KR101998906B1

KR101998906B1 - Method for manufacturing liquid-crystal display element for use with in-plane switching

Info

Publication number: KR101998906B1
Application number: KR1020147020123A
Authority: KR
Inventors: 아츠히코 만다이; 료이치 아시자와; 히로카즈 야마노우치; 사토시 미나미
Original assignee: 닛산 가가쿠 가부시키가이샤
Priority date: 2011-12-22
Filing date: 2012-12-21
Publication date: 2019-07-10
Also published as: KR20140107521A; CN104136976A; JPWO2013094734A1; TW201333604A; JP6274407B2; TWI476490B; WO2013094734A1

Abstract

A liquid crystal aligning agent is applied to a substrate to form a liquid crystal alignment film and subjected to alignment treatment. Thereafter, a pair of substrates having the liquid crystal alignment film formed thereon are disposed opposite to each other via a liquid crystal so that the liquid crystal alignment film is opposed, And irradiating the liquid crystal cell with light to cause a photo-polymerizable group in the liquid crystal and / or the liquid crystal alignment film to react with the liquid crystal cell.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a liquid crystal display device,

The present invention relates to a method of manufacturing a liquid crystal display element for driving a transverse electric field.

In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of the liquid crystal is usually formed in the element.

At present, in the most industrially popular method, this liquid crystal alignment film can be formed by laminating the surface of a polyamic acid film formed on an electrode substrate and / or a polyimide film imidized thereon with a cloth such as cotton, nylon, polyester, So-called rubbing treatment.

The rubbing treatment of the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method which is simple and excellent in productivity. However, the demand for higher performance, higher definition, and larger size of liquid crystal display elements is further increased, and the surface of the liquid crystal alignment film caused by the rubbing process is affected by scratches, oscillation, mechanical force or static electricity, Various problems such as nonuniformity are becoming clear.

As an alternative to the rubbing treatment, there is known a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized ultraviolet rays. The liquid crystal alignment treatment by the photo alignment method has been proposed by using a photoisomerization mechanism, a photo-dimerization mechanism, and a photo-decomposition reaction (see Non-Patent Document 1).

For example, in Patent Document 1, it has been proposed to use a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain for the photo alignment method. When a polyimide film using this photo alignment method is used for a liquid crystal alignment film, its usefulness is expected because it has higher heat resistance than the other.

Such a polyimide film having an alicyclic structure such as a cyclobutane ring exhibits high anisotropy by irradiating ultraviolet rays of a short wavelength, particularly polarized ultraviolet rays of about 254 nm, to obtain a liquid crystal alignment film excellent in liquid crystal alignability. However, since ultraviolet rays in the vicinity of 254 nm have high energy and require a large amount of power for irradiation, the cost for the photo-alignment treatment is large, and the load on the environment is large. In addition, since ultraviolet rays of a short wavelength having a stronger energy are used, there is a possibility that damage may be given to electrodes and thin film transistors (hereinafter also referred to as TFTs) formed on the substrate.

On the other hand, an optical anisotropy using photoisomerization or photo-dimerization can impart anisotropy by irradiating polarized ultraviolet rays having a wavelength of 300 nm or more. However, a liquid crystal alignment film obtained by a photo-alignment method using photo-isomerization or photo-dimerization has a problem that an alignment regulating force is weak and an after-image is generated when it is used in a liquid crystal display element.

Here, there is known a liquid crystal display element of IPS (In-Plane Switching) in which liquid crystal molecules are switched by applying an electric field to the substrate in the horizontal direction (transverse direction). This liquid crystal display element of the transverse electric field driving method is useful because it has a wide viewing angle, but is susceptible to the orientation state of the liquid crystal, so that the above-described afterimage is liable to occur particularly.

Japanese Patent Application Laid-Open No. 9-297313

"Liquid crystal optical alignment film" Kidowaki, Ichimura Functional material November, 1997 issue Vol.17 No.11 13 - 22 pages

An object of the present invention is to provide a method of manufacturing a liquid crystal display element for driving a transverse electric field capable of suppressing the generation of afterimage by enhancing the alignment restraining force of liquid crystal.

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that, by using a liquid crystal to which a polymerizable compound having a photopolymerizable group is added, or by using a liquid crystal alignment film obtained from a liquid crystal aligning agent having a photopolymerizable group, After the liquid crystal cell is manufactured by performing the rubbing or alignment treatment by the photo alignment method, light is irradiated to cause a photo-polymerizable group present at a portion where the liquid crystal alignment film and the liquid crystal are in contact to react, A liquid crystal display element for driving a transverse electric field obtained by a method of immobilizing a liquid crystal can achieve the above object, thereby completing the present invention. Thus, the present invention has the following points.

1. A liquid crystal alignment film is formed by applying a liquid crystal aligning agent to a substrate to form an alignment layer, and then a pair of substrates on which the liquid crystal alignment layer is formed are disposed opposite to each other with the liquid crystal alignment layer being opposed to each other And then irradiating the liquid crystal cell with light to react the photopolymerizable group in the liquid crystal and / or the liquid crystal alignment film.

2. The method for manufacturing a liquid crystal display element for transverse electric field driving according to 1, wherein the liquid crystal contains the polymerizable compound having the photopolymerizable group.

3. The method for manufacturing a liquid crystal display element for transverse electric field driving according to 1 or 2, wherein the liquid crystal aligning agent contains the photopolymerizable group.

4. The method for producing a liquid crystal display element for transverse electric field driving according to any one of 1 to 3, wherein the liquid crystal aligning agent contains a polymer having the photopolymerizable group as a side chain.

5. A process for producing a liquid crystal display element for transverse electric field driving according to any one of 1 to 4, wherein the liquid crystal aligning agent contains the polymerizable compound having the photopolymerizable group.

6. The process for producing a liquid crystal display element for transverse electric field driving according to any one of 3 to 5, wherein the photopolymerizable group is a group selected from the following photopolymerizable groups.

[Chemical Formula 1]

(Wherein, Me represents a methyl group)

7. The method for manufacturing a liquid crystal display element for transverse electric field driving according to any one of 1 to 6, wherein the alignment treatment is carried out by irradiation with polarized ultraviolet light.

8. The transverse electric field driving liquid crystal display according to any one of 1 to 7, wherein in the alignment treatment, a photoreactive group having a structure selected from the following formulas (A-1) to (A-7) / RTI >

(2)

9. The liquid crystal display element for transverse electric field driving according to any one of 1 to 8, wherein the polymer contained in the liquid crystal aligning agent contains at least one selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor Gt;

10. A process for producing a liquid crystal display element for transverse electric field driving according to any one of 1 to 9, wherein the polymer contained in the liquid crystal aligning agent contains a polysiloxane.

