polyoxane (B) can be produced by continuously stirring. . Heating the solution at this time further promotes the hydrolysis and condensation reaction. The heating temperature and heating time at this time can be appropriately selected as desired. For example, heating at 50 ° C, stirring for 24 hours, or heating under reflux, stirring for 1 hour, etc.

The solvent used in the polycondensation of the alkoxy decane (hereinafter also referred to as a polymerization solution) is the same as the polymerization solvent described in the above [Production Method of Polyoxane (A)], and a plurality of the same may be used. These solvents.

[Polyoxane (AB), polyoxane (A) and polyoxane (B) solutions]

In the present invention, the polymerization solution obtained by the above method can be directly used as a solution of polyoxane (AB), polyoxane (A) and polyoxyalkylene (B), if necessary, can be concentrated, diluted with a solvent or added The other solvent is substituted and used as a solution of polyoxyalkylene (AB), polyoxyalkylene (A) and polyoxyalkylene (B).

The solvent (hereinafter also referred to as an additive solvent) used at this time may be the same as the polymerization solvent or other solvent. The solvent to be added is not particularly limited as long as it can uniformly dissolve polyoxane (AB), polyoxyalkylene (A), and polyoxyalkylene (B), and one or more kinds can be arbitrarily selected.

Specific examples of the above additives may be ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate and ethyl lactate, in addition to the above-mentioned polymerization solvents.

These solvents can adjust the viscosity of the liquid crystal alignment agent or enhance the coatability when the liquid crystal alignment agent is applied onto the substrate by spin coating, flexographic printing, ink jet or the like.

[Other ingredients]

The liquid crystal alignment agent of the present invention may contain other components other than polysiloxane (AB), polyoxyalkylene (A) and polyoxyalkylene (B), such as inorganic fine particles and metals, within the range not impairing the effects of the present invention. An oxide oligomer, a metal oxide polymer, a leveling agent, a surfactant, and the like.

The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles or magnesium fluoride fine particles, and are particularly preferably in the form of a colloidal solution. The colloidal solution may be one in which inorganic fine particles are dispersed in a dispersing agent, or a commercially available colloidal solution. The present invention can impart the surface shape and other functions of the formed hardened film by containing inorganic fine particles. The average particle diameter of the inorganic fine particles is preferably 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by using the coating liquid prepared by the preparation is lowered.

The dispersing agent of the inorganic fine particles, for example, water and an organic solvent, forms the viewpoint of the stability of the coating liquid for a film, and the colloidal solution is preferably adjusted to pH or pKa of 1 to 10, more preferably 2 to 7.

The organic solvent used for the dispersing agent of the above colloidal solution is, for example, methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, ethylene glycol. Alcohols such as monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N- An amide such as methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or γ-butyrolactone; or an ether such as tetrahydrofuran or 1,4-dioxane. Among them, preferred are alcohols or ketones. These organic solvents may be used singly or in combination of two or more kinds as a dispersing agent.

As the metal oxide oligomer or metal oxide polymer, a single or composite oxide precursor of ruthenium, titanium, aluminum, ruthenium, osmium, iridium, tin, indium, zinc or the like can be used. The metal oxide oligomer or the metal oxide polymer may be a commercially available product or a product obtained by a usual method such as hydrolysis from a monomer such as a metal alkoxide, a nitrate, a hydrochloride or a carboxylate.

Specific examples of the metal oxide oligomer and the metal oxide polymer are, for example, commercially available methyl phthalate 51, methyl phthalate 53A, ethyl phthalate 40, ethyl hydrazine. A titanium oxide oligomer such as a phthalate oligomer such as an acid ester 48, an EMS-485 or an SS-101 or a siloxane polymer or a titanium-n-butoxide tetramer produced by Kanto Chemical Co., Ltd. These may be used alone or in combination of two or more.

Further, known materials can be used as the above-mentioned leveling agent, surfactant, etc., and a commercially available product which is easy to obtain is particularly preferable.

