KR102082525B1 - Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(Y¹, Y², Y³ 은 단결합 등, Y⁴, Y⁵ 는 벤젠 고리 등, Y⁶ 은 수소 원자 등, n 은 0 ∼ 4 의 정수)
R³Si(OR⁴)₃ (3)
(R³ 은 아크릴기 등, R⁴ 는 탄소수 1 ∼ 5 의 알킬기 등)Even in a liquid crystal display device having a liquid crystal containing no polymerizable compound and treated in the same manner as the PSA method to improve the response speed after UV irradiation, the response speed after UV irradiation can be improved without lowering the vertical alignment force. The liquid crystal aligning agent which can form the liquid crystal aligning film which exists, and a liquid crystal aligning film, and a liquid crystal display element are provided.
The liquid crystal aligning agent containing the polysiloxane (A) obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)
[Formula 1]

(Y ¹ , Y ² , Y ³ are single bonds, Y ⁴ , Y ⁵ are benzene rings, Y ⁶ is a hydrogen atom, n is an integer of 0 to 4)
R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an acryl group, R ⁴ is an alkyl group having 1 to 5 carbon atoms.)

Description

Silicon-based liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {SILICON-BASED LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL Display ELEMENT}

This invention relates to the liquid crystal aligning agent containing the polysiloxane obtained by hydrolyzing and polycondensing an alkoxysilane, the liquid crystal aligning film obtained from the said liquid crystal aligning agent, and the liquid crystal display element which has this liquid crystal aligning film.

In recent years, the vertical (VA) type liquid crystal display element is widely used among the display system of a liquid crystal display element, such as a big screen liquid crystal television and high-precision mobile use (display part of a digital camera or a mobile telephone). In the VA method, an MVA method (Multi Vertical Alignment) in which projections for controlling the direction of falling down of a liquid crystal are formed on a TFT substrate or a color filter substrate, or a direction in which the liquid crystal falls by an electric field by forming slits on an ITO electrode of the substrate. A PVA (Patterned Vertical Alignment) method for controlling is known. Another alignment method is PSA (Polymer sustained Alignment) method. Among the VA methods, the PSA method is a technology that is recently attracting attention. This system adds a photopolymerizable compound to a liquid crystal, and after manufacture of a liquid crystal panel, UV is irradiated to a liquid crystal panel in the state which applied an electric field and the liquid crystal fell. As a result, the orientation direction of a liquid crystal is fixed by photopolymerization of a polymeric compound, pretilt generate | occur | produces, and a response speed improves. A slit is manufactured on the electrode on one side constituting the liquid crystal panel, and the electrode pattern on the opposite side can be operated even in a structure without forming a protrusion such as MVA or a slit such as PVA, thereby simplifying manufacturing and obtaining excellent panel transmittance. (Refer patent document 1).

However, in the liquid crystal display element of this system, there exists a problem that the solubility of the polymeric compound added to a liquid crystal is low, and when it increases the addition amount, it will precipitate at low temperature. On the other hand, when the addition amount of a polymeric compound is reduced, a favorable orientation state and a response speed will no longer be obtained. Moreover, there exists also a problem that the unreacted polymeric compound which remains in a liquid crystal becomes an impurity in a liquid crystal, and reduces the reliability of a liquid crystal display element.

Then, the liquid crystal aligning agent using the polymer which introduce | transduced the photoreactive side chain in the polymer molecule was apply | coated to a board | substrate, the liquid crystal layer made to contact the liquid crystal aligning film obtained by baking, was formed, and an ultraviolet-ray was irradiated, applying a voltage to this liquid crystal layer. By manufacturing a liquid crystal display element, the technique which can obtain the liquid crystal display element with a quick response speed without adding a polymeric compound in a liquid crystal is proposed (refer patent document 2).

On the other hand, an inorganic liquid crystal aligning film material is also known with organic liquid crystal aligning film materials, such as polyimide conventionally used. For example, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid is proposed as a material of the coating type inorganic alignment film, and the vertical alignment, heat resistance, and uniformity on the electrode substrate of the liquid crystal display device are proposed. Formation of the liquid crystal aligning film excellent in the property is reported (refer patent document 3).

Japanese Unexamined Patent Publication No. 2004-302061 Japanese Unexamined Patent Publication No. 2011-95697 Japanese Patent Application Laid-Open No. 09-281502

In the VA mode for vertical alignment, strong vertical alignment force is required for vertical alignment, but in this method without using a polymerizable compound, when the vertical alignment force is improved, the response speed after UV irradiation becomes slow, and the response speed after UV irradiation Improving the lowering of the vertical alignment force. Vertical alignment force and response speed improvement after UV irradiation are in a trade off relationship.

The problem of the present invention is that, even in a liquid crystal display device having a method of improving the response speed after UV irradiation by using a liquid crystal containing no polymerizable compound and treating in the same manner as the PSA method, the UV is not lowered in the vertical alignment force. It is providing the liquid crystal display element which has the liquid crystal aligning agent which can form the liquid crystal aligning film which can improve the response speed after irradiation, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

This invention makes the following a summary.

[1] A liquid crystal aligning agent containing the following polysiloxane (A).

Polysiloxane (A): Polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3).

R ¹ Si (OR ² ) ₃ (1)

(R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

[Formula 1]

(Formula (2) of, Y ¹ represents a single bond, - (CH _{2) a} -. (A is an integer of 1 to 15), is -O-, -CH ₂ O-, -COO- or OCO-. and (b is an integer of ^{1 ~ 15, R 17, -} Y 2 is a single bond, a carbon number of the divalent hydrocarbon groups of 3 to 8 linear or branched in the, or (CR ¹⁷ R ¹⁸⁾ _b which contains a double bond R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, is -CH ₂ O-, -COO- or OCO-. Y ⁴ has a carbon number of 12-25 with a bivalent cyclic group, or steroid skeleton is selected from the group consisting of a benzene ring, a cyclohexyl ring, and the heterocyclic ring 2 A valent organic group is represented, and arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, And fire Is optionally substituted by is selected from the atoms comprising the group. Y ⁵ is a benzene ring, a cyclohexyl ring, a divalent cyclic group selected from the group consisting of heterocyclic, any of the hydrogen atoms on these cyclic groups, having 1 to of 3 alkyl groups, 1 to 3 carbon atoms in the alkoxy group, the number of carbon atoms or may be substituted by 1 to 3 fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom having 1 to 3. n is an integer of 0 ~ 4. Y ⁶ is A hydrogen atom, a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group.)