11. The process for producing a liquid crystal display element for transverse electric field driving according to any one of claims 1 to 10, wherein the polymer contained in the liquid crystal aligning agent contains poly (meth) acrylate.

According to the present invention, there is provided a liquid crystal display device comprising a liquid crystal alignment film which has been subjected to alignment treatment by rubbing or photo alignment, in particular alignment by light alignment, and which is capable of suppressing the occurrence of afterimage by enhancing alignment control force of liquid crystal A liquid crystal display element can be obtained.

The present invention relates to a method of manufacturing a liquid crystal display element for driving a transverse electric field, which comprises applying a liquid crystal aligning agent to a substrate to form a liquid crystal alignment film and subjecting the alignment treatment to a pair of substrates having the liquid crystal alignment film thereon, Characterized in that the liquid crystal cell is prepared by arranging the liquid crystal alignment film so as to face the liquid crystal alignment film so as to be opposed to each other and then irradiating light to the liquid crystal cell to react the photo polymerizable group in the liquid crystal and / Hereinafter, each constituent requirement will be described in detail.

The liquid crystal aligning agent and / or the liquid crystal used in the production method of the present invention contains a photopolymerizable group. A liquid crystal containing a photopolymerizable group is obtained by adding a compound containing a photopolymerizable group (hereinafter also referred to as a polymerizable compound) to a liquid crystal. In order to obtain a liquid crystal aligning agent containing a photopolymerizable group, a polymerizable compound may be added to the liquid crystal aligning agent, a photopolymerizable group may be introduced into the side chain of the polymer contained in the liquid crystal aligning agent, do. The liquid crystal alignment film obtained by using such a liquid crystal aligning agent contains a photopolymerizable group. When the polymerizable compound is added to the liquid crystal, the addition ratio may be, for example, 0.1 to 30 (mass)% of the polymerizable compound with respect to the liquid crystal. When the polymerizable compound is added to the liquid crystal aligning agent, the addition ratio may be, for example, 0.1 to 30 (mass%) of the polymerizable compound relative to the liquid crystal aligning agent.

When light such as ultraviolet rays is irradiated to a liquid crystal display element containing a photopolymerizable group in a liquid crystal alignment film and / or in a liquid crystal, a photopolymerizable group located on a surface in contact with the liquid crystal alignment film reacts with the surface of the liquid crystal alignment film The orientation of the liquid crystal to be positioned is fixed. As a result, as shown in Examples described later, good liquid crystal alignability is obtained, and the alignment regulating force of the liquid crystal is strengthened. As a result, electric characteristics such as afterimage phenomenon caused by alignment disorder of the liquid crystal are improved.

The photopolymerizable group is a group capable of undergoing a polymerization reaction with light such as ultraviolet rays, for example, a group capable of being polymerized by light such as ultraviolet light (hereinafter also referred to as a photopolymerizable group) or a photocrosslinking group ), The following structure is preferably used, although it is not particularly limited.

(3)

(Wherein, Me represents a methyl group)

Specific examples of the polymerizable compound include a compound having a group capable of photo-polymerizing at each of two terminals as shown by the following formula (I), a compound having a group capable of photo-crosslinking with a terminal having a group capable of photo- Group or a compound having a group capable of photo-crosslinking at each of two terminals as shown by the following formula (III). In the following formulas (I) to (III), R ¹² is H or an alkyl group having 1 to 4 carbon atoms, and Z ¹ is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms Z ² is a monovalent aromatic ring or heterocyclic ring which may be substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and Q ¹ is a divalent organic group. Q ¹ has a cyclic structure such as a phenylene group (-C ₆ H ₄ -), a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -) or a cyclohexylene group (-C ₆ H ₁₀ -) . This is because the interaction with the liquid crystal tends to become large.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Specific examples of the polymerizable compound represented by the formula (I) include polymerizable compounds represented by the following formulas (I-1) to (I-5). In the formula, V represents a single bond or represents a -R ¹ O-, R ¹ is a straight-chain or branched having 1 to 10 carbon atoms in the alkylene group, preferably represents a -R ¹ O-, R ¹ is straight- Chain or branched alkylene group having 2 to 6 carbon atoms. W is a single bond or -OR ² -, R ² is an alkylene group having 1 to 10 carbon atoms in the linear or branched form, preferably -OR ² -, and R ² is a linear or branched carbon number Is an alkylene group having 2 to 6 carbon atoms. V and W may have the same structure or may be different, but if they are the same, synthesis is easy.

(7)

Further, even if the polymer is a polymerizable compound which is not a? -Methylene-? -Butyrolactone group and has an acrylate group or a methacrylate group as a photopolymerizable group or photo crosslinking group, the acrylate group or the methacrylate group may be an oxyalkylene group or the like In the case of a polymerizable compound having a structure bonded to a phenylene group via a spacer of the polymerizable group, the after-image characteristic due to AC stress is greatly worsened as in the case of the polymerizable compound having the? -Methylene-? -Butyrolactone group at both ends It is possible to largely suppress the afterimage caused by application of the alternating current (AC). A polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group via a spacer such as an oxyalkylene group may be used for the purpose of improving the stability against heat, It can withstand temperatures well.

Specific examples of the polymerizable compound represented by the formula (I) include a polymerizable compound represented by the following formula.

[Chemical Formula 8]

(Wherein R ¹² , V and W are as defined above)

The method for producing such a polymerizable compound is not particularly limited and can be produced, for example, according to a synthesis example described later. For example, the polymerizable compound represented by the formula (I-1) can be synthesized by combining the techniques in organic synthetic chemistry. For example, using 2- (bromomethyl) pyridine using SnCl ₂ by the method suggested by Taraga, M.Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990) Can be synthesized by reacting 2- (bromomethyl) propenoic acid with aldehyde or ketone. Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas, and THF is tetrahydrofuran.

[Chemical Formula 9]

(Wherein R 'represents a monovalent organic group)

In addition, 2- (bromomethyl) acrylic acid can be prepared by reacting lanthanum represented by the following reaction formula with K. Ramarajan, K. Kamalingam, DJO Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983) . &Lt; / RTI >

[Chemical formula 10]

As a specific synthesis example, when a polymerizable compound represented by the above formula (I-1) wherein V is -R ¹ O-, W is -OR ² - and R ¹ and R ² are the same is synthesized, There are two ways to represent it.

(11)

[Chemical Formula 12]

In the case of synthesizing a polymerizable compound represented by the above formula (1) in which R ¹ and R ² are different from each other, a method represented by the following reaction formula can be mentioned.

