KR20110104535A - Liquid-crystal alignment material for ink-jet coating, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Liquid-crystal alignment material for ink-jet coating, liquid-crystal alignment film, and liquid-crystal display element Download PDF

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KR20110104535A
KR20110104535A KR1020117017292A KR20117017292A KR20110104535A KR 20110104535 A KR20110104535 A KR 20110104535A KR 1020117017292 A KR1020117017292 A KR 1020117017292A KR 20117017292 A KR20117017292 A KR 20117017292A KR 20110104535 A KR20110104535 A KR 20110104535A
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solvent
liquid crystal
formula
crystal aligning
group
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KR101708949B1 (en
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겐이치 모토야마
가즈키 에구치
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닛산 가가쿠 고교 가부시키 가이샤
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/14Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds

Abstract

Providing a silicon-based liquid crystal aligning film and a liquid crystal aligning agent which are suitable for the inkjet coating method and are excellent in in-plane uniformity of a film | membrane, and edge straightness of a film edge part.
Containing a polysiloxane (A) having a side chain composed of a hydrocarbon group having 8 to 30 carbon atoms substituted or unsubstituted with a fluorine atom, a glycol solvent having 2 to 7 carbon atoms (B), a solvent (C) and a solvent (D) The liquid crystal aligning agent for inkjet coating characterized by the above-mentioned.
Solvent (C): solvent represented by formula (A1),
K 1 O (CH 2 ) w OH (A1)
(In formula, K <1> is a C1-C4 alkyl group and w is an integer of 1-3.)
Solvent (D): It consists of at least 1 sort (s) of compound chosen from the group which consists of a formula (T1), a formula (T2), and a formula (T3), a ketone which has 3-6 carbon atoms, and a C5-C12 alkyl alcohol. Solvent selected from the group.
Figure pct00004

(In formula, X <1> , X <3> and X <5> are a C1-C4 alkyl group, X <2> and X <6> are a hydrogen atom or a C1-C4 alkyl group, X <4> is a C1-C4 alkyl group, P Is an alkyl group having 1 to 3 carbon atoms, m, n, j, k are each independently an integer of 1 to 3, and h is an integer of 2 to 3)

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element for inkjet coating TECHNICAL FIELD [LIQUID-CRYSTAL ALIGNMENT MATERIAL FOR INK-JET COATING, LIQUID-CRYSTAL ALIGNMENT FILM, AND LIQUID-CRYSTAL DISPLAY ELEMENT}

The present invention mainly contains a polysiloxane obtained by polycondensation of polysiloxane, particularly an alkoxysilane, and a liquid crystal aligning agent capable of forming a uniform film by inkjet coating, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal having the liquid crystal aligning film. A display element is related.

It is generally known that a liquid crystal display element has a structure in which two substrates on which a liquid crystal alignment film is formed on a transparent electrode are disposed to face each other, and a liquid crystal substance is filled in the gap.

In recent years, metal halide lamps with strong irradiation intensity have been used as light sources for business applications and liquid crystal projectors for home theaters (rear projection TVs called third thin televisions). Therefore, not only high heat resistance but also high light resistance as a characteristic of a liquid crystal aligning film is calculated | required.

Although the liquid crystal aligning film material generally used has a polyamic acid and polyimide as a main component, the inorganic liquid crystal aligning film is also proposed. For example, a liquid crystal aligning film is formed by vapor deposition (for example, refer patent document 1).

Moreover, as the coating-type inorganic type liquid crystal aligning film, the aligning agent composition containing the reaction product of tetraalkoxysilane, a trialkoxysilane, alcohol, and oxalic acid is proposed, and excellent in the vertical alignment property, heat resistance, and uniformity on the electrode substrate of a liquid crystal display element. Forming a liquid crystal aligning film is reported (for example, refer patent document 2).

In addition, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane and water and a glycol ether solvent has been proposed, which prevents display defects and lowers the ability to orient the liquid crystal having good afterimage properties even after long time driving. It is reported to form a liquid crystal aligning film with few fall of the voltage retention with respect to light and heat, without making it (refer patent document 3).

Generally, spin coat, dip coat, flexographic printing, etc. are mentioned as a film formation method of a liquid crystal aligning film, In fact, flexographic printing is used in many cases. However, in flexographic printing, there are problems such as the need to replace the printing plate according to the size of the substrate for forming the liquid crystal alignment film, and to perform a caustic film in order to stabilize the film forming process.

Therefore, the inkjet coating method attracts attention as a new coating method which does not use a printing plate. The inkjet coating method is a method of dropping fine droplets onto a substrate and forming a film by wetness of the liquid. In addition to not using a printing plate, the inkjet coating method can freely set a printing pattern. It can be simplified. In addition, since the caustic film becomes unnecessary, there is an advantage that the waste of the coating liquid is small. Therefore, cost reduction of liquid crystal panel and improvement of production efficiency are anticipated.

In such a situation, the introduction of the process of forming a liquid crystal aligning film by inkjet coating with the request | requirement of the inorganic liquid crystal aligning film excellent in heat resistance and light resistance is desired, and the inorganic liquid crystal aligning agent which can respond to such a request is calculated | required. have.

Japanese Unexamined Patent Publication No. 2003-50397 Japanese Patent Application Laid-Open No. 09-281502 Japanese Laid-Open Patent Publication 2005-250244

SUMMARY OF THE INVENTION An object of the present invention is to provide a silicon-based liquid crystal aligning agent that can be formed using an inkjet coating method, and to provide a liquid crystal aligning film excellent in in-plane uniformity of the film and edge straightness of the film edge by inkjet coating. .

That is, this invention has the following summary.

(1) Polysiloxane (A) which has a side chain consisting of a C8-C30 hydrocarbon group which the fluorine atom substituted or unsubstituted, the C2-C7 glycol solvent (B), the following solvent (C), and the solvent (D) It contains, The liquid crystal aligning agent for inkjet coatings characterized by the above-mentioned.

Solvent (C): solvent represented by formula (A1),

K 1 O (CH 2 ) w OH (A1)

(In formula, K <1> is a C1-C4 alkyl group and w is an integer of 1-3.)

Solvent (D): It consists of at least 1 sort (s) of compound chosen from the group which consists of a formula (T1), a formula (T2), and a formula (T3), a ketone which has 3-6 carbon atoms, and a C5-C12 alkyl alcohol. Solvent selected from the group.

[Formula 1]

Figure pct00001

(In formula, X <1> , X <3> and X <5> are a C1-C4 alkyl group, X <2> and X <6> are a hydrogen atom or a C1-C4 alkyl group, X <4> is a C1-C4 alkyl group, P Is an alkyl group having 1 to 3 carbon atoms, m, n, j, k are each independently an integer of 1 to 3, and h is an integer of 2 to 3)

(2) The inkjet according to the above (1), wherein the solvent (D) is a solvent selected from a compound represented by formulas (T1) to (T3), a ketone having 3 to 6 carbon atoms, and an alkyl alcohol having 5 to 12 carbon atoms. Liquid crystal aligning agent for application | coating.