R ³ Si (OR ⁴ ) ₃ (3)

(R ³ is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, acryloxy group, methacryl group, methacryloxy group, or styryl group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)

[2] Furthermore, the liquid crystal aligning agent as described in said [1] containing polysiloxane (B).

Polysiloxane (B): Polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing 50-100 mol% of the alkoxysilane represented by Formula (5).

Si (OR ¹⁵ ) ₄ (5)

(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)

[3] The liquid crystal aligning agent according to the above [2], wherein the polysiloxane (B) is a polysiloxane obtained by further hydrolyzing and polycondensing an alkoxysilane containing an alkoxysilane represented by formula (3).

[4] The liquid crystal aligning agent according to the above [2] or [3], wherein the polysiloxane (B) is a polysiloxane obtained by further hydrolyzing and polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (6).

R ¹⁶ Si (OR ¹⁷ ) ₃ (6)

(R ¹⁶ is an alkyl group having 1 to 5 carbon atoms. R ¹⁷ represents an alkyl group having 1 to 5 carbon atoms.)

[5] The above [2] to [5], wherein at least one of polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by further hydrolyzing and polycondensing an alkoxysilane containing an alkoxysilane represented by the following formula (4). The liquid crystal aligning agent in any one of 4].

(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)

(In formula (4), R <^13> is a C1-C10 hydrocarbon group which may be substituted by the hydrogen atom, the hetero atom, the halogen atom, the amino group, the glycidoxy group, the mercapto group, the isocyanate group, and the ureide group. ¹⁴ is a C1-C5 alkyl group, n represents the integer of 0-3.)

[6] The alkoxysilane represented by the formula (1) contains 2 to 20 mol% of all alkoxysilanes used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) is a polysiloxane (A). The liquid crystal aligning agent in any one of said [1]-[5] contained in 5-70 mol% of all the alkoxysilanes used for the.

[7] The liquid crystal aligning agent according to any one of [1] to [6], in which the solvent is further contained, and the content of all polysiloxanes is 0.5 to 15% by weight in terms of SiO ₂ .

[8] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of the above [1] to [7] to a substrate, drying and baking.

[9] A liquid crystal display device having the liquid crystal alignment film according to the above [8].

[10] A liquid crystal display device wherein the liquid crystal aligning agent according to any one of [1] to [7] is coated and UV is irradiated in a state where voltage is applied to a liquid crystal cell in which a liquid crystal is sandwiched between two baked substrates. .

[11] Production of a liquid crystal display device wherein the liquid crystal aligning agent according to any one of the above [1] to [7] is applied, the liquid crystal is sandwiched between two baked substrates, and UV is irradiated in a state where a voltage is applied. Way.

ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent which can improve the response speed after UV irradiation, without reducing a vertical alignment force by irradiating UV like a PSA system using the liquid crystal which does not add a polymeric compound, the liquid crystal The liquid crystal aligning film obtained from an aligning agent, and the liquid crystal display element which has this liquid crystal aligning film can be provided.

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

This invention is invention regarding the liquid crystal aligning agent containing the following polysiloxane (A).

Polysiloxane (A): Polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3).

R ¹ Si (OR ² ) ₃ (1)

(R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

[Formula 2]

R ³ Si (OR ⁴ ) ₃ (3)

(R ³ is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, acryloxy group, methacryl group, methacryloxy group, or styryl group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)

Moreover, this invention is invention about the liquid crystal aligning agent containing polysiloxane (A) and the following polysiloxane (B).

Polysiloxane (B): Polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing 50-100 mol% of the alkoxysilane represented by Formula (5).

Si (OR ¹⁵ ) ₄ (5)

(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)

<Polysiloxane (A)>

The polysiloxane (A) contained in the liquid crystal aligning agent of this invention is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3).

R ¹ Si (OR ² ) ₃ (1)

(R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

[Formula 3]

R ³ Si (OR ⁴ ) ₃ (3)

(R ³ is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, acryloxy group, methacryl group, methacryloxy group or styryl group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)

R ¹ (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by Formula (1) represents a structure represented by Formula (2).

Formula (2) of, Y ¹ represents a single bond, - to any one of (a is an integer of 1 ~ 15.), -O-, -CH 2 O-, -COO- or OCO- - (CH _{2) a} . Among them, Y ¹ is a single bond, - (CH _{2) a} - The selection of which of the (. A is an integer of 1-15), -O-, -CH ₂ O- or COO-, side chain structure It is preferable from the viewpoint of facilitating the synthesis. And Y ¹ is more preferably selected from a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O- or COO-. Y ¹ represents a single bond, or _{(CH 2) a - (.} A is an integer of 1 to 10) which is especially preferred.

A (b is 1 to 15 formula (2) of, Y ² is a single bond, 2 of 3 to 8 carbon atoms linear or branched of containing a double bond, divalent hydrocarbon group, or (CR ¹⁷ R ¹⁸⁾ _b It is an integer and R <^17> , R <^18> represents a hydrogen atom or a C1-C3 alkyl group each independently.)

to be. Among them, Y ² is the viewpoint of remarkably improved than the response speed of the liquid crystal display _{element, - (CH 2) b -} (. B is an integer of 1 to 10) are preferred. It is preferable that Y <^2> is a single bond.

Formula (2) of, Y ³ represents a single bond, - to any one of (c is an integer of 1 ~ 15.), -O-, -CH 2 O-, -COO- or OCO- - (CH _{2) c} . Among them, Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- to select any It is preferable from the viewpoint of facilitating the synthesis of the side chain structure. And Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or OCO- is selected more desirable. It is particularly preferable that Y ³ is a single bond or O-.