[Chemical Formula 13]

In the case of synthesizing the polymerizable compound represented by the above formula (I-1) in which V and W are single bonds, the following reaction scheme can be mentioned.

[Chemical Formula 14]

When the photo-polymerizable group is introduced into the side chain of the polymer contained in the liquid crystal aligning agent, the effects of the present invention can be obtained even when there is little or no polymerizable compound in the liquid crystal or the liquid crystal aligning agent. Of course, the polymerizable compound may exist in the liquid crystal or in the liquid crystal aligning agent, and in that case, an additional effect can be expected. (Hereinafter, also referred to as photopolymerizable side chains) to which a photopolymerizable group is introduced (hereinafter also referred to as a photopolymerizable side chain) is a polymer having a polymerizable group selected from methacrylic group, acrylic group, vinyl group, allyl group, styryl group, and alpha -methylene-gamma -butyrolactone group Is a side chain containing at least one species. As described above, when a polymer such as a polyimide precursor contained in the liquid crystal aligning agent and at least one kind of polyimide obtained by imidizing the polyimide precursor is mixed with a methacrylic group, an acrylic group, a vinyl group, an allyl group, a styryl group, Methylene-gamma -butyrolactone group and having a photopolymerizable side chain containing at least one kind selected from the group consisting of methylene-gamma -butyrolactone and methylene-gamma -butyrolactone. By using this polymerizable compound in the liquid crystal aligning agent, It is possible to remarkably improve afterimage characteristics due to stress or the like.

The photopolymerizable side chain may be directly bonded to the main chain of the polymer such as a polyimide precursor or polyimide, or may be bonded via a suitable bonding group. The photo-polymerizable side chain includes, for example, those represented by the following formula (b).

[Chemical Formula 15]

(In the formula (b), R ⁸ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ) -, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, and R ⁹ represents a single bond or an unsubstituted or fluorine-substituted An alkylene group, -CH ₂ - of the alkylene group may be optionally substituted with -CF ₂ - or -CH═CH-, and in the case where any of the groups shown below are not adjacent to each other, these groups may be substituted A divalent carbon ring, a divalent heterocyclic ring, R ¹⁰ is a group selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, A styryl group, and an? -Methylene-? -Butyrolactone group.

R ⁸ in the above formula (b) can be formed by a common organic synthetic method, but from the viewpoint of ease of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH -, -CH ₂ O-.

Specific examples of the carbon ring or heterocyclic ring of the divalent carbon ring or the divalent heterocyclic ring substituting any -CH ₂ - in R ⁹ include, but are not limited to, the following structures .

[Chemical Formula 16]

R ¹⁰ is preferably a methacryl group, an acrylic group, a vinyl group or an? -Methylene-? -Butyrolactone group from the viewpoint of photopolymerization.

It is preferable that the existing amount of the photopolymerizable side chain is within a range capable of fixing the orientation by reacting with irradiation of light such as ultraviolet light to form a covalent bond and in order to further improve the AC afterimage characteristic, To the extent that it does not go far, as much as possible is preferable.

Such polyimide precursors having a photopolymerizable side chain containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group and an? -Methylene-? -Butyrolactone group, A method for producing at least one kind of polymer selected from polyimides obtained by imidizing the polyimide precursor is not particularly limited. For example, a method of obtaining a polyamic acid by reaction of a diamine and a tetracarboxylic acid dianhydride , A diamine or methacryl group having a photopolymerizable side chain containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group and an? -Methylene-? -Butyrolactone group , A tetracarboxylic acid dianhydride having a photopolymerizable side chain containing at least one selected from an acryl group, a vinyl group, an allyl group, a styryl group and an? -Methylene-? -Butyrolactone group When the copolymerization is.

As the polymer contained in the liquid crystal aligning agent used in the present invention, polysiloxane and poly (meth) acrylate are preferably used in addition to the polyimide precursor and the polyimide obtained by imidizing it. Here, the polyimide precursor refers to polyamic acid (also referred to as polyamide acid) or polyamic acid ester. The liquid crystal aligning agent may contain these different polymers at the same time, and the content ratio thereof may be variously selected depending on the characteristics of the liquid crystal display element. The total amount of the polymer contained in the liquid crystal aligning agent is preferably 0.1 to 20 (mass%). The polymer such as polyimide precursor, polyimide, polysiloxane or poly (meth) acrylate contained in the liquid crystal aligning agent of the present invention needs to be soluble in a solvent contained in the liquid crystal aligning agent.

When polarizing ultraviolet rays are used in the alignment process in the production process of the present invention, it is necessary that a polymer containing a liquid crystal aligning agent be introduced with a photoreactive group which exhibits liquid crystal aligning ability by the use of polarized ultraviolet rays. Such a photoreactive group may be introduced into the main chain of the polymer or may be introduced into the side chain.

A polarizing ultraviolet ray is irradiated to a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer into which a photoreactive group is introduced so that the light reaction proceeds and anisotropy is imparted in the same direction as the polarization direction or in the direction perpendicular to the polarization direction to orient the liquid crystal . The photoreaction includes photo decomposition, photo dimerization, and photo isomerization. Specific examples include the structures represented by the following formulas (A-3), (A-4), and (A-5) as the structure in which the photodimerization reaction proceeds. Examples of structures in which the photoisomerization reaction proceeds include the structures represented by the following formulas (A-6) and (A-7). Examples of the structure in which the photodegradation reaction proceeds include structures represented by the following formulas (A-1) and (A-2). The photoreactive group having a structure selected from the following formulas (A-1) to (A-7) is a group in which any number of H is removed from the structures of these formulas (A-1) to (A- In the formulas (A-1) to (A-2), N is a bonding hand group, O is a bonding hand in formula (A-3) or a group in which these structures are bonded to other structures (for example, an alkylene group) .

[Chemical Formula 17]

The polyimide precursor contained in the liquid crystal aligning agent used in the present invention has, for example, a repeating unit (structural unit) represented by the following formula (1).

[Chemical Formula 18]

In the formula (1), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easiness of imidization by heating, a hydrogen atom or a methyl group is particularly preferable. X ₂ is a tetravalent organic group, and its structure is not particularly limited. Specific examples include the following formulas (X-1) to (X-43). X ₂ is preferably (X-1) to (X-10), (X-26) to (X-28), and (X-31) to (X-37) from the viewpoint of liquid crystal alignability. From the viewpoint that a liquid crystal alignment film having a faster relaxation of the residual charge accumulated by the direct current voltage can be obtained, the tetracarboxylic acid dianhydride having an aromatic ring structure is preferably used as the starting material, and X ₂ of formula (1) (X-26), (X-27), (X-28), (X-32), (X-35) or (X-37).