(3) The liquid crystal aligning agent for inkjet coating as described in said (1) or (2) whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1).

R 1 Si (OR 2 ) 3 (1)

(R 1 is a C8-30 hydrocarbon group having a substituted or unsubstituted fluorine atom, and R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.)

(4) The liquid crystal aligning agent for inkjet coating as described in said (3) whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by following formula (2).

(R 3 ) n Si (OR 4 ) 4-n (2)

(R 3 is a hydrogen atom, a halogen atom, a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms, wherein any hydrogen atom of the hydrocarbon group is a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group May be substituted with an isocyanate group, an amino group or a ureido group, or may have a hetero atom, R 4 is a hydrocarbon group of 1 to 5 carbon atoms, n represents an integer of 0 to 3)

(5) The inkjet coating according to the above (3) or (4), wherein the polysiloxane (A) is a polysiloxane obtained by polycondensing an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the following formula (3): Liquid crystal aligning agent.

Si (OR 4 ) 4 (3)

(R 4 represents a hydrocarbon group having 1 to 5 carbon atoms)

(6) glycol solvent (B) is ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3 -Pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3- Hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1,2-heptanediol, 2,3-heptanediol, 3,4-heptanediol, 1,3-heptane Diol, 2,4-heptane diol, 3,5-heptane diol, 1,4-heptane diol, 2,5-heptane diol, 1,5-heptane diol, 2,6-heptane diol, 1,6-heptane diol And the liquid crystal aligning agent for inkjet coating in any one of said (1)-(5) which is 1 or more types of solvent chosen from the group which consists of 1,7-heptane diol.

(7) The liquid crystal aligning agent for inkjet coating in any one of said (1)-(6) whose X <2> in the said Formula (T1) is a hydrogen atom.

(8) The polysiloxane (A) is about a silicon atom having on 100 parts by mass of the total of the values in terms of SiO 2, glycol solvent (B) from 20 to 18,000 parts by weight, the solvent (C) The part 2 ~ 17,500 by weight, The liquid crystal aligning agent for inkjet coating in any one of said (1)-(7) whose solvent (D) is 2-17,500 mass parts.

(9) The polysiloxane (A) is about a silicon atom having on 100 parts by mass of the total of the values in terms of SiO 2, glycol solvent (B) is from 2 to 16,800 120 ~ 17,000 parts by weight, the solvent (C) parts by weight, The liquid crystal aligning agent for inkjet coating in any one of said (1)-(8) whose solvent (D) is 2-16,800 mass parts.

(10) The liquid crystal aligning agent for inkjet coating in any one of said (1)-(9) whose viscosity of the said aligning agent is 1.8-18 mPa * s.

(11) The liquid crystal aligning agent for inkjet coating as described in any one of said (1)-(10) whose surface tension of the said aligning agent is 20-40 mN / m.

The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent for inkjet coating of any one of said (1)-(11) to a board | substrate using an inkjet apparatus, and baking it.

(13) The formation method of the liquid crystal aligning film obtained by apply | coating and baking the liquid crystal aligning agent for inkjet coatings in any one of said (1)-(11) to a board | substrate using an inkjet apparatus.

The liquid crystal display element which has a liquid crystal aligning film as described in said (12).

The liquid crystal aligning agent of this invention can form the liquid crystal aligning film excellent in the in-plane uniformity of a film and the edge straightness of a film edge part by inkjet coating.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

<Polysiloxane A>

Polysiloxane (A) used by this invention is a polysiloxane which has a side chain (henceforth called a specific organic group) which consists of a hydrocarbon group of 8-30, preferably 8-22 carbon atoms which a fluorine atom substituted or unsubstituted.

Although the said specific organic group has the effect of orienting a liquid crystal in 1 direction, if it has this effect, it will not specifically limit. Examples thereof include alkyl groups, fluoroalkyl groups, alkenyl groups, phenethyl groups, fluorophenylalkyl groups, styrylalkyl groups, naphthyl groups and the like.

Among these, an alkyl group is preferable because it is easy to obtain.

Polysiloxane (A) used for this invention may have two or more types of specific organic groups.

The polysiloxane (A) used for this invention aims at improving adhesiveness with a board | substrate, affinity with a liquid crystal molecule, etc., and does not impair the effect of this invention, A side chain different from a specific organic group (henceforth, Also referred to as 2 organic groups). The said 2nd organic group is C1-C7, Preferably it is 1-6, More preferably, it is an organic group of 1-5. The second organic group may have a ring structure such as an aliphatic hydrocarbon; an aliphatic ring, an aromatic ring, or a hetero ring; an unsaturated bond; a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom; The second organic group is a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms, and any hydrogen atom of the hydrocarbon group is a glycidoxy group, mercapto group, methacryloxy group, acryloxy group, isocyanate group, amino group or ureido group It may be substituted with and may have a hetero atom. Polysiloxane (A) used for this invention may have 1 type (s) or 2 or more types of 2nd organic groups.

Although the method of obtaining the polysiloxane (A) mentioned above is not specifically limited, Generally, it is obtained by polycondensing an alkoxysilane.

Specifically, polysiloxane (A) can be obtained by polycondensing the alkoxysilane which makes an alkoxysilane represented by following formula (1) an essential component.

R 1 Si (OR 2 ) 3 (1)

In formula (1), R <1> represents a specific organic group, The example is the same as that described as said specific organic group. Especially, since the alkoxysilane whose R <1> is an alkyl group is comparatively cheap and it is easy to obtain as a commercial item, it is preferable. R <2> is C1-C5, Preferably it is a hydrocarbon group of 1-4.

Although the specific example of the alkoxysilane represented by said formula (1) is given, it is not limited to this.

For example, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexa Decyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyl Triethoxysilane, undecyltrimethoxysilane, 21-docosenyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-vinylphenylethyltrimethoxysilane, p-vinylphenylethyltrimeth Oxysilane, (1 -Naphthyl) triethoxysilane, (1-naphthyl) trimethoxysilane, allyloxyundecyltriethoxysilane, benzoyloxypropyltrimethoxysilane, 3- (4-methoxyphenoxy) propyltrimeth Methoxysilane, 1-[(2-triethoxysilyl) ethyl] cyclohexane-3,4-epoxide, 2- (diphenylphosphino) ethyltriethoxysilane, diethoxymethyloctadecylsilane, dimethoxymethyl Octadecylsilane, diethoxydodecylmethylsilane, dimethoxydodecylmethylsilane, diethoxydecylmethylsilane, dimethoxydecylmethylsilane, diethoxyoctylmethylsilane, dimethoxyoctylmethylsilane, ethoxydimethyloctadecylsilane, meth Oxydimethyl octadecyl silane and the like.

Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyl Triethoxysilane, Heptadecyltrimethoxysilane, Heptadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, Nonadecyltrimethoxysilane, Nonadecyltriethoxysilane, Undecyltree Ethoxysilane or undecyl trimethoxysilane, diethoxymethyloctadecylsilane, and diethoxydodecylmethylsilane are preferable.

In this invention, you may use together multiple types of alkoxysilane represented by Formula (1).

Since the use rate of the alkoxysilane represented by Formula (1) is less than 0.1 mol% in all the alkoxysilanes used in order to obtain polysiloxane (A), since favorable liquid-crystal orientation may not be obtained, it is 0.1 mol % Or more is preferable. More preferably, it is 0.5 mol% or more. Moreover, when exceeding 30 mol%, since the liquid crystal aligning film formed may not fully harden, 30 mol% or less is preferable. More preferably, it is 22 mol% or less. More preferably, it is 15 mol% or less.

Moreover, in this invention, it is preferable that it is polysiloxane obtained by polycondensing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by following formula (2).

(R 3 ) n Si (OR 4 ) 4-n (2)

R <3> is a hydrogen atom, a halogen atom, a vinyl group, or a C1-C7 hydrocarbon group, Preferably it is a hydrogen atom or a C1-C7 hydrocarbon group. The arbitrary hydrogen atom of the said hydrocarbon group may be substituted by the glycidoxy group, the mercapto group, the methacryloxy group, the acryloxy group, the isocyanate group, the amino group, or the ureido group, and may have a hetero atom. R <4> is C1-C5, Preferably it is 1-4, More preferably, it is a hydrocarbon group of 1-3, n is 0-3, Preferably it represents the integer of 0-2.

Moreover, when R <3> of Formula (2) is a vinyl group or a hydrocarbon group, R <3> represents the 2nd organic group mentioned above. In this case, therefore, the example of R 3 is the same as that described as the second organic group.

Examples of the alkoxysilane represented by the formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane and propyltrie. Methoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) tri Methoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-mercaptopropyl Triethoxysilane, mercaptomethyl trimethoxysilane, 3-ureidopropyl tree Ethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri Methoxysilane, 3-acryloxypropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mer Captopropyl trimethoxysilane etc. are mentioned.

In the alkoxysilane of Formula (2), a trimethoxysilane, a triethoxysilane, a tripropoxysilane, a tributoxysilane etc. are mentioned as a specific example of the alkoxysilane when R <3> is a hydrogen atom. .

In the alkoxysilane of Formula (2), the alkoxysilane whose n is 0 represents the tetraalkoxysilane of Formula (3).

Si (OR 4 ) 4 (3)

In formula (3), R <4> is C1-C5, Preferably it is 1-4, More preferably, it is a hydrocarbon group of 1-3. Since the tetraalkoxysilane represented by Formula (3) tends to be condensed with the alkoxysilane represented by Formula (1), in order to obtain polysiloxane (A), it is preferable. As a specific example of the tetraalkoxysilane of Formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. are mentioned.

When using the alkoxysilane represented by said Formula (2) or Formula (3), it can use suitably 1 type or multiple types as needed.

When using the alkoxysilane represented by Formula (2) or Formula (3) together, the total usage-amount of the alkoxysilane represented by Formula (2) or Formula (3) is in all the alkoxysilanes used in order to obtain polysiloxane (A), It is preferable that it is 70-99.7 mol%. More preferably, it is 78-99.7 mol%. More preferably, the alkoxysilane represented by Formula (2) or Formula (3) is 85-99.7 mol%.

Polysiloxane (A) used for this invention is obtained by condensing the alkoxysilane containing the alkoxysilane represented by said Formula (1) as an essential component in an organic solvent. In that case, the alkoxysilane containing the alkoxysilane represented by Formula (1), Formula (2), and Formula (3) is preferable. Usually, polysiloxane (A) polycondenses such alkoxysilane and is obtained as a solution which melt | dissolved in the organic solvent uniformly.

Although the method of condensing the polysiloxane (A) used for this invention is not specifically limited, For example, the method of hydrolyzing and condensing an alkoxysilane in alcohol or a glycol solvent is mentioned. In that case, any of partial hydrolysis and complete hydrolysis may be sufficient as a hydrolysis-condensation reaction. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all the alkoxy groups in an alkoxysilane may be added, but an excess amount of water is usually added more than 0.5 times mole.

In this invention, although the quantity of the water used for the said reaction can be suitably selected as desired, 0.5-2.5 times mole of all the alkoxy groups in an alkoxysilane is preferable normally.

Normally, for the purpose of promoting hydrolysis and condensation reactions, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid and fumaric acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like Catalysts such as alkali and hydrochloric acid, metal salts such as sulfuric acid and nitric acid. Moreover, it is also common to accelerate hydrolysis and condensation reaction by heating the solution which the alkoxysilane melt | dissolved. In that case, heating temperature and a heat time can be suitably selected as desired, For example, methods, such as heating and stirring at 50 degreeC for 24 hours, or heating and stirring for 1 hour under reflux, are mentioned.

Moreover, as another method, the method of heating and polycondensing the mixture of an alkoxysilane, a solvent, and oxalic acid is mentioned, for example. Specifically, oxalic acid is added to the alcohol in advance to form an alcohol solution of oxalic acid, and then alkoxysilane is mixed in a state in which the solution is heated. In that case, 0.2-2 mol is preferable with respect to 1 mol of all the alkoxy groups which the alkoxysilane has in the quantity of oxalic acid to be used. Heating in this method can be performed at 50-180 degreeC of liquid temperature, Preferably it is tens of minutes under reflux in the container provided with a reflux tube so that evaporation, volatilization, etc. of a liquid may not generate | occur | produce, for example. To several tens of hours.

When obtaining polysiloxane (A), when using two or more types of alkoxysilanes, you may mix an alkoxysilane as a mixture previously and may mix several types of alkoxysilanes one by one.

The solvent (henceforth a polymerization solvent) used when polycondensing an alkoxysilane is not specifically limited as long as it dissolves an alkoxysilane. Moreover, what is necessary is just to melt | dissolve with advancing of the polycondensation reaction of an alkoxysilane, even if an alkoxysilane does not melt | dissolve. Generally, since alcohol is produced | generated by the polycondensation reaction of an alkoxysilane, the organic solvent with favorable compatibility with alcohols, glycols, glycol ethers, and alcohols is used.

Specific examples of such a polymerization solvent include methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl carbitol, and butyl carbitol , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol 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 mono Butyl ether, propylene glycol dimethyl ether, propylene glycol di Butyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide And tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

In this invention, you may mix and use multiple types of the said polymerization solvent.

Solution obtained this way, after the same way and is common to the one (hereinafter referred to, SiO 2 in terms of concentration) of the total alkoxy concentration in terms of silicon atom to SiO 2 of the silane injected as a raw material to less than 20% by mass, preferably 15 parts by mass It is% or less. By selecting an arbitrary concentration in this concentration range, formation of a gel can be suppressed to obtain a homogeneous solution.