In formula (2), Y <^4> is bivalent cyclic group chosen from the group which consists of a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group and carbon number It may be substituted by either a 1-3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. In addition, Y ⁴ may be a divalent organic group selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. Among these, Y ⁴ is preferably an organic group having 12 to 25 carbon atoms having any of a benzene ring, a cyclohexyl ring, or a steroid skeleton. It is especially preferable that Y ⁴ is a divalent cyclic group consisting of a benzene ring.

In formula (2), Y <^5> is a bivalent cyclic group chosen from the group which consists of a benzene ring, a cyclohexyl ring, and a heterocyclic ring, The arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, C1-C1 It may be substituted by any of the alkoxy group of -3, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, or a fluorine atom. It is especially preferable that Y ⁵ is a divalent cyclic group consisting of a cyclohexyl ring.

In formula (2), n is an integer of 0-4. Preferably, it is an integer of 0-2 and it is especially preferable that it is 1.

In formula (2), Y <^6> is either a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group. Especially, it is preferable that Y <^6> is either a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C10 fluorine-containing alkoxy group. Y ⁶ is more preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Y ⁶ is more preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms. It is especially preferable that Y <^6> is a C1-C9 alkyl group.

R <^2> of the alkoxysilane represented by Formula (1) is C1-C5, Preferably it is an alkyl group of 1-3. More preferably, R ² is a methyl group or an ethyl group.

The alkoxysilane represented by such a formula (1) can be synthesize | combined by a well-known synthetic | combination method (Unexamined-Japanese-Patent No. 61-286393). Although the specific example is given to the following, it is not limited to this.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

(Formula [1-19] - formula [1-21] of, R ⁵ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 - or represents a CH ₂ OCO-, R ⁶ is a carbon atoms It is an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group of 1-22.)

[Formula 10]

(Formula [1-22] - formula [1-24] of, R ⁷ represents a single _{bond, -COO-, -OCO-, -COOCH 2 -} , -CH 2 OCO-, - (CH 2) n O- ( n is an integer of 1 ~ 5), -OCH ₂ - or CH ₂ - represents a, R ⁸ is an alkoxy group containing an alkyl group, an alkoxy group, fluorine-containing alkyl group or fluorine group having a carbon number of 1 to 22).

[Formula 11]

(Formula [1-25] and formula [1-26] of, R ⁹ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ -or O-, and R ¹⁰ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.)

[Formula 12]

(In formula [1-27] and formula [1-28], R <^11> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.)

[Formula 13]

(In formula [1-29] and formula [1-30], R <^12> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.)

[Formula 14]

(Formula [1-31] of, B ₄ is an alkyl group having 3 to 20 carbon atoms that may be substituted by fluorine atoms, B ₃ is 1,4-cyclohexyl, and xylene group or 1,4-phenylene group, B ₂ is oxygen Atom or COO- * (wherein a bond with "*" is bonded to B ₃ ) and B ₁ is an oxygen atom or COO- * (with bond (* ₂ ) is (CH ₂ ) a ₂ )). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

The said compound is one type, or two or more types according to the property, such as the solubility with respect to the solvent when it is set as a siloxane polymer, the orientation property of the liquid crystal, the pretilt angle characteristic, the voltage retention, the accumulation charge, etc. when it is set as a liquid crystal aligning film. It can also be mixed and used. Moreover, combined use with the alkoxysilane containing a C10-18 long-chain alkyl group is also possible.

The alkoxysilane represented by Formula (1) which has the specific organic group mentioned above can be manufactured by a well-known method.

In the alkoxysilane represented by Formula (1) which has the specific organic group mentioned above, in all the alkoxysilanes used in order to obtain polysiloxane, 2 mol% or more is preferable in order to acquire favorable liquid-crystal orientation. The alkoxysilane represented by Formula (1), More preferably, it is 3 mol% or more. Moreover, in order for the alkoxysilane represented by Formula (1) to acquire sufficient hardening characteristic of the liquid crystal aligning film formed, 20 mol% or less is preferable. More preferably, it is 15 mol% or less.

R <^3> of the alkoxysilane represented by Formula (3) is a C1-C5 alkyl group, Preferably it is C1-C3, Especially preferably, it is C1-C2.

In the alkoxysilane represented by Formula (3), in all the alkoxysilanes used in order to obtain polysiloxane, 5 mol% or more is preferable in order to acquire favorable liquid crystal response speed. The alkoxysilane represented by the formula (3) is more preferably 10 mol% or more, more preferably 20 mol% or more, but 70 mol% or less is preferable, and 50 mol% or less is more preferable.

In addition to the alkoxysilane represented by Formula (1) and Formula (3), the manufacture of polysiloxane (A) aims at the adhesiveness with a board | substrate, the improvement of affinity with a liquid crystal molecule, etc., unless the effect of this invention is impaired. And the alkoxysilane represented by following formula (4) can also be used 1 type or multiple types. Since the alkoxysilane represented by Formula (4) can provide various characteristics to polysiloxane, 1 type or multiple types can be selected and used according to a required characteristic.

(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)

(In formula (4), R <^13> is a C1-C10 hydrocarbon group which may be substituted by the hydrogen atom, the hetero atom, the halogen atom, the amino group, the glycidoxy group, the mercapto group, the isocyanate group, and the uraid group. R <^14> is C1-C5, Preferably it is an alkyl group of 1-3. N is 0-3, Preferably the integer of 0-2 is represented.)

R ¹³ of the alkoxysilane represented by the formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group). Examples of the third organic group include aliphatic hydrocarbons; Ring structures such as aliphatic rings, aromatic rings and hetero rings; Unsaturated bonds; And an organic group having 1 to 6 carbon atoms that may contain a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, or the like and may have a branched structure. In addition, the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureide group, or the like.

Although the specific example of the alkoxysilane represented by such Formula (4) is given, it is not limited to this. For example, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2- Aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxy Silane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, di Phenyldimethoxysilane, Diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethyl ethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-uradepropyltriethoxysilane, γ -Uraid profile Methoxy, and the like silane and γ- ureido propyltriethoxysilane propoxysilane.