[Chemical Formula 19]

(In the formula (X-1), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, R ₂ , R ₃ , R ₄ and R ₅ are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, Is at least one selected from the group consisting of the structures represented by the formulas (X1-1) to (X1-2)

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

When polarizing ultraviolet rays are used for the alignment treatment in the production method of the present invention, preferable structures of X ₂ include (X1-1), (X1-2), (X-2) 3, X-5, X-7, X-8, X-9 and X- X-6) is particularly preferable.

In the above formula (1), Y ₂ is a divalent organic group and its structure is not particularly limited. Specific examples of Y _{2 include} the following formulas (Y-1) to (Y-73).

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(Wherein, Me represents a methyl group)

(Y-20), (Y-21), (Y-22), and (Y-28) , (Y-29), or (Y-30).

The polyimide precursor contained in the liquid crystal aligning agent used in the present invention can be obtained by reacting a diamine component (for example, a diamine having a photopolymerizable side chain or a diamine having a photoreactive group, which will be described later) and a tetracarboxylic acid dianhydride (For example, a tetracarboxylic acid dianhydride, a tetracarboxylic acid diester dichloride, a tetracarboxylic acid diester or the like) described below. Specifically, the polyamic acid is obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride. The polyamic acid ester is obtained by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base, or by reacting a tetracarboxylic acid diester and a diamine component in the presence of a suitable condensing agent or a base. The polyimide is obtained by subjecting the polyamic acid to dehydration ring closure, or by heating and closing the polyamic acid ester. Such a polyamic acid, a polyamic acid ester, and a polyimide are both useful as a polymer for obtaining a liquid crystal alignment film.

&Lt; Diamine having a photopolymerizable side chain >

Examples of the diamine having a photopolymerizable side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group and an? -Methylene-? -Butyrolactone group include, for example, And diamines having a side chain represented by the above formula (b). More specifically, it may, for example, be a diamine represented by the following general formula (2), but it is not limited thereto.

(32)

(The definitions of R ⁸ , R ⁹ and R ^{10 in} the formula (2) are the same as those in the formula (b)

The bonding position of two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, with respect to the coupler of the side chains, positions 2 and 3, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, positions 3 and 5 on the benzene ring . Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine is also considered, positions 2 and 4, or positions 3 and 5 are more preferable.

Specific examples of the diamine having a photopolymerizable side chain containing at least one member selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a styryl group and an? -Methylene-? -Butyrolactone group , But are not limited thereto.

(33)

(Wherein X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is a single bond or an alkylene group having 1 to 20 carbon atoms which is substituted by an unsubstituted or fluorine atom Lt; / RTI >

The diamine having a photopolymerizable side chain containing at least one selected from the methacryl group, the acrylic group, the vinyl group, the allyl group, the styryl group and the? -Methylene-? -Butyrolactone group is a liquid crystal alignment layer One kind or two or more kinds of them may be mixed and used depending on the properties such as the liquid crystal alignability at the time of use, the pretilt angle, the voltage holding characteristic, the charge accumulation, and the response speed of the liquid crystal when the liquid crystal display device is used.

The diamine having a photopolymerizable side chain containing at least one selected from the methacryl group, acrylic group, vinyl group, allyl group, styryl group and? -Methylene-? -Butyrolactone group is preferably a poly It is preferable to use an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol%, based on the total amount of the diamine components used in the synthesis of the nitric acid.

&Lt; Diamine having photoreactive group >

When polarizing ultraviolet rays are used in the alignment treatment step in the production method of the present invention, it is necessary that a photoreactive group is introduced into the polymer contained in the liquid crystal aligning agent.

(A-1) and (A-2) are used as the main chain of the polyimide precursor and the polyimide when the orientation treatment method which generates the anisotropy by the irradiation of the polarizing ultraviolet ray proceeds, .

(A-3) to (A-7) is used as the main chain of the polymer when the orientation treatment method in which the photo-dimerization reaction or photoisomerization reaction proceeds by irradiation of polarized ultraviolet rays to generate anisotropy is used, Or introduced into the side chain.

When a polyimide precursor and a polyimide obtained by imidizing it are used as the polymer to be contained in the liquid crystal aligning agent, the structure of the formulas (A-3) to (A-7) A carboxylic acid dianhydride or a diamine is used. From the viewpoint of ease of synthesis, it is preferable to use a diamine containing the structure of the above formulas (A-3) to (A-7) in the side chain. The side chain of the diamine is a structure branched from a structure connecting two amino groups of the diamine. Specific examples of such diamines include, but are not limited to, compounds represented by the following formulas.

(34)

(Wherein X is a single bond or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, and Y is a single bond or an alkylene group having 1 to 20 carbon atoms which is substituted by an unsubstituted or fluorine atom R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms or an alkyl ether group substituted by an unsubstituted or fluorine atom,

&Lt; Tetracarboxylic acid dianhydride component >

The tetracarboxylic acid dianhydride to be reacted with the diamine component in order to obtain the polyamic acid contained in the liquid crystal aligning agent used in the present invention is not particularly limited. Specific examples thereof are given below.

Examples of the tetracarboxylic acid dianhydride having an alicyclic or aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,2,4,5 -Cyclohexanetetracarboxylic acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-Dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7- Butylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, tricyclo [4.2.1.02,5] nonane-3,4,7,8-tetracarboxylic acid-3 , 4: 7,8-2 anhydride, hexacyclo [6.6.0.12,7.03,6.19,14.010,13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-2 Anhydride, and 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

Further, when the aromatic tetracarboxylic acid dianhydride is used in addition to the tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure, the liquid crystal alignability can be improved and the charge accumulated in the liquid crystal cell can be reduced. Do.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid Biphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4- Benzophenone tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid 2-anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and the like.

The tetracarboxylic acid dianhydride can be used singly or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

The tetracarboxylic acid dialkyl ester to be reacted with the diamine component in order to obtain the polyamic acid ester contained in the liquid crystal aligning agent used in the present invention is not particularly limited. Specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester , 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl Ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid Dicarboxy-1-cyclohexylsuccinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2, Butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-dicyclo Diethyl hexyltetracarboxylate Stearyl, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, Tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [6.6.0.12,7.03,6.19,14.010,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran- , 3,4-tetrahydronaphthalene-1,2-dicarbodioalkyl ester, and the like.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2', 3,3'-biphenyltetracarboxylic acid Biphenyltetracarboxylic acid dialkyl ester, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3', 4 (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfonyl alkyl ester, 1,2,5,6-naphthalene tetra Carboxylic acid dialkyl esters, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl esters and the like.