<Solution of Polysiloxane (A)>

In the present invention, the solution obtained by the above-described method may be used as the solution of polysiloxane (A) as it is, and if necessary, the solution obtained by the above-described method is concentrated or diluted by adding a solvent or another solvent. It is good also as a solution of polysiloxane (A).

In that case, the solvent (henceforth an addition solvent) to be used may be the same solvent as what was used for polycondensation, and may be another solvent. This solvent is not specifically limited as long as polysiloxane (A) is melt | dissolving uniformly, It can select arbitrarily whether it is 1 type or multiple types.

Specific examples of such an added solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethylene glycol, diethylene glycol, propylene glycol, Glycols such as 2-methyl-2,4-pentanediol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Glycol ethers such as monopropyl ether and propylene glycol monobutyl ether Esters such as methyl acetate, ethyl acetate and ethyl lactate; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, and dimethyl; Sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

In this invention, 1 type of solutions of the polysiloxane (A) obtained as mentioned above may be used, and multiple types may be used.

<Glycol Solvent (B)>

The glycol solvent (B) used by this invention is a C2-C7, preferably 2-5 glycol solvent, For example, ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2, 4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1 , 4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1, 2-heptane diol, 2,3-heptane diol, 3,4-heptane diol, 1,3-heptane diol, 2,4-heptane diol, 3,5-heptane diol, 1,4-heptane diol, 2,5 -Heptanediol, 1,5-heptanediol, 2,6-heptanediol, 1,6-heptanediol, 1,7-heptanediol and the like. A glycol solvent (B) may use multiple types together. Among them, ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol , 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2, 4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4 Preference is given to -hexanediol, 2,5-hexanediol, 3,4-hexanediol, or mixed solvents thereof.

Such a glycol solvent (B) may be used as all or part of the polymerization solvent and addition solvent at the time of polycondensing polysiloxane (A), and may be added later to the polysiloxane (A) synthesize | combined with another solvent.

The content of the glycol solvent (B) used in the present invention, in the liquid crystal alignment, the polysiloxane (A) is about a silicon atom having on 100 parts by mass of the total of the values in terms of SiO 2, glycol solvent (B) is 20 -18,000 mass parts, Preferably it is 120-17,000 mass parts, More preferably, it is 150-16,000 mass parts. When it is less than 20 mass parts, favorable applicability may not be obtained.

The glycol solvent (B) used for this invention has the effect of suppressing the spread of the liquid at the time of apply | coating especially, and the film | membrane excellent in edge straightness especially can be obtained.

<Solvent (C)>

Solvent (C) used by this invention is 1 or more types of solvent chosen from the group which consists of a solvent represented by Formula (A1).

K 1 O (CH 2 ) w OH (A1)

In formula, K <1> is a C1-C4 alkyl group and w is an integer of 1-3.

As a specific example of a solvent (C), 2-methoxy ethanol, 2-ethoxy ethanol, 2-propoxy ethanol, 2-butoxy ethanol, etc. are mentioned.

The solvent (C) used in the present invention may be used as all or part of the polymerization solvent and the addition solvent when polycondensation of the polysiloxane (A), or may be added later to the polysiloxane (A) synthesized with another solvent.

The content of the solvent (C) is 2 to 17,500 parts by mass of the solvent (C), preferably 2 to 16,800 parts by mass based on 100 parts by mass of the total amount of the silicon atoms of the polysiloxane (A) in terms of SiO 2 . Part, More preferably, it is 2-16,000 mass parts. When less than 2 mass parts, favorable applicability | paintability may not be obtained.

These solvents (C) have the effect of spreading the liquid at the time of application, and in particular, a film excellent in in-plane uniformity can be obtained.

<Solvent (D)>

The solvent (D) used in the present invention is at least one compound selected from the group consisting of the following formula (T1), formula (T2) and formula (T3), a ketone having 3 to 6 carbon atoms, and a carbon having 5 to 12 carbon atoms. It is 1 or more types of solvent chosen from the group which consists of alkyl alcohols.

[Formula 2]

Figure pct00002

In formula, X <1> , X <3> and X <5> are a C1-C4 alkyl group, X <2> and X <6> are a hydrogen atom or a C1-C4 alkyl group, X <4> is a C1-C4 alkyl group, P is It is a C1-C3 alkyl group, m, n, j, k are the integers of 1-3 each independently, and h is an integer of 2-3.

The solvent (D) used in the present invention is preferably at least one solvent selected from the group consisting of a compound of formulas (T1) to (T3), a ketone having 3 to 6 carbon atoms, and an alkyl alcohol having 5 to 12 carbon atoms. Do.

Solvent (D) used by this invention is a compound represented by the said Formula (T1), the compound represented by the said Formula (T3), a C3-C6 ketone, or a C5-C12 alkyl alcohol solely, for example. A solvent may be sufficient. Moreover, the mixed solvent of the compound represented by Formula (T1) and the compound represented by Formula (T2) may be sufficient, and also the mixed solvent of the compound represented by Formula (T1) and a C5-C12 alkyl alcohol may be sufficient.

Moreover, it is preferable that X <2> and X <6> of said Formula (T1) and (T3) are hydrogen atoms.

Specific examples of the compound represented by formula (T1) include 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-ethoxy-2-propanol (propylene glycol monoethyl ether) and 1-propoxy-2- Propanol (propylene glycol monopropyl ether), 1-butoxy-2-propanol (propylene glycol monobutyl ether), 1,2-dimethoxy propane (propylene glycol dimethyl ether), 1,2- diethoxy propane (propylene glycol di Ethyl ether), 1,2-dipropoxy propane (propylene glycol dipropyl ether), and 1,2-dibutoxy propane (propylene glycol dibutyl ether) are preferable. Especially, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, or 1-butoxy-2-propanol is preferable.

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, etc. are mentioned as a specific example of a compound represented by Formula (T2). Especially, ethylene glycol dimethyl ether or ethylene glycol dibutyl ether is preferable.

As a specific example of a compound represented by Formula (T3), 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 and the like. Especially, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, or diethylene glycol dibutyl ether is preferable.

Methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned as a specific example of C3-C6 ketone of a solvent (D).

Specific examples of the alkyl alcohols having 5 to 12 carbon atoms in the solvent (D) include hexanol, heptanol, octanol, nonanol, decanol, undecanol, and dodecanol. Especially, hexanol, heptanol, octanol, nonanol, or decanol is preferable.

The solvent (D) used in the present invention may be used as all or part of the polymerization solvent and addition solvent when polycondensation of the polysiloxane (A), or may be added later to the polysiloxane (A) synthesized with another solvent.

The content of the solvent (D) is 2 to 17,500 parts by mass of the solvent (D), preferably 2 to 16,800 parts by mass based on 100 parts by mass of the total amount of the value of the silicon atom of the polysiloxane (A) in terms of SiO 2 . Part, More preferably, it is 2-16,000 mass parts. When less than 2 mass parts, favorable applicability | paintability may not be obtained.