Further, the method of mixing the polyoxyalkylene oxide and the above other components may be carried out simultaneously with or after the polyoxyalkylene oxide.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention is a solution containing the above polyoxyalkylene (AB) or polyoxyalkylene (A) and polyoxyalkylene (B), and other components used as necessary. The solvent to be used at this time is at least one solvent selected from the group consisting of the above-mentioned polymerization solvent and added solvent. The content of the polyoxyalkylene (AB) in the liquid crystal alignment agent, or the total content of the polyoxyalkylene (A) and the polyoxyalkylene (B) is preferably SiO ₂ conversion of each polyoxyalkylene (AB). The concentration in terms of SiO _{2 in terms of the} atomic weight of the total amount of the polyoxyalkylene (A) and the polyoxyalkylene (B) is from 0.5 to 15% by mass, more preferably from 1 to 6% by mass. Within the range of the concentration in terms of SiO _{2 ,} it is easy to obtain a desired film thickness by one application, and a sufficient solution pot life.

In the present invention, the mixture of polyoxyalkylene (A) and polyoxyalkylene (B) in the liquid crystal alignment agent is preferred, and is contained in the polyoxane (A) and the polyoxane (B). The atomic total amount of the ruthenium atom contained in the polyoxyalkylene (A) is 5 mol% or more. When the amount of the ruthenium atom contained in the polyoxyalkylene (A) is less than 5 mol%, it is difficult to obtain good vertical alignment. Further, when the amount of the ruthenium atom contained in the polyoxyalkylene (A) exceeds 99.5 mol%, the content of the polyoxane (B) is too small, and it is difficult to obtain good reliability with respect to water, so it is preferred. It is 99.5% or less.

The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and may be a polyoxyalkylene (AB), a polyoxyalkylene (A) or a polyoxyalkylene (B) which can be used in the present invention, and if necessary. The other ingredients added are in a state of uniform mixing. Generally, polycondensed polyoxane (AB), polyoxyalkylene (A) and polyoxyalkylene (B) are used in a solvent, so polyoxyalkylene (AB) or polyoxyalkylene (A) can be directly used. And a solution of polyoxyalkylene (B), or simply add other ingredients as necessary, to the solution, but the easiest method is to use the aforementioned polymerization solution directly.

Further, when the content of the polyoxane (AB), the polyoxane (A), and the polyoxyalkylene (B) in the liquid crystal alignment agent is adjusted, at least 1 selected from the group consisting of the above-mentioned polymerization solvent and added solvent can be used. a solvent.

[Liquid alignment film]

The liquid crystal alignment film of the present invention is obtained by using the liquid crystal alignment agent of the present invention. For example, the liquid crystal alignment agent of the present invention can be directly applied to a substrate, and then a cured film obtained by drying and baking can be used as a liquid crystal alignment film. Further, the cured film may be brushed, irradiated with polarized light or light of a specific wavelength, or the like, or treated with an ion beam or the like as a liquid crystal alignment film.

The substrate on which the liquid crystal alignment agent is applied is not particularly limited as long as the substrate having high transparency, but a substrate on which a transparent electrode for driving a liquid crystal is formed is preferably formed on the substrate.

Specifically, for example, glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyacrylates, polyurethanes, polybenzazoles, polyethers, polyether ketones, trimethylpentene, poly A substrate on which a transparent electrode is formed, such as a plastic plate such as olefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose or acetate butyrate cellulose.

The coating method of the liquid crystal alignment agent is, for example, a spin coating method, a printing method, an inkjet method, a spray method, a roll coating method, etc., but a copy printing method is widely used in terms of productivity, and the present invention is also applicable.

The drying step after the application of the liquid crystal alignment agent is not essential, but it is preferable to include a drying step when the substrate is not yet shaped during the baking after the coating, or when it is not immediately baked after the coating. This drying may be carried out by removing the solution to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like, and the drying method is not particularly limited. For example, it is dried on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The coating film formed by coating the liquid crystal alignment agent by the above method can be fired to form a cured film. The calcination temperature at this time may be any temperature of from 100 ° C to 350 ° C, but is preferably from 140 ° C to 300 ° C, more preferably from 150 ° C to 230 ° C, still more preferably from 160 ° C to 220 ° C. The calcination time for baking may be any time from 5 minutes to 240 minutes. It is preferably from 10 to 90 minutes, more preferably from 20 to 90 minutes. A commonly known method such as a hot plate, a hot air circulating oven, an IR oven, a conveying furnace, or the like can be used for heating.