Polyamic acid which is a polyimide precursor can be synthesized by the following method.

Specifically, the tetracarboxylic acid dianhydride and the diamine are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours Can be synthesized.

The organic solvent to be used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone as the solubility of the monomer and the polymer, May be mixed and used. The concentration of the polymer is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained.

The polyamic acid thus obtained can be recovered by precipitating a polymer by injecting the reaction solution into a poor solvent while stirring well. In addition, precipitation is carried out several times, followed by washing with a poor solvent, followed by drying at room temperature or by heating, whereby a purified polyamic acid powder can be obtained. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

The polyamic acid ester which is a polyimide precursor can be synthesized by the following methods (1) to (3).

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine.

Concretely, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours .

The esterifying agent is preferably one which can be easily removed by purification. Examples of the esterifying agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone in the solubility of the polymer, They may be used in combination. The concentration at the time of the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass% from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained.

(2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

Polyamic acid esters can be synthesized from tetracarboxylic acid diester dichloride and diamines.

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable for the reaction to proceed mildly. The amount of the base to be added is an amount that is easy to remove and is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easily obtaining a high molecular weight material.

As the solvent to be used in the above-mentioned reaction, N-methyl-2-pyrrolidone and? -Butyrolactone are preferable as the solubility of the monomer and the polymer, and they may be used alone or in combination. The concentration of the polymer in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent the introduction of the outside air in a nitrogen atmosphere.

(3) When polyamic acid is synthesized from tetracarboxylic acid diester and diamine

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.

Specifically, the tetracarboxylic acid diester and the diamine are reacted in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes to 24 hours, For 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) (2,3-dihydro-2-thioxo-3-benzoxazolyl) diphenylphosphonate, and the like can be used, Can be used. The addition amount of the condensing agent is preferably 2 to 3 times the molar amount with respect to the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be added is an amount that is easy to remove, and from the viewpoint of easily obtaining a high molecular weight material, the base is preferably 2 to 4 times the amount of the diamine component.

In addition, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably from 0 to 1.0 times the amount of the diamine component.

Among the methods for synthesizing the above three polyamic acid esters, the synthesis method of the above (1) or (2) is particularly preferable because a high molecular weight polyamic acid ester can be obtained.

The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. After the precipitation is repeated several times, the polyamic acid ester powder is washed with a poor solvent and then heated or dried at room temperature to obtain a purified polyamic acid ester powder. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

&Lt; Preparation of soluble polyimide >

The polyimide may be prepared by imidizing the polyamic acid or polyamic acid ester. In the case of producing a polyimide from a polyamic acid ester, chemical imidization by adding a basic catalyst to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester powder in an organic solvent is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not decrease during the imidization process.

The chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferred because it has sufficient basicity to proceed the reaction.

The temperature at which the imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles per mole of the amic ester group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidization reaction, it is preferable to recover the imidized polymer obtained by means described below and re-dissolve it in an organic solvent to obtain a liquid crystal aligning agent.

When a polyimide is produced from polyamic acid, chemical imidization by adding a catalyst to a solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not lowered in the process of imidization.

The chemical imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred since it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy.

The temperature at which the imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 molar times, preferably 2 to 20 molar times, and the amount of the acid anhydride is 1 to 50 molar equivalents, preferably 3 to 30 molar equivalents, of the amic acid group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.

Since the added catalyst remains in the solution after the imidization reaction of the polyamic acid ester or polyamic acid, the imidized polymer thus obtained is recovered and redissolved in an organic solvent, It is preferable to use an orientation agent.

The solution of the polyimide obtained as described above can be precipitated by pouring into a poor solvent while stirring well. After the precipitation is repeated several times, the polyamic acid ester powder is washed with a poor solvent and then heated or dried at room temperature to obtain a purified polyamic acid ester powder.

Examples of the poor solvent include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene and benzene.

&Lt; Process for producing polysiloxane >

The method for obtaining the polysiloxane to be used in the present invention is not particularly limited and can be obtained, for example, by condensation of an alkoxysilane in an organic solvent. The polysiloxane is usually obtained as a solution in which the alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.

The polycondensation method of the alkoxysilane includes, for example, a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or a glycol.

At this time, the hydrolysis-condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, in theory, 0.5-fold molar water of the total alkoxy group in the alkoxysilane may be added, but it is generally preferable to add an excess amount of water in excess of 0.5-molar mol.

In the present invention, the amount of water to be used in the reaction can be appropriately selected according to the desired amount, but is preferably 0.5 to 2.5 times the molar amount of the total alkoxy groups in the alkoxysilane.

For the purpose of promoting the hydrolysis and condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid; Alkali such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like; Metal salts such as hydrochloric acid, sulfuric acid, and nitric acid; Is used. It is also common to accelerate the hydrolysis and condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, heating and stirring under reflux for 1 hour, and the like.

As another method, for example, a method of polycondensation by heating a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, oxalic acid is added to the alcohol in advance to prepare an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while heating the solution. At this time, the amount of oxalic acid to be used is preferably 0.2 to 2 mol per 1 mol of the total alkoxy group of the alkoxysilane. The heating in this method can be carried out at a liquid temperature of 50 to 180 ° C. Preferably heating for several tens of minutes to several tens of hours under reflux so as not to cause evaporation or volatilization of the liquid.

When a plurality of alkoxysilanes are used to obtain the polysiloxane, they may be mixed as a mixture of alkoxysilanes in advance, or a plurality of alkoxysilanes may be mixed in sequence.

As the alkoxysilane used for obtaining the polysiloxane, the following compounds are exemplified.

Examples of the alkoxysilane compound having a photopolymerizable group in the side chain include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltri Acryloxypropyltrimethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltrimethoxysilane, styrylethyltrimethoxysilane, styrylethyltrimethoxysilane, Ethyl triethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, vinylphenylethyltrimethoxysilane, vinylphenylethyltriethoxysilane, vinyltrimethoxysilane, .

Examples of other alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, Aminoethylaminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2- ) Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyl Triethoxysilane, bromopropyltriethoxy Include silane compounds such as 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropyl Methyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane and γ-ureidopropyltri Propoxysilane, and the like.

The solvent used for polycondensing the alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. Also, even when the alkoxysilane does not dissolve, it may be any one that dissolves along with the progress of the polycondensation reaction of the alkoxysilane. Generally, an organic solvent having good compatibility with alcohols, glycols, glycol ethers, or alcohols is used because alcohol is produced by the polycondensation reaction of alkoxysilane.

Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol; alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, Butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, Glycols such as diol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol and the like: 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 monobutyl Ether, diethylene glycol Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, Glycol ethers such as ethylene glycol dimethyl ether, glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether, and N-methyl-2-pyrrolidone, N, Acetamide,? -Butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide and m-cresol.

In the present invention, a plurality of the above-mentioned polymerization solvents may be mixed and used.

&Lt; Process for producing poly (meth) acrylate >

The method for obtaining the poly (meth) acrylate used in the present invention is not particularly limited. Acrylic acid ester compound or methacrylic acid ester compound, a monomer having a photopolymerizable group, a photoreactive group, and a polymerization initiator if desired, in the presence of a polymerization initiator in a solvent at a temperature of 50 ° C to 110 ° C . The solvent to be used at this time is not particularly limited as long as it dissolves the monomer and the resulting polymer.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2- ethoxy ethyl acrylate , 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- methoxyethyl methacrylate, 2-methoxybutyl methacrylate, 2- Methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone,? -Butyrolactone, 2- Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, Ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, lactose Butyl, and the like can be mentioned N, N- dimethylformamide, N, N- dimethylacetamide and N- methylpyrrolidone.

The solution of the polymer thus obtained is added to the solution under stirring with methanol, ethanol, water and the like to re-precipitate the resulting precipitate, and the resultant precipitate is filtered and washed, and then dried under normal pressure or reduced pressure at room temperature or by heating and drying. can do. By such an operation, the polymerization initiator coexisting with the polymer and the unreacted monomer can be removed, and as a result, a purified polymer powder can be obtained. When the powder can not be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

When a polyimide precursor or polyimide is used as the polymer contained in the liquid crystal aligning agent, the molecular weight of the polyimide precursor or polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, Is 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

When a polysiloxane is used as the polymer contained in the liquid crystal aligning agent, the weight average molecular weight of the polysiloxane is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

When poly (meth) acrylate is used as the polymer contained in the liquid crystal aligning agent, the molecular weight of the poly (meth) acrylate is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, Is 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

The organic solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as the polymer and the polymerizable compound contained in the liquid crystal aligning agent are uniformly dissolved. Specifically, when a polyimide precursor or polyimide is used as the polymer, it is preferable to use N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, , 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. When a polysiloxane is used as the polymer, for example, polyhydric alcohol compounds such as ethylene glycol and 1,2-propylene glycol, amide compounds such as N-methylformamide and N, N-dimethylformamide, . When a poly (meth) acrylate is used as the polymer, for example, an alcohol compound, a ketone compound, an amide compound, an ester compound, or other aprotic compound may be used. These may be used alone or in combination of two or more. Further, even a solvent which can not uniformly dissolve the polymer or the polymerizable compound alone can be mixed with the organic solvent as long as the solvent does not precipitate the polymer or the polymerizable compound.

The liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer or the polymerizable compound, a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a lower surface tension than the organic solvent. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, lactic acid, isobutyl lactate, cyclohexanone, And a wheat ester. These solvents may be used in combination of two kinds of phases.

The liquid crystal aligning agent used in the present invention may contain a dielectric or conductive material for changing electrical properties such as dielectric constant and conductivity of a polymer other than the above-mentioned polymer and a liquid crystal alignment film, as long as the effect of the present invention is not impaired. A silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate, and a crosslinkable compound for enhancing the hardness and denseness of the film when the film is used as a liquid crystal alignment film; and further, a polyimide precursor is imidized efficiently Or the like may be added to the reaction mixture.

&Lt; Production of liquid crystal alignment film &

The liquid crystal alignment film used in the production method of the present invention can be obtained by applying the above liquid crystal aligning agent to a substrate, drying it if necessary, and then firing to give an orientation treatment to the obtained film surface.

The substrate to which the liquid crystal aligning agent is applied is not specifically limited as long as it is a substrate having high transparency. A glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. Indium Tin Oxide (ITO) ) Electrode or the like is preferably used from the viewpoint of simplification of the process. In a reflection type liquid crystal display element, if it is only a substrate on one side, it can be used as an opaque material such as a silicon wafer. In this case, a material that reflects light such as aluminum can also be used. Examples of the application method of the liquid crystal aligning agent described in the present invention include a spin coating method, a printing method, and an ink jet method.

The drying and firing steps after application of the liquid crystal aligning agent can be carried out at arbitrary temperature and time. Usually, in order to sufficiently remove the contained organic solvent, it is preferably dried at 50 ° C to 120 ° C, preferably for 1 minute to 10 minutes, then at 150 ° C to 300 ° C, preferably for 5 minutes to 120 ° C And is sprayed. The thickness of the coated film after firing is not particularly limited, but the thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm because the reliability of the liquid crystal display element may deteriorate if it is too thin.

The orientation treatment used in the production method of the present invention includes an orientation treatment by rubbing and an orientation treatment by so-called photo alignment method by irradiating polarized ultraviolet rays.

As a preferable specific example of the alignment treatment by the photo alignment method, an ultraviolet ray having a wavelength of 200 to 400 nm, preferably 210 to 380 nm, for example, 300 to 350 nm is contained on the surface of the above- Polarized ultraviolet rays are irradiated in a predetermined direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C to give liquid crystal aligning ability. In order to improve the liquid crystal alignment property, ultraviolet rays may be irradiated while the coated film substrate is heated at 50 to 250 ° C. The dose of the ultraviolet rays is preferably in the range of 1 to 10,000 mJ / cm2, and particularly preferably in the range of 1 to 2,000 mJ / cm2.

The film irradiated with ultraviolet rays polarized by UV rays may be subsequently subjected to a contact treatment with water or a solution containing a specific organic solvent. Examples of the organic solvent include, but are not limited to, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy- , Ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Of the above solvents, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, At least one member selected from the group consisting of diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate is preferable. Particularly, at least one species selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate is preferable.

The contact treatment of a film irradiated with polarized ultraviolet rays and a solution containing an organic solvent is carried out by a treatment in which the film and the liquid preferably sufficiently come into contact with each other such as immersion treatment, spray (spray) treatment and the like. Among them, a method in which a film is immersed in a solution containing an organic solvent, preferably for 10 seconds to 1 hour, more preferably for 1 minute to 30 minutes is preferable. The contact treatment may be carried out at room temperature or warmed, preferably at 10 to 80 캜, more preferably at 20 to 50 캜. It is also possible to implement means for increasing the contact of ultrasonic waves or the like as necessary.

After rinsing and drying with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone or the like, or both, for removing the organic solvent in the used solution, . The temperature for drying is preferably 80 to 250 ° C, more preferably 80 to 150 ° C.

The liquid crystal alignment film obtained as described above can stably orient liquid crystal molecules in a certain direction.