These solvents (D) have the effect of spreading the liquid at the time of application, and in particular, a film excellent in in-plane uniformity can be obtained.

<Other solvent>

In this invention, you may use together solvents other than a glycol solvent (B), a solvent (C), and a solvent (D), unless the effect of this invention is impaired. Specific examples of other solvents include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; esters such as acetone, methyl acetate, ethyl acetate, and ethyl lactate; N-methyl-2-pi Rollidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

&Lt; Other components &gt;

In the present invention, other components other than the polysiloxane (A), glycol solvent (B), solvent (C), and solvent (D), for example, inorganic fine particles and metal, as long as the effects of the present invention are not impaired. Components, such as a siloxane oligomer, a metal siloxane polymer, a leveling agent, and surfactant, may contain.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles and magnesium fluoride fine particles are preferable, and a colloidal solution of these inorganic fine particles is particularly preferable. This colloidal solution may disperse | distribute inorganic fine particle powder to a dispersion medium, and may be a colloidal solution of a commercial item.

In this invention, by containing an inorganic fine particle, it becomes possible to provide the surface shape of the cured film formed, or another function. As inorganic fine particles, it is preferable that the average particle diameter is 0.001-0.2 micrometer, More preferably, it is 0.001-0.1 micrometer. When the average particle diameter of an inorganic fine particle exceeds 0.2 micrometer, transparency of the hardened film formed using the coating liquid prepared may fall.

Water and an organic solvent are mentioned as a dispersion medium of inorganic fine particles. As a colloidal solution, it is preferable that pH or pKa is adjusted to 1-10 from a stability viewpoint of the coating liquid for film formation. More preferably, it is 2-7.

Examples of the organic solvent used in the dispersion medium of the colloidal solution include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, Alcohols such as ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone Ester, such as ethyl acetate, butyl acetate, (gamma) -butyrolactone; Ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned. Among these, alcohols and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

As the metal siloxane oligomer or the metal siloxane polymer, single or complex oxide precursors such as silicon, titanium, zirconium, aluminum, tantalum, antimony, bismuth, tin, indium and zinc are used. As a metal siloxane oligomer or a metal siloxane polymer, a commercial item may be sufficient and what was obtained by conventional methods, such as hydrolysis, from monomers, such as a metal alkoxide, a nitrate, a hydrochloride, and a carboxylate.

In this invention, the refractive index of a cured film can be improved or photosensitivity can be provided by containing a metal siloxane oligomer or a metal siloxane polymer. When using a metal siloxane oligomer or a metal siloxane polymer, when synthesize | combining a polysiloxane (A), you may use simultaneously, and may add it later to a polysiloxane (A).

Examples of commercially available metal siloxane oligomers or metal siloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcot Co., Ltd. Polymer; titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Canto Chemical Company. You may use these individually or in mixture of 2 or more types.

Moreover, a leveling agent, surfactant, etc. can use a well-known thing, Especially since a commercial item is easy to obtain, it is preferable.

Moreover, the method of mixing said other components with polysiloxane (A) may be simultaneous with the solution of polysiloxane (A), glycol solvent (B), and after mixing them, and is not specifically limited.

<Preparation of liquid crystal aligning agent>

The method of preparing the liquid crystal aligning agent of this invention is not specifically limited. The polysiloxane (A) and the glycol solvent (B), the solvent (C), the solvent (D) and other components may be in a state in which they are uniformly mixed.

Usually, since polysiloxane (A) is polycondensed in a solvent, it is obtained in solution. Therefore, the method of using the polymerization solution of polysiloxane (A) mentioned above as it is is easy. When the polymerization solvent of polysiloxane (A) is a glycol solvent (B) or a solvent (C) or a solvent (D), you may not add a glycol solvent (B) or a solvent (C) or a solvent (D) after that. Moreover, when the solution of polysiloxane (A) does not contain a glycol solvent (B), a solvent (C), or a solvent (D), when preparing a liquid crystal aligning agent, a glycol solvent (B) or a solvent (C) or A solvent (D) can be added and used.

When preparing a liquid crystal aligning agent, a liquid crystal aligning agent of SiO 2 in terms of concentrations and 0.5 to 15% by weight preferably, and more preferably 1-6% by weight. In a range of concentration in terms of SiO 2, it is possible to easily obtain a desired film thickness by one time of coating, it is possible to easily obtain a sufficient pot life of the solution.

Further, at that time, the solvent to be used in the adjustment of the concentration in terms of SiO 2 may be used at least one kind of solvent selected from the group consisting of a polymerization solvent, it added solvents and glycol solvents (B) of the polysiloxane (A).

The liquid crystal aligning agent of this invention can form the liquid crystal aligning film excellent in the in-plane uniformity of a film and the edge straightness of a film edge part by inkjet coating.

<Liquid crystal aligning film and its formation method>

As a coating method of the liquid crystal aligning agent for forming a liquid crystal aligning film, the spin coat method, the printing method, the inkjet coating method, the spray method, the roll coating method, etc. are mentioned, The inkjet coating method which the expectation of the improvement of productivity more is focused. I am getting it.

The inkjet coating method is a method of dropping fine droplets onto a substrate and forming a film by wet spreading of the liquid.

The liquid crystal aligning agent of this invention has favorable applicability, and when an inkjet coating method is used, it can apply | coat stably and a liquid crystal aligning film can be obtained by the coating method. Moreover, it can be set as a cured film by baking after application | coating.

In order to form a film more uniformly using the inkjet coating method, it is necessary to stably discharge the liquid from the nozzle of the inkjet. One of the factors for stably discharging liquid is the involvement of liquid viscosity. Although the preferable liquid viscosity of a liquid crystal aligning agent changes with inkjet coating apparatus to be used, it is the range of about 1.8-18 mPa * s (measurement temperature 25 degreeC) with an E-type viscometer (for example, the viscometer TV-20 by Toki Industries Co., Ltd.). Is preferred. More preferably, it is 3-15 mPa * s.

In addition, as one of the factors for expanding the dropped droplets, the surface tension of the liquid also greatly influences. Although the surface tension of the liquid of the liquid crystal aligning agent is different depending on the kind of material to be used, it is a method of enactment (for example, AUTO DISPENCER AD-3 by Kyowa Interface Science, Ltd., measurement temperature 25 degreeC), The range of about 20-40 mN / m is preferable.

It is especially preferable that the liquid crystal aligning agent of this invention is 1.8-18 mPa * s (measurement temperature 25 degreeC), and surface tension is 20-40 mN / m (measurement temperature 25 degreeC).

Although the process of drying after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not fixed for every board | substrate, or is not immediately baked after application | coating, it is preferable to include a drying process. The solvent should just be removed to such an extent that a coating-film shape does not deform | transform by conveyance of a board | substrate etc., and this drying is not specifically limited about the drying means. For example, the method of drying for 0.5 to 30 minutes, Preferably 1 to 5 minutes is mentioned on the hotplate of temperature 40-150 degreeC, Preferably it is 60-100 degreeC.