In the alkoxysilane represented by Formula (4), the alkoxysilane whose n is 0 is tetraalkoxysilane. Since tetraalkoxysilane is easy to condensate with the alkoxysilane represented by Formula (1) and (3), it is preferable in order to obtain the polysiloxane of this invention.

In such formula (4), as alkoxysilane where n is 0, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and especially tetramethoxysilane or tetra Preferred are oxysilanes.

In the present invention, the alkoxysilane represented by the formula (1) is preferably 2 to 20 mol%, particularly preferably 3 to 15 mol%, in all the alkoxysilanes used for the production of the polysiloxane (A), and It is preferable that the alkoxysilane represented by Formula (3) contains 5-70 mol%, Most preferably, 10-50 mol% in all the alkoxysilanes used for manufacture of polysiloxane (A).

<Polysiloxane (B)>

Polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing 50-100 mol% of the alkoxysilane represented by Formula (5).

Si (OR ¹⁵ ) ₄ (5)

(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)

As a specific example of the alkoxysilane represented by such Formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, In particular, tetramethoxysilane or tetraethoxy Silanes are preferred.

In addition to the alkoxysilane represented by Formula (5), polysiloxane (B) may be polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (3).

In addition to the alkoxysilane represented by Formula (5), polysiloxane (B) may be polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (6) further.

R ¹⁶ Si (OR ¹⁷ ) ₃ (6)

(R ¹⁶ is an alkyl group having 1 to 5 carbon atoms. R ¹⁷ represents an alkyl group having 1 to 5 carbon atoms.)

R <^16> of the alkoxysilane represented by Formula (6) is a C1-C5 alkyl group. As for carbon number of an alkyl group, 1-4 are preferable, More preferably, it is 1-3.

R <^17> of the alkoxysilane represented by Formula (6) is a C1-C5 alkyl group, Preferably it is C1-C3, Especially preferably, it is C1-C2.

Although the specific example of the alkoxysilane represented by Formula (6) is given, it is not limited to these. For example, they are methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane.

In particular, in addition to the alkoxysilane represented by Formula (5), the liquid crystal aligning agent containing the polysiloxane (B) obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (6) has a perpendicular alignment force. High is preferable.

In order to improve the response speed of a liquid crystal display element by UV-irradiating, applying a voltage using the liquid crystal to which a polymeric compound is not added, the alkoxysilane represented by Formula (3) which has a 2nd specific organic group acquires polysiloxane. In all the alkoxysilanes used for these, 10 mol% or more is preferable. More preferably, it is 20 mol% or more. More preferably, it is 30 mol% or more. Moreover, in order to fully harden the liquid crystal aligning film formed, 75 mol% or less is preferable.

In addition to the alkoxysilane represented by Formula (3), Formula (5), and Formula (6), manufacture of polysiloxane (B) aims at improving adhesiveness with a board | substrate, affinity with a liquid crystal molecule, etc. As long as an effect is not impaired, the alkoxysilane represented by the said Formula (4) can also be used 1 type or multiple types. Since the alkoxysilane represented by Formula (4) can provide various characteristics to polysiloxane, 1 type or multiple types can be selected and used according to a required characteristic.

When manufacturing the liquid crystal aligning agent which mixed polysiloxane (A) and polysiloxane (B), about the mixing ratio of polysiloxane (A) and polysiloxane (B), the weight ratio of (A) and (B) is 10 in conversion of the same solid content. : It is preferable that it is 90-50: 50.

<Method for producing polysiloxane>

The method of obtaining the polysiloxane used for this invention is not specifically limited. In polysiloxane (A) of this invention, it is obtained by condensing the alkoxysilane which makes said formula (1) and formula (3) an essential component in an organic solvent. Usually, polysiloxane is obtained as a solution which hydrolyzed and polycondensed such an alkoxysilane and melt | dissolved uniformly in the organic solvent.

As a method of hydrolyzing and polycondensing polysiloxane, the method of hydrolyzing and polycondensation of an alkoxysilane in solvent, such as alcohol or glycol, is mentioned, for example. In that case, any of partial hydrolysis and complete hydrolysis may be sufficient as a hydrolysis and polycondensation 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 it is preferable to add excess water more than 0.5 times mole normally.

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

In addition, acids, such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid and fumaric acid, for the purpose of promoting hydrolysis and polycondensation reactions; Alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine; Metal salts of acids such as hydrochloric acid, sulfuric acid and nitric acid; Catalysts are used. In addition, it is also common to promote the hydrolysis / polycondensation 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 hydrolyzing 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 the alkoxysilane is mixed while the solution is heated. In that case, it is preferable that the quantity of the oxalic acid to be used shall be 0.2-2 mol with respect to 1 mol of all the alkoxy groups which an alkoxysilane has. Heating in this method can be performed at liquid temperature of 50-180 degreeC. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation, volatilization, etc. of a liquid do not occur.

When obtaining a polysiloxane, when using multiple types of alkoxysilanes, it may mix as a mixture which mixed the alkoxysilane previously, and may mix several types of alkoxysilanes sequentially.

The solvent (henceforth a polymerization solvent) used when hydrolyzing and 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 hydrolysis and polycondensation reaction of an alkoxysilane, even if an alkoxysilane does not melt | dissolve. Generally, since alcohol is produced | generated by the hydrolysis and polycondensation reaction of an alkoxysilane, the organic solvent with favorable compatibility with alcohol, glycol, glycol ether, or alcohol is used.

Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5- Glycols such as pentanediol, 2,4-pentanediol, 2,3-pentanediol and 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, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, die Ethylene 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 ether, Glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N- Dimethylacetamide, gamma -butyrolactone, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.

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

The polymerization solution (hereinafter also referred to as polymerization solution) of the polysiloxane obtained by the above method is preferably a concentration (hereinafter referred to as SiO ₂ conversion concentration) in which silicon atoms of all the alkoxysilanes injected as raw materials are converted into SiO ₂ . Preferably it is 20 weight% or less, Furthermore, it is more preferable to set it as 5-15 weight%. By selecting an arbitrary concentration in this concentration range, formation of a gel can be suppressed to obtain a homogeneous solution.