The polyoxyalkylene in the liquid crystal alignment film is subjected to polycondensation in the baking step. However, in the present invention, complete polycondensation is not required within the range which does not impair the effects of the present invention. Preferably, however, the heat treatment temperature of the sealant hardening or the like necessary for the step of producing the liquid crystal cell is performed at a temperature higher than 10 ° C or higher.

The thickness of the cured film may be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more. In this case, the liquid crystal display element is preferably reliable. Further, the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less. In this case, the power consumption of the liquid crystal display element is not extremely increased.

The cured film may be used as a liquid crystal alignment film as it is, or may be used as a liquid crystal alignment film by brushing the cured film, irradiating a polarized light or a light of a specific wavelength, or the like after treatment with an ion beam or the like.

[Liquid Crystal Display Element]

The liquid crystal display device of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then forming a liquid crystal cell by a known method. For example, a method in which a liquid crystal cell is produced is a method in which a pair of substrates for forming a liquid crystal alignment film is held by a distance aligner, and a sealing agent is fixed, and then liquid crystal is resealed. The size of the positioner used at this time is 1 to 30 μm, preferably 2 to 10 μm.

The method of injecting the liquid crystal is not particularly limited, and may be, for example, a vacuum method in which the inside of the obtained liquid crystal cell is depressurized, a vacuum method in which a liquid crystal is injected, or a dropping method in which a liquid crystal is dropped and sealed.

The substrate used for the liquid crystal display device is not particularly limited as long as the substrate having high transparency, but generally a substrate on which a transparent electrode for driving a liquid crystal is formed is formed on the substrate.

Specific examples are the substrates described in the above [Liquid Crystal Alignment Film].

Further, a high-performance functional element such as a TFT-type element is used, and a transistor-like element is formed between an electrode for driving a liquid crystal and a substrate.

Generally, the above-described general substrate is used for the transmissive liquid crystal element, but the reflective liquid crystal display element may be a single crystal substrate. The electrode formed on the substrate at this time can be used, and can reflect the aluminum-like material of light.

Further, in a PSA type display device using a liquid crystal containing a polymerizable compound, a pretilt angle of the liquid crystal can be found when a voltage is applied to the liquid crystal cell while irradiating ultraviolet rays or deflecting energy rays such as ultraviolet rays.

The present invention will be specifically described below by way of Synthesis Examples, Examples and Comparative Examples. However, the invention is not limited by the following examples.

The code description in this embodiment is as follows.

TEOS: tetraethoxy decane

TBC: (3-triethoxydecylpropyl)-t-butylcarbamate

BISA: bis(triethoxy decylpropylamino)

DMAPS: 3-(N,N-dimethylaminopropyl)trimethoxydecane

C12: dodecyltriethoxydecane

C18: octadecyltriethoxydecane

F13: tridecafluorooctyltrimethoxydecane

MC18: diethoxymethyl octadecane

MTES: methyl triethoxy decane

Phe: phenethyltrimethoxydecane

Ben: phenoxypropyltrimethoxydecane

ACPS: (3-propenyloxypropyl)trimethoxydecane

MAPS: 3-methacryloxypropyltriethoxydecane

HG: hexanediol (alias: 2-methyl-2,4-pentanediol)

BCS: butyl cellosolve (alias: ethylene glycol monobutyl ether)

PGME: propylene glycol monoethyl ether

PB: propylene glycol monobutyl ether

EtOH: ethanol

APS: γ-aminopropyl triethoxy decane

<Synthesis Example 1>

In a 200 mL (ml) four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 22.52 g, BCS: 7.51 g, TEOS: 39.17 g, C18: 4.17 g, and TBC: 0.64 g of alkoxydecane monomer were mixed. Solution. A solution obtained by premixing HG: 11.26 g, BCS: 3.75 g, water: 10.80 g and catalyst oxalic acid: 0.18 g at room temperature for 30 minutes was dropped into the solution. The solution was stirred for 30 minutes, and then refluxed for 1 hour, and then cooled to obtain a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ .

After mixing the obtained polyoxane solution: 30 g, HG: 48.68 g, and BCS: 11.32 g, a liquid crystal alignment agent (K1) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 2>

A solution of alkoxysilane monomer was prepared by mixing HG: 21.5 g, BCS: 7.17 g, TEOS: 35.42 g, C18: 4.17 g, and TBC: 0.643 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. A solution obtained by premixing HG: 10.75 g, BCS: 3.58 g, water: 10.80 g and catalyst oxalic acid: 0.18 g at room temperature for 30 minutes was dropped into the solution. The solution was stirred for 30 minutes, and then refluxed for 1 hour, and then cooled to obtain a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ .

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g, a liquid crystal alignment agent (K2) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 3>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 21.11 g, BCS: 7.04 g, TEOS: 38.75 g, and C18: 4.17 g of alkoxydecane monomer was mixed. A solution obtained by previously mixing HG: 10.55 g, BCS: 3.52 g, water: 10.80 g, and oxalic acid: 0.90 g of a catalyst was added dropwise to the solution at room temperature for 30 minutes. The solution was stirred for 30 minutes, refluxed for 30 minutes, and a mixed solution of BISA: 1.37 g, HG: 1.97 g, BCS: 0.66 g was further added. Thereafter, the mixture was heated under reflux for 30 minutes, and after cooling, a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ was obtained.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g, a liquid crystal alignment agent (K3) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 4>

A solution of HG: 21.69 g, BCS: 7.23 g, TEOS: 38.75 g, and C18: 4.17 g of alkoxydecane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 10.85 g, BCS: 3.62 g, water: 10.80 g and catalyst oxalic acid: 0.9 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 30 minutes. Further, a mixed solution of DMAPS: 0.83 g, HG: 0.88 g, and BCS: 0.29 g was added. Thereafter, the mixture was heated under reflux for 30 minutes, and after cooling, a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ was obtained.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g, a liquid crystal alignment agent (K4) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 5>

A solution of HG: 18.88 g, BCS: 6.29 g, TEOS: 27.08 g, C18: 4.17 g, and TBC: 19.29 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 9.44 g, BCS: 3.15 g, water: 10.80 g, and oxalic acid: 0.90 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.57 g, and BCS: 11.43 g, a liquid crystal alignment agent (K5) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 6>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 22.10 g, BCS: 7.37 g, TEOS: 36.67 g, MC18: 1.55 g, and TBC: 6.43 g of alkoxy decane monomer was mixed. The solution obtained by premixing HG: 11.05 g, BCS: 3.685 g, water: 10.80 g, and oxalic acid: 0.36 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g, a liquid crystal alignment agent (K6) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 7>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 22.10 g, BCS: 7.37 g, TEOS: 35.42 g, Phe: 2.26 g, and TBC: 6.43 g of alkoxy decane monomer was mixed. The solution obtained by premixing HG: 11.05 g, BCS: 3.68 g, water: 10.8 g and catalyst oxalic acid: 0.90 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g, a liquid crystal alignment agent (K7) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 8>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 21.81 g, BCS: 7.27 g, TEOS: 35.42 g, Ben: 2.84 g, and TBC: 6.43 g of alkoxy decane monomer was mixed. The solution obtained by premixing HG: 10.90 g, BCS: 3.63 g, water: 10.80 g and catalyst oxalic acid: 0.90 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g, a liquid crystal alignment agent (K8) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 9>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 22.29 g, BCS: 7.43 g, TEOS: 37.08 g, F13: 0.94 g, and TBC: 6.43 g of alkoxy decane monomer was mixed. The solution obtained by premixing HG: 11.14 g, BCS: 3.71 g, water: 10.80 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.67 g, and BCS: 11.33 g, a liquid crystal alignment agent (K9) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 10>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 22.16 g, BCS: 7.39 g, TEOS: 32.50 g, ACPS: 4.69 g, C18: 1.67 g, and TBC: 6.43 g of alkoxydecane. A solution of the monomer. The solution obtained by premixing HG: 11.08 g, BCS: 3.69 g, water: 10.21 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 26.68 g, BCS: 4.01 g, and PB: 29.32 g, a liquid crystal alignment agent (K10) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 11>

Hg: 22.02 g, BCS: 7.34 g, TEOS: 32. A solution of the monomer. The solution obtained by premixing HG: 11.01 g, BCS: 3.67 g, water: 10.21 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g, a liquid crystal alignment agent (K11) having a concentration of SiO ₂ of 4% by mass was obtained.