The coating film formed by apply | coating a liquid crystal aligning agent by the said method can be baked, and it can be set as a cured film. In that case, although baking temperature can be performed at arbitrary temperature of 100-350 degreeC, Preferably it is 140-300 degreeC, More preferably, it is 150-230 degreeC, More preferably, it is 160-220 degreeC.

In the baking process, polycondensation of polysiloxane (A) in a liquid crystal aligning film advances. However, in the present invention, it is not necessary to completely polycondense unless the effect of the present invention is impaired. However, it is preferable to bake at a temperature 10 degreeC or more higher than the heat processing temperature, such as sealing compound hardening, which is required at the liquid crystal cell manufacturing process.

The thickness of this cured film can be selected as needed. When the thickness of a cured film is 5 nm or more, since the reliability of a liquid crystal display element can be obtained easily, it is preferable. More preferably, it is 10 nm or more. Moreover, in the case of 300 nm or less, since the power consumption of a liquid crystal display element does not become extremely large, it is preferable. More preferably, it is 150 nm or less.

Although such a cured film can also be used as a liquid crystal aligning film as it is, it can also be set as a liquid crystal aligning film by rubbing this cured film, irradiating polarized light, the light of a specific wavelength, etc., or performing an ion beam.

Since the liquid crystal aligning film of this invention formed by the said method shows high water repellency, favorable liquid-crystal vertical alignment property can be obtained.

<Liquid crystal display element>

The liquid crystal display element of this invention can form and obtain a liquid crystal cell by a well-known method after forming a liquid crystal aligning film in a board | substrate by said method.

As an example of liquid crystal cell preparation, the method of fixing a pair of board | substrates with which the liquid crystal aligning film was formed with a sealing agent across a spacer, and injecting and sealing a liquid crystal is common. In that case, although the size of the spacer to be used is 1-30 micrometers, Preferably it is 2-10 micrometers. The method for injecting the liquid crystal is not particularly limited, and the vacuum method for injecting the liquid crystal after the inside of the produced liquid crystal cell is reduced in pressure, the dropping method for sealing after dropping the liquid crystal, and the like can be exemplified.

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate used for a liquid crystal display element, Usually, it is a board | substrate with a transparent electrode for driving a liquid crystal on a board | substrate. Specific examples include glass plates; polycarbonate, poly (meth) acrylate, polyethersulfone, polyallylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) The board | substrate with which a transparent electrode was formed in plastic boards, such as an acrylonitrile, a triacetyl cellulose, a diacetyl cellulose, an acetate butyrate cellulose, etc. are mentioned.

In addition, in a high function device such as a TFT type liquid crystal display device, one in which an element such as a transistor is formed between an electrode for liquid crystal drive and a substrate is used.

In the case of a transmissive liquid crystal display element, it is common to use the above-mentioned board | substrate. However, in a reflection type liquid crystal display element, opaque board | substrates, such as a silicon wafer, can also be used if it is a board | substrate of one side only. In that case, the material like aluminum which reflects light can also be used for the electrode formed in the board | substrate.

Example

Although an Example of this invention demonstrates more concretely below, it limits to these and is not interpreted.

The abbreviation in the compound used by the present Example is as follows.

TEOS: Tetraethoxysilane

C18: octadecyl triethoxysilane

UPS: 3-ureidopropyltriethoxysilane

HG: 2-methyl-2,4-pentanediol

BCS: 2-butoxyethanol

PB: 1-butoxy-2-propanol

1,3-BDO : 1,3-butanediol

NMP: N-methyl-2-pyrrolidone

DEDE: diethylene glycol diethyl ether

EDM: Ethylene Glycol Dimethyl Ether

MIBK: Methyl Isobutyl Ketone

C8OH: 1-octanol

<Synthesis example 1>

4.2 g of HG 22.6 g, BCS 7.5 g, TEOS 39.6 g, and C18 were charged into a 1 liter (L) four-necked reaction flask equipped with a thermometer and a reflux tube, followed by stirring to prepare a solution of an alkoxysilane monomer. The oxalic acid solution which mixed oxalic acid 0.2g as HG 11.3g, BCS 3.8g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and after completion | finish of dripping, it stirred at room temperature for 30 minutes. Then, after heating for 1 hour under reflux, the mixture was allowed to cool and a polysiloxane solution (K1) having a SiO 2 equivalent solid content concentration of 12% by mass was obtained.

<Synthesis example 2>

Into a 1 L four-necked reaction flask equipped with a thermometer and a reflux tube, 4.2 g of HG 30.2 g, TEOS 39.6 g, and C18 were added and stirred to prepare a solution of an alkoxysilane monomer. The oxalic acid solution which mixed oxalic acid 0.2g as HG 15.1g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and after completion | finish of dripping, it stirred at room temperature for 30 minutes. Then, after heating for 1 hour under reflux, the mixture was left to cool to obtain a polysiloxane solution (K2) having a SiO 2 equivalent solid content concentration of 12% by mass.

<Synthesis example 3>

Into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, 4.2 g of BCS 30.2 g, TEOS 39.6 g, and C18 were added and stirred to prepare a solution of an alkoxysilane monomer. The oxalic acid solution which mixed oxalic acid 0.2g as BCS15.1g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and after completion | finish of dripping, it stirred at room temperature for 30 minutes. Then, after heating under reflux for 1 hour, the mixture was allowed to cool and a polysiloxane solution (K3) having a SiO 2 equivalent solid content concentration of 12 mass% was obtained.

<Synthesis example 4>

0.8 g of HG 23.0 g, BCS 7.7 g, TEOS 40.4 g, and C18 were charged into a 1 L four-neck reaction flask equipped with a thermometer and a reflux tube, followed by stirring to prepare a solution of an alkoxysilane monomer. The oxalic acid solution which mixed oxalic acid 0.2g as HG 11.5g, BCS 3.8g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and after completion | finish of dripping, it stirred at room temperature for 30 minutes. Thereafter, after heating at reflux for 30 minutes, a mixed solution of 1.15 g of a 92 mass% methanol solution of UPS, 0.48 g of HG, and 0.16 g of BCS was added thereto, and further, after overheating for 30 minutes under reflux, it was allowed to cool and solidified in terms of SiO 2. The polysiloxane solution (K4) which is 12 mass% was obtained.

Synthetic example Polysiloxane solution Alkoxysilane (mol) Formula (1) Formula (2) Formula (3) 1 K1 C18
(0.005)
TEOS
(0.095)
2 K2 C18
(0.005)
TEOS
(0.095)
3 K3 C18
(0.005)
TEOS
(0.095)
4 K4 C18
(0.001)
UPS
(0.002)
TEOS
(0.097)

<Examples 1-7, Comparative Examples 3 and 4>

The polysiloxane solution obtained in Synthesis Example 1 (K1) 50 g and each solvent a, mixed so that the solvent composition shown in Table 1, SiO 2 in terms of solid content of the liquid crystal orientation 3% claim (KL1 ~ 7, KM3 ~ 4 ) Got.