<Solution of polysiloxane>

In the present invention, the polymerization solution obtained by the above method may be used as a solution of polysiloxane as it is, and if necessary, the solution obtained by the above method is concentrated, diluted with the addition of a solvent, or substituted with another solvent, You may make it the solution of polysiloxane.

In that case, the solvent (henceforth an addition solvent) to be used may be the same as a polymerization solvent, and may be another solvent. This addition solvent is not specifically limited as long as polysiloxane is melt | dissolving uniformly, One type or multiple types can also be arbitrarily selected and used.

As a specific example of such an addition solvent, Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, in addition to the solvent mentioned as an example of the said polymerization solvent; Ester, such as methyl acetate, ethyl acetate, and an ethyl lactate, is mentioned.

These solvents can improve the applicability | paintability at the time of apply | coating a liquid crystal aligning agent on a board | substrate by adjustment of the viscosity of a liquid crystal aligning agent, or spin coating, flexographic printing, an inkjet, etc.

<Other components>

In the present invention, other components other than polysiloxane, such as inorganic fine particles, metal oxane oligomers, metal oxane polymers, leveling agents, and surfactants, are contained unless the effect of the present invention is impaired. You may be.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and in particular, the fine particles are preferably in a colloidal solution state. This colloidal solution may disperse | distribute an inorganic fine particle in a dispersion medium, and may be a colloidal solution of a commercial item. In this invention, by containing an inorganic fine particle, the surface shape and other function of the cured film formed can be provided. As the inorganic fine particles, the average particle diameter is preferably 0.001 to 0.2 µm, more preferably 0.001 to 0.1 µm. 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 viewpoint of stability 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 alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and 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; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned. Among these, alcohols or ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

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

Examples of commercially available metal oxane oligomers and metal oxane 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 Colecott Corporation. Titanoic acid oligomers, such as a polymer and the titanium-n-butoxide tetramer made by Canto Chemical Company, are mentioned. You may use these individually or in mixture of 2 or more types.

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

Moreover, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with polysiloxane, may be after, and is not specifically limited.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a polysiloxane mentioned above and the solution containing another component as needed. In that case, the solvent chosen from the group which consists of the superposition | polymerization solvent and addition solvent of the polysiloxane mentioned above is used as a solvent. The content of polysiloxane in the liquid crystal aligning agent is, SiO ₂ in terms of the concentration is preferably 0.5 to 15% by weight, more preferably 1 to 6% by weight. In a range of concentration in terms of SiO _2, and easily obtain a desired film thickness by one time of coating, it is easy to obtain a sufficient pot life of the solution.

The method of preparing the liquid crystal aligning agent of this invention is not specifically limited. The polysiloxane used for this invention and the other component added as needed should just be a state mixed uniformly. Usually, since polysiloxane hydrolyzes and polycondenses in a solvent, it is easy to use the solution of polysiloxane as it is, or to add another component to the solution of polysiloxane as needed. Moreover, the method of using the polymerization solution of polysiloxane as it is is the simplest.

Moreover, when adjusting content of the polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent and addition solvent of the polysiloxane mentioned above can be used.

<Liquid crystal aligning film>

The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention.

For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, the cured film obtained by performing drying and baking can also be used as a liquid crystal aligning film as it is. The cured film may be rubbed, irradiated with polarized light or a light having a specific wavelength, treated with an ion beam or the like, or irradiated with UV light while a voltage is applied to the liquid crystal display element after liquid crystal charging.

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate which apply | coats a liquid crystal aligning agent, the board | substrate with a transparent electrode for driving a liquid crystal on a board | substrate is preferable.

Specific examples include glass plates, polycarbonates, poly (meth) acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyetherketones, trimethylpentene, polyolefins, polyethylene terephthalates, and (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.

As a coating method of a liquid crystal aligning agent, a spin coat method, the printing method, the inkjet method, the spray method, the roll coating method, etc. are mentioned, In terms of productivity, the transfer printing method is industrially widely used, and also in this invention It is preferably used.

Although the drying process after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not constant for every board | substrate, or when it does not bake immediately 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 degreeC-150 degreeC, Preferably 60 degreeC-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 to 350 degreeC, Preferably it is 140 to 300 degreeC, More preferably, it is 150 to 230 degreeC, More preferably, it is 160 to 220 degreeC ℃. Firing time can be baked in arbitrary time for 5 minutes-240 minutes. Preferably it is 10 to 90 minutes, More preferably, it is 20 to 80 minutes. The heating can usually use a well-known method, for example, a hot plate, a hot air circulation oven, an IR oven, a belt furnace, etc.

The polysiloxane in a liquid crystal aligning film advances polycondensation in a baking process. 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 heat processing temperature, such as sealing compound hardening, which is required in a liquid crystal cell manufacturing process.

Although the thickness of this cured film can be selected as needed, Preferably it is 5 nm or more, More preferably, since it is easy to acquire the reliability of a liquid crystal display element, it is preferable. Moreover, when the thickness of a cured film becomes like this. Preferably it is 300 nm or less, More preferably, since the power consumption of a liquid crystal display element does not become extremely large, it is preferable.

<Liquid crystal display element>

After the liquid crystal aligning film is formed in a board | substrate by said method, the liquid crystal display element of this invention can manufacture and obtain a liquid crystal cell by a well-known method. As an example of liquid crystal cell manufacture, the method of fixing a pair of board | substrates with which the liquid crystal aligning film was formed with a sealing agent through 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 of injecting the liquid crystal is not particularly limited, and the vacuum method of injecting the liquid crystal after the inside of the manufactured liquid crystal cell is reduced in pressure, the dropping method of sealing after dropping the liquid crystal, and the like.