<Synthesis Example 12>

A solution of HG: 21.69 g, BCS: 7.23 g, TEOS: 38.75 g, and C18: 4.17 g of alkoxydecane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 10.85 g, BCS: 3.62 g, water: 10.80 g and catalyst oxalic acid: 0.90 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 30 minutes. Further, a mixed solution of APS: 0.89 g, HG: 0.83 g, and BCS: 0.28 g was added. Thereafter, the mixture was heated under reflux for 30 minutes, and after cooling, a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ was obtained.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g, a liquid crystal alignment agent (K12) having a concentration of SiO ₂ of 4% by mass was obtained.

<Comparative Synthesis Example 1>

A solution of HG: 22.63 g, BCS: 7.54 g, TEOS: 39.58 g, and C18: 4.17 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.32 g, BCS: 3.77 g, water: 10.8 g, and oxalic acid: 0.18 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 56.04 g, and BCS: 3.96 g, a liquid crystal alignment agent (L1) having a concentration of SiO ₂ of 4% by mass was obtained.

The addition of the alkoxydecane of Synthesis Examples 1 to 12 and Comparative Synthesis Example 1 is shown in Table 1.

The method for producing the liquid crystal cell, the method for evaluating the liquid crystal alignment property, and the method for measuring the electrical characteristics are as follows.

[Manufacturing method of liquid crystal cell]

The liquid crystal alignment agent was pressure-filtered using a membrane filter having a pore size of 0.45 μm, and then formed on a glass substrate with an ITO transparent electrode by spin coating. The substrate was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating sterile oven at 210 ° C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. Two substrates were prepared, and a pitcher having a particle diameter of 6 μm was spread on the liquid crystal alignment film surface of the single substrate, and then an epoxy-based adhesive was applied to the outer edge portion of the substrate by a screen printing method. Thereafter, the liquid crystal alignment film is bonded to the substrate in a face-to-face manner, and the air-molding unit is cured by press-fitting. The empty unit was placed in a room temperature of 23° C. and a humidity of 98% for 20 hours, and then water (water treatment) was adsorbed, and liquid crystal (MLC-6608 (trade name) manufactured by Meite Co., Ltd.) was injected by a vacuum injection method. At this time, the empty cells before the liquid crystal injection were degassed for 5 minutes. Thereafter, the liquid crystal cell was formed by sealing the injection hole with a UV-curable resin (water-treated).

Further, the empty unit prepared by the above method was placed in an environment of 23 ° C and a humidity of 43% for 20 hours, and then liquid crystal (MLC-6608 (trade name) manufactured by Meite Co., Ltd.) was injected by a vacuum injection method. The liquid crystal cell was produced by sealing the injection hole with a UV-curable resin (without water treatment).

[Liquid alignment]

The liquid crystal cell (water-treated) prepared by the method described in the above [Production of Liquid Crystal Cell] was observed using a polarizing microscope to confirm the alignment state of the liquid crystal. The state in which the entire liquid crystal cell is free of defects is regarded as ○, the alignment defect occurs in some liquid crystal cells, and the vertical alignment is regarded as ×.

[Electrical Characteristics]

A triangular wave having a voltage of ±10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell produced by the method described in the above [Production of Liquid Crystal Cell], and the ion density at this time was measured. The measurement temperature was 80 °C. The measuring device was a 6245 liquid crystal physical property evaluation device manufactured by Dongyang Technology Co., Ltd.

<Examples 1 to 12>

Using the liquid crystal alignment agents K1 to K12 obtained in Synthesis Examples 1 to 12, liquid crystal cells were produced by the above method, and liquid crystal alignment properties and electrical properties were measured. The results are shown in Table 2.

<Comparative Example 1>

The liquid crystal cell was produced by the above method using the liquid crystal alignment agent L1 obtained in Comparative Synthesis Example 1, and the liquid crystal alignment property and the electrical characteristics were measured. The results are shown in Table 2.

As is apparent from Table 2, in the liquid crystal cells of Examples 1 to 12, even when there was no water treatment, the ion density was not increased even when treated with water. Further, in the liquid crystal cell of Comparative Example 1, when the water treatment was not carried out, the ion density was greatly increased upon water treatment.