<Example 8>

A polysiloxane solution (K4) 50 g each of solvent and obtained in Synthesis Example 4, the mixed solvent so that the compositions shown in Table 2, SiO 2 in terms of solid content concentration of 3 mass% to obtain a liquid crystal aligning agent (KL8).

<Comparative Example 1>

50 g of polysiloxane solution (K2) obtained in Synthesis Example 2 and 150 g of HG were mixed and stirred to obtain a liquid crystal aligning agent (KM1) having a SiO 2 equivalent solid content concentration of 3 mass%.

<Comparative Example 2>

Mixing a polysiloxane solution (K3) 50 g and BCS 150 g obtained in Synthesis Example 3, and stirring them, SiO 2 in terms of solid content concentration of 3 mass% to obtain a liquid crystal aligning agent (KM2).

Liquid crystal aligning agent Polysiloxane solution SiO 2 conversion
(wt%)
Glycol solvent
(B)
(Wt%)
menstruum
(C)
(wt%)
Solvent (D)
(Wt%)
Other solvents
(Wt%)
Example 1 KL1 K1 3 HG
(43)

BCS
(9)
PB
(34)
Example 2 KL2 K1 3 HG
(26)

BCS
(9)
PB
(52)
Example 3 KL3 K1 3 HG
(43)
1,3-BDO
(17)
BCS
(9)
PB
(17)
Example 4 KL4 K1 3 HG
(43)

BCS
(9)
PB
(9)
MIBK
(26)
Example 5 KL5 K1 3 HG
(43)

BCS
(34)
C8OH
(9)
Example 6 KL6 K1 3 HG
(43)
BCS
(9)
DEDE
(34)
Example 7 KL7 K1 3 HG
(43)
BCS
(9)
PB
(17)
EDM
(17)
Example 8 KL8 K4 3 HG
(43)
BCS
(9)
PB
(34)
Comparative Example 1 KM1 K2 3 HG
(86)

Comparative Example 2 KM2 K3 3 BCS
(86)
Comparative Example 3 KM3 K1 3 HG
(26)

BCS
(60)
Comparative Example 4 KM4 K1 3 HG
(43)

BCS
(9)
NMP
(34)

Examples 1-8 and Comparative Examples 1-4 The solution viscosity and surface tension of the obtained liquid crystal aligning agent were shown in Table 3. In addition, solution viscosity and surface tension were measured with the following method.

[Solution viscosity]

It measured at the temperature of 25 degreeC using the E-type viscosity meter (Viscometer TV-20 by the Toki Sangyo company).

[Surface tension]

It measured using AUTO DISPENCER AD-3 by Kyowa Interface Science.

Liquid crystal aligning agent Viscosity
(MPas)
Surface tension
(M / m)
Example 1 KL1 7.5 26.9 Example 2 KL2 5.4 25.4 Example 3 KL3 14.4 7.4 Example 4 KL4 3.4 25.7 Example 5 KL5 7.3 7.1 Example 6 KL6 4.2 26.5 Example 7 KL7 5.3 25.4 Example 8 KL8 7.3 27.0 Comparative Example 1 KM1 21.3 27.7 Comparative Example 2 KM2 3.3 26.7 Comparative Example 3 KM3 6.1 26.8 Comparative Example 4 KM4 6.5 29.5

[Inkjet Coating]

Inkjet coating was performed on the apparatus and conditions shown below.

Apparatus name: Hitachi plant technology company make, fine pattern coating device HIS-200-1H

Coating board: 100 * 100mm ITO board

Coating area: 30 X 40mm

Coating conditions: Resolution 25 micrometers, stage speed 50mm / sec, frequency 1000Hz, pulse width 9.6microsec, droplet amount 42pl, pitch width 70.5micrometer, pitch length 125micrometer, applied voltage: 14-19V (film thickness 100nm) Nozzle gap 0.5 mm, leveling time 30 sec, drying temperature 60 ° C., drying time 2 min (hot plate)

[Applicability]

The obtained film was observed by visual observation and a microscope, and applicability was confirmed.

Membrane formationability: The thing which turned into a film | membrane without defect was made into (circle), and the other thing was made into x.

In-plane uniformity: The thing which (circle) and irregular surface nonuniformity and linear nonuniformity generate | occur | produced that the film was uniform in surface was made into x.

Edge straightness: The thing with very good straightness and (circle) and the thing lacking straightness were made into x.

LCD
Alignment agent
Film formation
Gabu
Applicability
In-plane uniformity Edge straightness Example 1 KL1 Example 2 KL2 Example 3 KL3 Example 4 KL4 Example 5 KL5 Example 6 KL6 Example 7 KL7 Example 8 KL8 Comparative Example 1 KM1 × - - Comparative Example 2 KM2 × × Comparative Example 3 KM3 × Comparative Example 4 KM4 ×

From Table 4, film formation was impossible in Comparative Example 1 and Comparative Example 4, and Examples 1 to 8 had better in-plane uniformity and edge straightness than Comparative Examples 2 and 3, and improved coating properties. I could see.

[Production of Liquid Crystal Cells]

After preparing two glass substrates with a transparent electrode on which the liquid crystal aligning film was formed, and spreading a spacer having a particle diameter of 6 μm on the liquid crystal aligning film surface of the other substrate, an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Then, the liquid crystal aligning film was stuck so that it might face, and it hardened after crimping | bonding, and produced the empty cell. After inject | pouring MLC-6608 (brand name) by Merck Corporation to this empty cell by the vacuum injection method, the injection hole was sealed with UV curable resin and the liquid crystal cell (element) was produced. At that time, in the Example, a coating film was formed by the method described in the above [Inkjet coating], dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and then calcined for 60 minutes in a hot air circulation clean oven at a temperature of 200 ° C. The liquid crystal aligning film of 80 nm of film thicknesses was used. In addition, in the comparative example, the liquid crystal aligning film of 100 nm of film thickness obtained by the method similar to Example was used except having used the spin coat method instead of inkjet coating.

[Liquid crystal orientation]

The liquid crystal cell produced by the above-mentioned [preparation of a liquid crystal cell] method was observed with the polarization microscope, and the orientation state of the liquid crystal was confirmed. When the uniform orientation state without a defect is shown in the whole liquid crystal cell, (circle) and the case where an orientation defect is seen by a part of liquid crystal cell, and it was not vertically aligned, it was set as x. The results are shown in Table 5.

[Contact angle]

3 microliters of pure waters were dripped at the liquid crystal aligning film, and the contact angle was measured using the automatic contact angle meter CA-Z type by Kyowa Interface Science Corporation. The results are shown in Table 5.