By irradiating UV in the state which applied the voltage between the electrodes of both board | substrates of the liquid crystal cell in which the liquid crystal was introduce | transduced, crosslinkable groups, such as an acryl group and a methacryl group, in an alignment film are polymerized on the spot and bridge | crosslinked, the response speed of a liquid crystal display becomes Faster. The voltage to be applied here is AC 5 to 50 Vp-p or DC 5 to 30 V, but preferably 5 to 30 Vp-p or DC 5 to 20 V. The UV irradiation amount to be irradiated is from 1 to 60 J using a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, etc., but is preferably 40 J or less, and the smaller the UV irradiation amount is due to the destruction of the member constituting the liquid crystal display. It is preferable because the manufacturing tact rises by reducing the deterioration in reliability and reducing the UV irradiation time.

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 the transparent electrode for driving a liquid crystal on the board | substrate. The specific example is the same as that of the board | substrate described by [liquid crystal aligning film]. Electrode patterns or projection patterns such as standard PVA and MVA may also be used. Similar to the liquid crystal display of the PSA system, it is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 µm is formed on one side substrate, and a slit pattern and a projection pattern are not formed on the opposing substrate, and the liquid crystal display of this structure The process at the time of manufacture can be simplified and high transmittance | permeability can be obtained by this.

Moreover, in the high functional element like TFT type element, the thing in which the transistor element was formed between the electrode and board | substrate for liquid crystal drive is used.

In the case of a transmissive liquid crystal device, it is common to use a substrate as described above, but in a reflective liquid crystal display device, a material such as aluminum that reflects light only on one substrate may be used, and an opaque substrate such as a silicon wafer may also be used. Can be used

Example

Hereinafter, although an Example of this invention demonstrates more concretely, it is not limited to these and interpreted.

[Formula 15]

<Synthesis example 1 of compound 8>

Into a 500 ml four-necked flask equipped with a magnetic stirrer, 1.71 g of metal magnesium was injected, and the inside of the vessel was sealed by nitrogen substitution. After 2 ml of THF (dehydration) was added, a solution in which 20.68 g of Compound 7 was dissolved in 155 ml of THF (dehydration) was added dropwise over 1 hour while being strongly stirred. Then, it heated up at 55 degreeC, stirred for 2 hours, and confirmed that the metal magnesium was missing. Next, after addition of 30.53 g of tetramethoxysilane under ice-cooling (internal temperature of 4 degreeC), it heated and refluxed and stirred for 3 hours. After cooling the reaction solution to room temperature, 210 ml of saturated aqueous ammonium chloride solution was added, and the resulting insoluble matter was removed by filtration under reduced pressure. Then, the filtrate was washed with 260 ml of n-hexane. The aqueous phase of the filtrate was removed and the organic phase was washed with 200 ml of pure water. The organic phase was concentrated to dryness to give 21.65 g of crude. The mixture was distilled under reduced pressure, and the mixture was distilled off under conditions of an external temperature of 220 to 230 ° C / pressure of 0.8 torr to obtain 5.74 g of compound 8 (yield 25%).

[Formula 16]

<Synthesis example 2 of compound 10>

Into a 500 mL four-necked flask equipped with a magnetic stirrer, 30.00 g of compound 9, 25.24 g of potassium carbonate, and 120 g of DMF were injected, and 22.10 g of allyl bromide was added dropwise at room temperature. Then, it stirred at 50 degreeC for 11 hours. The reaction solution was diluted with 500 g of ethyl acetate and the organic phase was washed three times with 200 g of pure water. The organic phase was dried over sodium sulfate, and the filtrate was concentrated to dryness, and 34.80 g of compound 10 was obtained (yield 100%).

<Synthesis example 3 of compound 11>

Into a 300 ml four-necked flask equipped with a magnetic stirrer, 20.00 g of compound 10 and 120 g of toluene were injected and stirred at room temperature. Next, after adding 700 microliters of a karstedt catalyst (platinum (0) -1,1,3,3- tetramethyldisiloxane complex 0.1 mol / L xylene solution), 12.4 ml of trimethoxysilane was dripped. After stirring at room temperature for 29 hours, the reaction solution was concentrated to dryness to obtain a crude product. The mixture was distilled under reduced pressure, and the mixture was distilled off under conditions of an external temperature of 245 ° C / pressure of 0.8 torr to obtain 12.15 g of compound 11 (yield 43%).

Hereinafter, although an Example of this invention demonstrates more concretely, it is not limited to these and interpreted.

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

TEOS: tetraethoxysilane

C18: octadecyltriethoxysilane

MPMS: 3-methacryloxypropyltrimethoxysilane

M8MS: 3-methacryloxyoctyltrimethoxysilane

MTES: Methyltriethoxysilane

HG: 2-methyl-2,4-pentanediol (alias hexylene glycol)

BCS: 2-butoxyethanol

UPS: 3-Auraidpropyltriethoxysilane

<Example Synthesis Example 1>

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 20.5 g of HG, 6.8 g of BCS, 22.5 g of TEOS, and 4.1 g of Compound 11 obtained in Compound Synthesis Example 3 and 19.9 g of MPMS were mixed to give an alkoxysilane. A solution of monomers was prepared. The solution which mixed oxalic acid 1.3g as HG10.2g, BCS3.4g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and also stirred at room temperature for 30 minutes. After heating and refluxing for 30 minutes using an oil bath, the liquid mixture of 0.6 g of UPS content 92 weight% methanol solutions, 0.3 g of HG, and 0.1 g of BCS was added previously. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, and 20.0 g BCS to, SiO ₂ in terms of a concentration of 4 to obtain a first intermediate [S1]% by weight of the liquid crystal alignment.

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 23.8 g of HG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare a solution of an alkoxysilane monomer. The solution which mixed oxalic acid 0.4g as HG 11.9g, BCS4.0g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and also stirred at room temperature for 30 minutes. After heating and refluxing for 30 minutes using an oil bath, the liquid mixture of 0.6 g of UPS solutions 92 weight% methanol solution, 0.3 g of HG, and 0.1 g of BCS was added previously. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (U1).

A liquid crystal aligning agent intermediate (S1) and the liquid crystal aligning agent intermediate (U1) obtained 2 were mixed at a ratio of 8 parts by weight, SiO ₂ in terms of a concentration of 4 to obtain a first [K1]% by weight of the liquid crystal alignment.