<Synthesis Example 21>

In a 1 L (liter) four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 113.17 g, BCS: 37.72 g, TEOS: 199.71 g, and C18: 20.84 g of alkoxy decane monomer was mixed. The solution obtained by premixing HG: 56.59 g, BS: 18.86 g, water: 54.0 g, and oxalic acid: 0.90 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 56.04 g, and BCS: 3.96 g, a polysiloxane solution (K21) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 22>

A solution of HG: 22.99 g, BCS: 7.66 g, TEOS: 27.78 g, and C12: 11.09 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.50 g, BS: 3.83 g, water: 15.0 g, and oxalic acid: 0.15 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then at 67 ° C. After heating for 30 minutes, the solution was cooled to obtain a polyoxymethane solution having a concentration of 10% by mass in terms of SiO ₂ .

After mixing the obtained polyoxane solution: 30.0 g, HG: 36.69 g, and BCS: 8.31 g, a polysiloxane solution (K22) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 23>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, a solution of HG: 22.26 g, BCS: 7.42 g, TEOS: 38.33 g, C18: 4.17 g, and C12: 2.00 g of alkoxysilane monomer was mixed. The solution obtained by premixing HG: 11.13 g, BS: 3.71 g, water: 10.8 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.67 g, and BCS: 11.33 g, a polysiloxane solution (K23) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 24>

A solution of HMC: 23.54 g, BCS: 7.85 g, TEOS: 27.08 g, C18: 4.17 g, and MTES: 10.7 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.77 g, BS: 3.92 g, water: 10.8 g, and oxalic acid: 0.18 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.71 g, and BCS: 11.29 g, a polysiloxane solution (K24) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 25>

A solution of HG: 22.79 g, BCS: 7.60 g, TEOS: 39.58 g, and MC18: 3.87 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.39 g, BS: 3.80 g, water: 10.80 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 60.0 g, HG: 97.37 g, and BCS: 22.63 g, a polysiloxane solution (K25) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 26>

A solution of HG: 23.42 g, BCS: 7.81 g, TEOS: 41.25 g, and F13: 0.94 g of alkoxysilane monomer was placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.71 g, BS: 3.90 g, water: 10.80 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 60.0 g, EtOH: 84.00 g, and PGME: 36.00 g, a polysiloxane solution (K26) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 27>

A 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube was charged with HG: 23.59 g, BCS: 7.86 g, TEOS: 39.58 g, and Phe: 2.26 g, and the solution of the alkoxydecane monomer was stirred and stirred. The solution obtained by premixing HG: 11.79 g, BS: 3.93 g, water: 10.80 g, and oxalic acid: 0.18 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 60.0 g, HG: 97.42 g, and BCS: 22.58 g, a polysiloxane solution (K27) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 28>

To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 23.30 g, BCS: 7.77 g, TEOS: 39.58 g, and Ben: 2.84 g were charged, and a solution of the alkoxydecane monomer was stirred and stirred. The solution obtained by premixing HG: 11.65 g, BS: 3.88 g, water: 10.80 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 60.0 g, HG: 97.40 g, and BCS: 22.60 g, a polysiloxane solution (K28) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 29>

To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 21.41 g, BCS: 7.143 g, TEOS: 33.33 g, and TBC: 12.86 g were charged, and a solution of the alkoxydecane monomer was stirred and stirred. The solution obtained by premixing HG: 10.71 g, BCS: 3.57 g, water: 10.8 g, and oxalic acid: 0.18 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.64 g, and BCS: 11.36 g, a polysiloxane solution (L21) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 30>

A solution of HG: 32.70 g, BCS: 10.90 g, and TEOS: 18.75 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 16.35 g, BCS: 5.45 g, water: 5.40 g and catalyst oxalic acid: 0.45 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and heated at 85 ° C. After 30 minutes, a solution obtained by premixing BISA: 1.71 g, HG: 6.22 g, BCS: 2.07 g was added. Thereafter, the mixture was heated at 85 ° C for 30 minutes, and then cooled to obtain a polyoxyalkylene solution having a concentration of 12% by mass in terms of SiO ₂ .