&Lt; Method of manufacturing liquid crystal display element for transverse electric field driving >

The transverse electric field driving liquid crystal display device manufactured by the manufacturing method of the present invention can be obtained by preparing a liquid crystal cell for driving a transverse electric field by a known method after obtaining the substrate with the liquid crystal alignment film attached thereto, The liquid crystal cell is used as a liquid crystal display element for driving a transverse electric field. In addition, a liquid crystal display element of an in-plane switching (IPS) type is a liquid crystal display element in which liquid crystal molecules are switched by applying an electric field in a horizontal direction (transverse direction) to a substrate.

As an example of a method of manufacturing a liquid crystal display element for driving a lateral electric field, a liquid crystal display element having a passive matrix structure will be described as an example. Further, the liquid crystal display element may be an active matrix liquid crystal display element for lateral electric field drive in which a switching element such as a TFT (Thin Film Transistor) is formed for each pixel portion constituting an image display.

The substrate used in the liquid crystal display device for transverse electric field drive manufactured by the present invention is not particularly limited as long as it is a substrate having high transparency. Usually, it is a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described in the production of the liquid crystal alignment film.

The liquid crystal alignment film is formed by applying the liquid crystal aligning agent on the substrate, baking it, and irradiating it with a radiation such as a rubbing treatment or a polarized ultraviolet ray if necessary. Next, the other substrate is superimposed on one substrate so that the liquid crystal alignment film faces thereof face each other, and the periphery is adhered to the substrate with a sealing material. In order to control the substrate clearance, a spacer is usually mixed in the sealing material. It is also preferable that a spacer for controlling the gap between the substrates is scattered on the in-plane portion on which the sealing material is not formed. In the part of the sealing material, an opening portion capable of filling the liquid crystal from the outside is formed.

Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening formed in the sealing material. As the liquid crystal material, for example, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) and the like can be mentioned. Thereafter, this opening is sealed with an adhesive. A vacuum injection method may be used for the injection, or a method using capillary phenomenon in the atmosphere may be used. Thereby, a liquid crystal cell for driving a transverse electric field is produced.

Subsequently, the liquid crystal cell for driving the transverse electric field is irradiated with light such as ultraviolet rays. Here, the irradiation amount of the ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less. When the ultraviolet ray irradiation amount is small, the decrease in reliability caused by the destruction of the members constituting the liquid crystal display element can be suppressed, The ultraviolet ray irradiation time can be reduced and the production efficiency is increased, which is preferable. The wavelength of the ultraviolet ray to be irradiated is, for example, 200 nm to 400 nm.

When the liquid crystal cell is irradiated with light such as ultraviolet rays, that is, when light such as ultraviolet rays is irradiated to the liquid crystal alignment film or the liquid crystal, the photo-polymerizable group located on the side in contact with the liquid crystal alignment film reacts with the liquid crystal alignment film, The orientation of the liquid crystal located on the surface is fixed. As a result, as shown in the later-described embodiments, the liquid crystal display element for transverse electric field drive is improved in electric characteristics such as afterimage phenomenon which is caused by the alignment restraining force of the liquid crystal being strengthened and the liquid crystal misalignment being caused.

Next, the polarizing plate is installed. Specifically, a pair of polarizers is attached to a surface of the two substrates opposite to the liquid crystal layer. Through the above steps, a liquid crystal display element for driving a transverse electric field can be obtained.

The transverse electric field driving liquid crystal display device manufactured by the method for manufacturing a transverse electric field driving liquid crystal display device of the present invention has strong alignment control force of liquid crystal and suppresses the generation of afterimage, Lt; / RTI >

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

&Lt; Preparation of liquid crystal aligning agent &

The abbreviations used in the preparation of the following liquid crystal aligning agent are as follows.

(Tetracarboxylic acid dianhydride)

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

(Diamine)

p-PDA: p-phenylenediamine

DA-1: (E) -2,4 diaminophenetyl 3- (4-cyclohexylphenyl) acrylate represented by the following formula

(35)

DA-2: diamine compound represented by the following formula

(36)

DA-3: diamine compound represented by the following formula

(37)

BEM-S: 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula

(38)

(Methacryl monomer)

MA1: methacryl monomer represented by the following formula

[Chemical Formula 39]

MA1 was synthesized by the synthesis method described in JP-A-2010-18807.

(Radical polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Polymerizable compound)

RM1: 5,5 '(4,4' - (bisphenyl-4,4'-diylbis (oxy)) bis (butane-4,1-diyl)) bis (3-methylene dihydrofuran -2 (3H) -one)

(40)

RM2: polymerizable compound represented by the following formula

(41)

RM3: polymerizable compound represented by the following formula

(42)

The conditions for measuring the molecular weight of the polymer (polyamic acid, polyimide) are as follows.

Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Corporation,

Column: Column (KD-803, KD-805) manufactured by Shodex Co.,

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard for the production of calibration curve Sample: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

(Synthesis Example 1)

NMP (22.0 g) was added to DA-1 (5.10 g, 14.0 mmol) and stirred at room temperature for complete dissolution. CBDA (2.66 g, 13.6 mmol) and NMP (22.0 g) Followed by reaction at room temperature for 10 hours to obtain a polyamic acid solution. NMP (40.0 g) and BCS (20.0 g) were added to the polyamic acid solution (40 g), and the mixture was stirred at room temperature for 5 hours to obtain liquid crystal aligning agent A1. The polyamic acid had a number average molecular weight of 6,500 and a weight average molecular weight of 26,000.

To 10.0 g of the liquid crystal aligning agent (A1), 60 mg (10% by mass relative to solid content) of a polymerizable compound RM1 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent A2 .

(Synthesis Example 2)

NMP (20.8 g) was added to DA-1 (3.57 g, 9.8 mmol) and BEM-S (1.11 g, 4.2 mmol) and stirred thoroughly at room temperature to dissolve CBDA (2.66 g, 13.6 m ㏖) and NMP (20.8 g) were added and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (40.0 g) and BCS (20.0 g) were added to the polyamic acid solution (40 g) and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent (B1). The polyamic acid had a number average molecular weight of 7,500 and a weight average molecular weight of 25,000.

To 10.0 g of the liquid crystal aligning agent (B1), 60 mg (10% by mass relative to solid content) of a polymerizable compound RM1 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent B2 .