<Example Synthesis Example 2>

In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, 17.9 g of HG, 6.0 g of BCS, 25.0 g of TEOS, and Compound 11 of compound 11 obtained in Synthesis Example 3 were mixed with 8.2 g and 19.1 g of M8MS. A solution of monomers was prepared. The solution which mixed oxalic acid 1.1g as HG 9.0g, BCS3.0g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and also stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath to reflux for 60 minutes, and then cooled to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight to obtain a liquid crystal aligning agent intermediate [S2].

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S2) of Synthetic Example 1, the obtained 2 were mixed in 8 parts by weight ratio of a, SiO ₂ in terms of concentration to obtain the [K2] of 4% by weight of the liquid crystal alignment.

<Example Synthesis Example 3>

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, Hg was 19.4 g, BCS 6.5 g, TEOS 22.5 g, 8.2 g of compound 11 obtained in Synthesis Example 3, 14.9 g of MPMS, and 3.2 g of M8MS. It mixed and prepared the solution of the alkoxysilane monomer. The solution which mixed oxalic acid 1.1g as HG 9.7g, BCS 3.2g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and also stirred at room temperature for 30 minutes. After heating and refluxing for 30 minutes using an oil bath, the liquid mixture of 0.6 g of UPS solutions 92 weight% methanol solution, 0.3 g of HG, and 0.1 g of BCS was added previously. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (S3).

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S3) as in Preparation Example 1. The resulting 2 were mixed in 8 parts by weight ratio of a, SiO ₂ in terms of a concentration of 4 to obtain a first [K3]% by weight of the liquid crystal alignment.

<Comparative Synthesis Example 1>

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 4.2 g of HG 22.6 g, BCS 7.5 g, TEOS 39.2 g, and C18 were mixed to prepare a solution of an alkoxysilane monomer. The 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 also stirred at room temperature for 30 minutes. After heating and refluxing for 30 minutes using an oil bath, the liquid mixture of 0.6 g of UPS solutions 92 weight% methanol solution, 0.3 g of HG, and 0.1 g of BCS was added previously. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (S4).

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S4) of Synthetic Example 1, the obtained 2 were mixed in 8 parts by weight ratio of a, SiO ₂ in terms of a concentration of 4 to obtain a first [L1]% by weight of the liquid crystal alignment.

<Comparative Synthesis Example 2>

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG 20.4 g, BCS 6.8 g, TEOS 22.5 g, and C18 4.2 g and MPMS 19.9 g were mixed to prepare a solution of an alkoxysilane monomer. The solution which mixed oxalic acid 1.3g as HG10.2g, BCS3.4g, water 10.8g, and a catalyst previously was dripped at this solution over 30 minutes under room temperature, and also stirred at room temperature for 30 minutes. After heating and refluxing for 30 minutes using an oil bath, the liquid mixture of 0.6 g of UPS solutions 92 weight% methanol solution, 0.3 g of HG, and 0.1 g of BCS was added previously. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal alignment was obtained the intermediate (S5).

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S5) of Synthetic Example 1, the obtained 2 were mixed in 8 parts by weight ratio of a, SiO ₂ in terms of concentration to obtain the [L2] of 4% by weight of the liquid crystal alignment.

<Example 1>

The liquid crystal aligning agent [K1] obtained by the synthesis example 1 was spin-coated to the ITO surface of the ITO electrode substrate in which the ITO electrode pattern whose pixel size is 100 x 300 microns and whose line / space is 5 microns, respectively is formed. After drying for 2 minutes with an 80 degreeC hotplate, baking was performed for 30 minutes by the 200 degreeC or 220 degreeC hot-air circulation type oven, and the liquid crystal aligning film with a film thickness of 100 nm was formed. After spin-coating the liquid-crystal aligning agent [K1] obtained by the synthesis example 1 to the ITO surface in which the electrode pattern is not formed, and drying it for 2 minutes with an 80 degreeC hotplate, it is 200 degreeC or 220 degreeC similarly to the said board | substrate. It baked for 30 minutes by the hot-air circulation type oven, and formed the liquid crystal aligning film of film thickness 100nm. These two board | substrates were prepared, after spread | dispersing a 4 micrometers bead spacer on the liquid crystal aligning film surface of one board | substrate, the sealing compound was printed from on. After attaching the liquid crystal aligning film surface of the other board | substrate inward, the sealing compound was hardened and the empty cell was manufactured. The liquid crystal cell which inject | poured the said liquid crystal into the empty cell by liquid crystal MLC-6608 (Merck & Co., Ltd. brand name) was carried out by the pressure reduction injection method.

The response speed characteristic of these liquid crystal cells was measured by the method of mentioning later.

Subsequently, in the state which applied the DC voltage of 20V to this liquid crystal cell, UV was irradiated 20J in 365 nm conversion using the ultrahigh pressure mercury lamp from the outside of this liquid crystal cell. Then, the response speed characteristic was measured again and the response speed before and behind UV irradiation was compared. The results are shown in Table 1.

Then, the obtained liquid crystal cell was annealed for 30 minutes in the circulating oven of 100 degreeC. The cell which carried out the microscope observation was performed in the state which made the polarizing plate the cross nicol, and the domain state in which the orientation of a liquid crystal is not uniform was observed. The results are also shown in Table 1.

<Example 2>

Except having changed the liquid crystal aligning agent [K1] into the liquid crystal aligning agent [K2] obtained by the Example synthesis example 2, the liquid crystal cell was produced like Example 1, a response speed is measured, and the orientation after annealing is not uniform. Domains were observed. The results are shown in Table 1.

<Example 3>

Except having changed the liquid crystal aligning agent [K1] into the liquid crystal aligning agent [K3] obtained by the Example synthesis example 3, the liquid crystal cell was produced like Example 1, a response speed is measured, and the orientation after annealing is not uniform. Domains were observed. The results are shown in Table 1.

<Comparative Example 1>

Except having changed the liquid crystal aligning agent [K1] into the liquid crystal aligning agent [L1] obtained by the comparative synthesis example 1, the liquid crystal cell was produced like Example 1, a response speed is measured, and the orientation after annealing is not uniform. Domains were observed. The results are shown in Table 1.