After mixing the obtained polyoxane solution: 60.0 g, HG: 25.96 g, and BCS: 4.04 g, a polysiloxane solution (L22) having a concentration of 4% by mass in terms of SiO ₂ was obtained.

<Synthesis Example 31>

A solution of HG: 22.88 g, BCS: 7.63 g, TEOS: 38.75 g, and MTES: 1.78 g of alkoxydecane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.44 g, BCS: 3.81 g, water: 10.80 g, and oxalic acid: 0.90 g of the catalyst was added dropwise to the solution at room temperature for 30 minutes, and the solution was stirred for 30 minutes and refluxed for 30 minutes. Further, a solution obtained by premixing DMAPS: 0.83 g, HG: 0.88 g, and BCS: 0.29 g was added. Thereafter, the mixture was refluxed for 30 minutes, and after cooling, a polyoxymethane solution having a concentration of 12% by mass in terms of SiO ₂ was obtained.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.69 g, and BCS: 11.31 g, a polysiloxane solution (L23) having a concentration of 4% by mass in terms of SiO ₂ was obtained.

<Synthesis Example 32>

A solution of HG: 17.65 g, BCS: 5.89 g, TEOS: 20.83 g, and TBC: 32.15 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 8.83 g, BCS: 2.94 g, water: 10.80 g and catalyst oxalic acid: 0.90 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.53 g, and BCS: 11.47 g, a polysiloxane solution (L24) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 33>

A solution of HG: 21.15 g, BCS: 7.05 g, TEOS: 29.17 g, ACPS: 4.69 g, and TBC: 12.86 g of alkoxy decane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 10.58 g, BCS: 3.53 g, water: 10.80 g and catalyst oxalic acid: 0.18 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 1 hour. Then, a polysiloxane solution having a concentration of 12% by mass in terms of SiO _{2 was} released.

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.63 g, and BCS: 11.37 g, a polysiloxane solution (L25) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

<Synthesis Example 34>

A solution of HG: 22.88 g, BCS: 7.63 g, TEOS: 38.75 g, and MTES: 1.78 g of alkoxydecane monomer was mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. The solution obtained by premixing HG: 11.44 g, BCS: 3.81 g, water: 10.80 g and catalyst oxalic acid: 0.90 g in 30 minutes at room temperature was dropped into the solution, and the solution was stirred for 30 minutes and then refluxed for 30 minutes. Further, a solution obtained by premixing APS: 0.89 g, HG: 0.83 g, and BCS: 0.28 g was added. Thereafter, the mixture was refluxed for 30 minutes, and then cooled to obtain a polyoxane solution having a concentration of 12% by mass in terms of SiO ₂ .

After mixing the obtained polyoxane solution: 30.0 g, HG: 48.69 g, and BCS: 11.31 g, a polysiloxane solution (L26) having a concentration of 4 mass% in terms of SiO ₂ was obtained.

The addition ratio of the alkoxydecane of the above Synthesis Examples 21 to 34 is shown in Tables 3 and 4.

<Example 21 and Example 35>

The polyoxonane solution (K21 to K28) having a SiO ₂ conversion concentration of 4% by mass and the polyoxonane having a concentration of 4% by mass in terms of SiO ₂ obtained by mixing the synthesis examples 21 to 34 in the ratios shown in Table 5 were mixed. (L21 to L26), a liquid crystal alignment agent (LK1 to LK15) of a polyoxyalkylene having a concentration of 4% by mass in terms of SiO ₂ was obtained.

Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced by the above method, and the liquid crystal alignment property and the electrical characteristics were measured. The results are shown in Table 5.

<Comparative Example 21>

Using the polyoxane solution (K21) obtained in Synthesis Example 21, a liquid crystal cell was produced by the above method, and the liquid crystal alignment property and the electrical characteristics were measured. The results are shown in Table 6.

As is apparent from Table 6, in the liquid crystal cells of Examples 21 to 35, when the water treatment was not carried out, the ion density was not increased even when treated with water. Further, in the liquid crystal alignment unit of Comparative Example 21, when the water treatment was not performed, the ion density was greatly increased by the water treatment.

Industrial use possibility

The liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can have high reliability, and in particular, can be formed into a high-quality liquid crystal display device having high reliability of electrical characteristics, and is suitable for TN type, STN type, IPS type, Various types of display elements such as liquid crystal display elements such as VA type, OCB type, and PSA type.