In Example, the film thickness 80 obtained by forming a coating film by the method described in the said [Inkjet coating], drying for 5 minutes on a hotplate of 80 degreeC, and baking for 60 minutes in a 200 degreeC hot-air circulation type clean oven was carried out. Nm liquid crystal aligning film was used. In addition, in the reference example, the liquid crystal aligning film of 100-nm-thick film obtained by the method similar to Example was used except having used the spin coat method instead of inkjet coating.

Alignment agent Application method Liquid crystal alignment Contact angle of water / ° Example KL1 Inkjet Coating 89 Reference Example KL1 Spin coat method 87

From Table 5, it turned out that even the liquid crystal aligning film obtained by the inkjet coating method shows the vertical alignment property equivalent to the film obtained by the other coating method.

Industrial availability

Since the liquid crystal aligning film obtained by the liquid crystal aligning agent for inkjet coating of this invention is excellent in in-plane uniformity of a film and the edge straightness of a film edge part, the liquid crystal display element using this is used suitably as a highly reliable liquid crystal display device.

Also, the entire contents of the specifications, claims, and summaries of Japanese Patent Application No. 2008-329123, filed December 25, 2008 and Japanese Patent Application No. 2009-001359, filed January 7, 2009, are hereby incorporated by reference. It quotes and takes in as an indication of the specification of this invention.

Claims (14)

  1. Containing a polysiloxane (A) having a side chain composed of a hydrocarbon group having 8 to 30 carbon atoms substituted or unsubstituted with a fluorine atom, a glycol solvent having 2 to 7 carbon atoms (B), the following solvent (C) and a solvent (D) The liquid crystal aligning agent for inkjet coating characterized by the above-mentioned.
    Solvent (C): solvent represented by formula (A1),
    K 1 O (CH 2 ) w OH (A1)
    (In formula, K <1> is a C1-C4 alkyl group and w is an integer of 1-3.)
    Solvent (D): It consists of at least 1 sort (s) of compound chosen from the group which consists of a formula (T1), a formula (T2), and a formula (T3), a ketone which has 3-6 carbon atoms, and a C5-C12 alkyl alcohol. Solvent selected from the group.
    [Formula 1]
    Figure pct00003

    (In formula, X <1> , X <3> and X <5> are a C1-C4 alkyl group, X <2> and X <6> are a hydrogen atom or a C1-C4 alkyl group, X <4> is a C1-C4 alkyl group, P Is an alkyl group having 1 to 3 carbon atoms, m, n, j, k are each independently an integer of 1 to 3, and h is an integer of 2 to 3)
  2. The method of claim 1,
    The liquid crystal aligning agent for inkjet coating whose solvent (D) is a solvent chosen from the compound of formula (T3), the ketone which has 3-6 carbon atoms, and the C5-C12 alkyl alcohol in Formula (T1).
  3. The method according to claim 1 or 2,
    The liquid crystal aligning agent for inkjet coating whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1).
    R 1 Si (OR 2 ) 3 (1)
    (R 1 is a C8-30 hydrocarbon group having a substituted or unsubstituted fluorine atom, and R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.)
  4. The method of claim 3, wherein
    The liquid crystal aligning agent for inkjet coating whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by following formula (2).
    (R 3 ) n Si (OR 4 ) 4-n (2)
    (R 3 is a hydrogen atom, a halogen atom, a vinyl group or a hydrocarbon group having 1 to 7 carbon atoms, wherein any hydrogen atom of the hydrocarbon group is a glycidoxy group, a mercapto group, a methacryloxy group, an acryloxy group May be substituted with an isocyanate group, an amino group or a ureido group, or may have a hetero atom, R 4 is a hydrocarbon group of 1 to 5 carbon atoms, n represents an integer of 0 to 3)
  5. The method according to claim 3 or 4,
    The liquid crystal aligning agent for inkjet coating whose polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by following formula (3).
    Si (OR 4 ) 4 (3)
    (R 4 represents a hydrocarbon group having 1 to 5 carbon atoms)
  6. 6. The method according to any one of claims 1 to 5,
    Glycol solvent (B) is ethylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol , 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1,2-heptanediol, 2,3-heptanediol, 3,4-heptanediol, 1,3-heptanediol, 2 , 4-heptane diol, 3,5-heptane diol, 1,4-heptane diol, 2,5-heptane diol, 1,5-heptane diol, 2,6-heptane diol, 1,6-heptane diol and 1, Liquid crystal aligning agent for inkjet coatings which is 1 or more types of solvent chosen from the group which consists of 7-heptane diol.
  7. The method according to any one of claims 1 to 6,
    Liquid crystal aligning agent for inkjet coating whose X <2> in the said Formula (T1) is a hydrogen atom.
  8. The method according to any one of claims 1 to 7,
    The polysiloxane (A) is about a silicon atom having on 100 parts by mass of the total of the values in terms of SiO 2, glycol solvent (B) from 20 to 18,000 parts by weight, the solvent (C) from 2 to 17,500 parts by weight, the solvent (D ) Is a liquid crystal aligning agent for inkjet coating wherein 2 to 17,500 parts by mass.
  9. The method according to any one of claims 1 to 8,
    The polysiloxane (A) is about a silicon atom having on 100 parts by mass of the total of the values in terms of SiO 2, glycol solvent (B) is 120 ~ 17,000 parts by weight, the solvent (C) from 2 to 16,800 parts by weight, the solvent (D ) Liquid crystal aligning agent for inkjet coating whose 2-16,800 mass parts.
  10. The method according to any one of claims 1 to 9,
    The liquid crystal aligning agent for inkjet coating whose viscosity of the said aligning agent is 1.8-18 mPa * s.
  11. The method according to any one of claims 1 to 10,
    The liquid crystal aligning agent for inkjet coating whose surface tension of the said aligning agent is 20-40 mN / m.
  12. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent for inkjet coating of any one of Claims 1-11 to a board | substrate using an inkjet apparatus, and baking it.
  13. The formation method of the liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent for inkjet coating of any one of Claims 1-11 to a board | substrate using an inkjet apparatus, and baking it.
  14. The liquid crystal display element which has a liquid crystal aligning film of Claim 12.
KR1020117017292A 2008-12-25 2009-12-25 Liquid-crystal alignment material for ink-jet coating, liquid-crystal alignment film, and liquid-crystal display element KR101708949B1 (en)

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JP6107661B2 (en) * 2011-11-17 2017-04-05 日産化学工業株式会社 Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP6146135B2 (en) * 2012-08-30 2017-06-14 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display element
WO2014054748A1 (en) * 2012-10-03 2014-04-10 日産化学工業株式会社 Application liquid capable of fine application, for forming inorganic oxide coating film, and method for manufacturing fine inorganic oxide coating film
TWI636973B (en) * 2012-10-05 2018-10-01 日商日產化學工業股份有限公司 Method for manufacturing substrate having liquid crystal alignment film for transverse electric field drive type liquid crystal display element
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