<Comparative Example 2>

Except having changed the liquid crystal aligning agent [K1] into the liquid crystal aligning agent [L2] obtained by the comparative synthesis example 2, the liquid crystal cell was produced like Example 1, a response speed is measured, and the orientation after annealing is not uniform. Domains were observed. The results are shown in Table 1.

[Response speed characteristic]

The time change of the luminance of the liquid crystal panel when an AC voltage of ± 5 V and a rectangular wave of frequency 1 Hz was applied to the liquid crystal cell was measured with an oscilloscope. When the voltage is not applied, a luminance of 0% and a voltage of ± 5 V are applied, the value of saturated luminance is set to 100%, and the time at which the luminance changes from 10% to 90% is used as the response speed of the rise. It was.

○ determination of response speed: fast (good) ×: slow (bad)

Domain observation after annealing

X: Many domains are observed

○: good

◎ very good

As can be seen from Table 1, in Example 1, the response speed after UV irradiation was fast, and even in the domain observation result after annealing, the result was good. On the other hand, in Comparative Example 1, the domain observation result after annealing was very good, but the response speed was slow. In the comparative example 2, although the response speed was fast, many domains were observed after annealing. Moreover, also in Examples 2 and 3, the response speed after UV irradiation was quick, and the very favorable result also showed in the domain observation result after annealing.

Industrial availability

The liquid crystal display element manufactured using the liquid crystal aligning agent of this invention uses the liquid crystal which does not add a polymeric compound, and also the liquid crystal display element of the system which processes in the same manner as a PSA system, and improves the response speed after UV irradiation. It provides the liquid crystal aligning agent which can form the liquid crystal aligning film which can improve the response speed after UV irradiation, without reducing a vertical alignment force, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element which has this liquid crystal aligning film. can do. Therefore, it is useful for the TFT liquid crystal display element, TN liquid crystal display element, VA liquid crystal display element manufactured by the said method.

In addition, the JP Patent application 2011-251377, the claim, and all the content of the abstract for which it applied on November 17, 2011 are referred here, and it takes in as an indication of the specification of this invention.

Claims (11)

The following polysiloxane (A) is contained and the following polysiloxane (B) is contained, The liquid crystal aligning agent characterized by the above-mentioned.
Polysiloxane (A): As a polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (3),
2-20 mol% is contained in the alkoxysilane represented by Formula (1) in all the alkoxysilanes used for polysiloxane (A), and the alkoxysilane represented by Formula (3) is all the alkoxy used for polysiloxane (A) Polysiloxane containing 5-70 mol% in silane.
R ¹ Si (OR ² ) ₃ (1)
(R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

(Formula (2) of, Y ¹ represents a single bond, - (CH _{2) a} -. (A is an integer of 1 to 15), is -O-, -CH ₂ O-, -COO- or OCO-. and (b is an integer of ^{1 ~ 15, R 17, -} Y 2 is a single bond, a carbon number of the divalent hydrocarbon groups of 3 to 8 linear or branched in the, or (CR ¹⁷ R ¹⁸⁾ _b which contains a double bond R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, is -CH ₂ O-, -COO- or OCO-. Y ⁴ has a carbon number of 12-25 with a bivalent cyclic group, or steroid skeleton is selected from the group consisting of a benzene ring, a cyclohexyl ring, and the heterocyclic ring 2 A valent organic group is represented, and arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxy group, And fire Is optionally substituted by is selected from the atoms comprising the group. Y ⁵ is a benzene ring, a cyclohexyl ring, a divalent cyclic group selected from the group consisting of heterocyclic, any of the hydrogen atoms on these cyclic groups, having 1 to of 3 alkyl groups, 1 to 3 carbon atoms in the alkoxy group, the number of carbon atoms or may be substituted by 1 to 3 fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom having 1 to 3. n is an integer of 0 ~ 4. Y ⁶ is A hydrogen atom, a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxy group, or a C1-C18 fluorine-containing alkoxy group.)
R ³ Si (OR ⁴ ) ₃ (3)
(R ³ is an alkyl group having 5 to 10 carbon atoms substituted with an acryl group, acryloxy group, methacryl group, methacryloxy group, or styryl group. R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)
Polysiloxane (B): Polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing 50-100 mol% of the alkoxysilane represented by Formula (5).
Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.) delete The method of claim 1,
The liquid crystal aligning agent whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (3). The method of claim 1,
The liquid crystal aligning agent whose polysiloxane (B) is polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (6).
R ¹⁶ Si (OR ¹⁷ ) ₃ (6)
(R ¹⁶ is an alkyl group having 1 to 5 carbon atoms. R ¹⁷ represents an alkyl group having 1 to 5 carbon atoms.) The method of claim 1,
At least one of polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by hydrolyzing and polycondensing the alkoxysilane containing the alkoxysilane represented by following formula (4) further.
(R ¹³ ) _n Si (OR ¹⁴ ) _4-n (4)
(In formula (4), R <^13> is a C1-C10 hydrocarbon group which may be substituted by the hydrogen atom, the hetero atom, the halogen atom, the amino group, the glycidoxy group, the mercapto group, the isocyanate group, or the ureide group. ¹⁴ is a C1-C5 alkyl group, n represents the integer of 0-3.) delete The method of claim 1,
In addition, the first containing the solvent, and further 0.5 to 15% by weight of the liquid crystal when the content of the total polysiloxane in terms of SiO _2. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of Claims 1, 3-5, and 7 to a board | substrate, drying, and baking. The liquid crystal display element which has a liquid crystal aligning film of Claim 8. UV in the state which apply | coated the liquid crystal aligning agent in any one of Claims 1, 3-5, and 7, and applied the voltage to the liquid crystal cell in which the liquid crystal was clamped between the two board | substrates which were baked. The liquid crystal display element which irradiated. The liquid crystal aligning agent of any one of Claims 1, 3-5, and 7 is apply | coated, the liquid crystal is clamped between two baked board | substrates, and UV irradiation is carried out in the state which applied the voltage. The manufacturing method of a liquid crystal display element.