Claims (7)

A liquid crystal alignment agent comprising a polycondensation comprising an alkoxydecane represented by the formula (1), an alkoxydecane represented by the formula (2), and an alkoxydecane represented by the formula (3) a polyoxyalkylene (AB) derived from oxydecane, and a polypyrene having a concentration of 0.5 to 15% by mass in terms of SiO ₂ , X ¹ (X ² ) _p Si(OR ¹ ) _3-p ( 1) (X ¹ is a hydrocarbon group of 8 to 30 carbon atoms which may be substituted by a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group having 1 to 5 carbon atoms, and R ¹ is carbon An alkyl group having an atomic number of 1 to 5, p is an integer of 0 to 2) X ³ {Si(OR ² ) ₃ } _q (2) (X ³ has 1 nitrogen atom and the nitrogen atom is 1st, 2nd order Or a 3-stage nitrogen atom, and may have an oxygen atom or a sulfur atom of a hydrocarbon group of 2 to 20 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2) (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom or may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a decyl group, a methacryloxy group, an isocyanate group or an acryloxy group , hetero atoms and may have a number of carbon atoms of the hydrocarbon group having 1 to 6, R ³ is an alkyl group having 1 to 5 carbon atoms, n-is an integer of 0 to 3 ). A liquid crystal alignment agent containing the following polyoxyalkylene (A) and polyoxyalkylene (B), and the content of polyoxyalkylene is 0.5 to 15% by mass in terms of SiO ₂ , polyoxyalkylene oxide (A): a polyfluorene oxide obtained by polycondensing an alkoxydecane represented by the above formula (1) and an alkoxydecane of the alkoxydecane represented by the above formula (3); B): Polyoxyalkylene obtained by polycondensation of the alkoxydecane represented by the above formula (2) and the alkoxydecane of the alkoxydecane represented by the above formula (3). The liquid crystal alignment agent of claim 1 or 2, wherein X ³ in the above formula (2) is selected from the group consisting of aminopropyl, 2-aminoethylthioethyl, N,N-diethyl 3-aminopropyl, 3-(N,N-dimethylaminopropyl), diethylaminomethyl, N-methylaminopropyl, N-ethylaminoisobutyl , n-butylaminopropyl, t-butylaminopropyl, bis(2-hydroxyethyl)-3-aminopropyl, 3-(N-allylamino)propyl, 3 -(t-butoxycarbonylamino)propyl, 3-(ethoxycarbonylamino)propyl, 3-(4-hydroxybutaneguanamine)propyl, N-phenylaminopropyl, 3-cyclohexylaminopropyl, N-(3-methylpropenyloxy-2-hydroxypropyl)-3-aminopropyl, N-(3-propenyloxy-2-hydroxypropyl --3-aminopropyl, 3-((2-methylpropenyloxy)ethoxy)carbonylamino)propyl, 3-((vinyloxymethoxy)carbonylamino)propyl , (E)-3-(3-carboxypropenylamine)propyl, -CH ₂ -CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -CH ₂ - At least one group of N(CH ₃ )-CH ₂ -CH ₂ -CH ₂ - groups. A liquid crystal alignment film obtained by a liquid crystal alignment agent according to any one of claims 1 to 3. A liquid crystal display element comprising a liquid crystal alignment film according to item 4 of the patent application. The liquid crystal alignment agent of claim 1, wherein the polyoxyalkylene (AB) is hydrolyzed and condensed in an organic solvent to condense the alkoxysilane represented by the above formula (1) and the above formula (3) After the alkoxydecane shown, the alkoxydecane represented by the above formula (2) is added and subjected to a hydrolysis and condensation step. The liquid crystal alignment agent of the second aspect of the invention, wherein the polyoxyalkylene (A) is added to the above formula after hydrolyzing and condensing the alkoxydecane represented by the above formula (3) in an organic solvent. 1) The alkoxydecane shown is produced by a method of hydrolyzing and condensing, and the polyoxyalkylene (B) is obtained by hydrolyzing and condensing the alkoxydecane represented by the formula (3) in an organic solvent. Thereafter, the alkoxydecane represented by the above formula (2) is added to carry out a method of hydrolysis and condensation.