(Comparative Example 1)

Using the liquid crystal aligning agent (A2) obtained in Synthesis Example 1, a liquid crystal cell was produced in the following order. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm and a comb-shaped pixel electrode formed by patterning an ITO film was disposed. The pixel electrode has a comb-like shape formed by arranging a plurality of <-like electrode elements bent at the center portion. The width of each electrode element in the short direction is 3 占 퐉, and the interval between the electrode elements is 6 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of <-like electrode elements bent at the center portion, the shape of each pixel is not a rectangle shape but a bold text Like shape. Each pixel is divided into upper and lower portions with the central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared with each other, the formation direction of the electrode elements of the pixel electrodes constituting the first region and the second region is different. That is, in the first region of the pixel, the electrode element of the pixel electrode is formed so as to form an angle of +10 degrees (clockwise direction) in the alignment direction of the liquid crystal alignment film to be described later, Is formed so as to form an angle (clockwise direction) of -10 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation (inflation / switching) of the liquid crystal in the substrate plane caused by the application of the voltage between the pixel electrode and the counter electrode is reversed . The liquid crystal aligning agent (A2) obtained in Synthesis Example 1 was spin-coated on the prepared substrate having the electrodes. Subsequently, the substrate was dried with a hot plate at 90 DEG C for 60 seconds, and then fired in a hot air circulating oven at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. Then, ultraviolet rays of 313 nm were irradiated at 20 mJ / cm 2 through the polarizing plate to the coated film surface to obtain a substrate with a liquid crystal alignment film attached. A glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, was subjected to aligning treatment by forming a coating film in the same manner using the liquid crystal aligning agent (A2). A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was adhered such that the liquid crystal alignment film surface faced and the alignment direction was 0 °, and then the sealant was cured to prepare an empty cell. The liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method and the injection port was sealed to form an IPS (In-Plane Switching) mode liquid crystal display element To obtain a liquid crystal cell.

(Example 1)

The liquid crystal cell produced by performing the same operation as in Comparative Example 1 was irradiated with ultraviolet light of 365 nm from the outside of the liquid crystal cell at 20 J / cm 2 (secondary irradiation) to obtain the liquid crystal cell of Example 1.

(Comparative Example 2)

A liquid crystal cell of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the liquid crystal aligning agent (B2) was used in place of the liquid crystal aligning agent (A2).

(Example 2)

The liquid crystal cell produced by carrying out the same operation as in Comparative Example 2 was irradiated with ultraviolet light of 365 nm from the outside of the liquid crystal cell at 20 J / cm 2 (secondary irradiation) to obtain the liquid crystal cell of Example 2.

(Comparative Example 3)

A liquid crystal cell of Comparative Example 3 was obtained in the same manner as in Comparative Example 1 except that the liquid crystal aligning agent (A1) was used in place of the liquid crystal aligning agent (A2).

(Residual image evaluation 1)

The liquid crystal cell for IPS mode prepared in each of Examples 1 to 2 and Comparative Examples 1 to 3 was installed between two polarizing plates arranged so that the polarization axes thereof were orthogonal to each other and the backlight was turned on in a voltage unapplied state, The arrangement angle of the liquid crystal cell was adjusted. The rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the pixel is darkest to the angle at which the first area is darkest is calculated as the initial alignment azimuth angle. Subsequently, an AC voltage of 8 V _PP was applied for 24 hours at a frequency of 30 Hz under a room temperature environment. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. After being left standing, the orientation azimuth was similarly measured, and the difference in orientation azimuth before and after the AC drive was calculated as an angle DELTA (deg.).

As a result, as shown in Table 1, in Examples 1 and 2 in which a polymerizable compound was added and UV was irradiated after the production of a liquid crystal cell, UV irradiation (secondary irradiation ), And Comparative Examples 1 and 2 in which UV irradiation was not performed after production of a liquid crystal cell, the difference in orientation azimuth angle before and after AC driving was very small. Therefore, in Examples 1 and 2, the alignment regulating force is strong and the afterimage characteristic is extremely excellent. It is considered that this is due to the fact that the added photopolymerizable compound forms a polymerized layer on the surface of the alignment film by irradiation with UV light externally after the production of the liquid crystal cell and the alignment is fixed accordingly. Further, in both Example 1 and Example 2, it is difficult to compare because the difference in orientation azimuth angle before and after the AC drive is zero. However, in Comparative Example 2 using the polymer in which BEM-S having the photopolymerization property was used, From the point of view that the difference in orientation azimuth angle before and after driving is small, the use of a polymer incorporating BEM-S having photopolymerization property can be used to confirm the improvement of the afterimage characteristic.

(Synthesis Example 3)

CBDA (1.94 g, 10.0 mmol) and DA-2 (4.49 g, 10.0 mmol) were mixed in NMP (25.7 g) and reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (32.1 g) and BCS (42.9 g) were added to the polyamic acid solution (32.1 g) and diluted to 6 wt%, followed by stirring at room temperature for 10 hours to obtain liquid crystal aligning agent (C). The polyamic acid had a number average molecular weight of 13,000 and a weight average molecular weight of 19,000.

To 10.0 g of the liquid crystal aligning agent (C), 30 mg (5% by mass relative to solid content) of a polymerizable compound RM1 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (C1).

To 10.0 g of the liquid crystal aligning agent (C), 30 mg (5% by mass relative to solid content) of a polymerizable compound RM2 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (C2).

To 10.0 g of the liquid crystal aligning agent (C), 30 mg (5% by mass relative to solid content) of a polymerizable compound RM3 was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (C3).

(Synthesis Example 4)

BODA (2.50 g, 10.0 mmol) and DA-3 (9.65 g, 20.0 mmol) were mixed in NMP (42.3 g) and reacted at 80 ° C for 5 hours. CBDA (1.92 g, 10.0 mmol) NMP (14.1 g) was added and reacted at 40 占 폚 for 10 hours to obtain a polyamic acid solution. NMP (70.4 g) and BCS (93.8 g) were added to the polyamic acid solution (70.4 g) and diluted to 6 wt%, followed by stirring at room temperature for 10 hours to obtain a liquid crystal aligning agent (D). The polyamic acid had a number average molecular weight of 12,000 and a weight average molecular weight of 21,000.

Further, 30 mg (5% by mass relative to solid content) of the polymerizable compound RM1 was added to 10.0 g of the liquid crystal aligning agent (D) and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (D1).

(Synthesis Example 5)

(1.92 g, 10.0 mmol), p-PDA (0.54 g, 5.0 mmol) and DA-2 (2.24 g, 5.0 mmol) were mixed in NMP (18.9 g) and reacted at room temperature for 10 hours, To obtain a mixed acid solution. NMP (23.6 g) and BCS (31.5 g) were added to the polyamic acid solution (23.6 g) and diluted to 6 wt%, followed by stirring at room temperature for 10 hours to obtain a liquid crystal aligning agent (E). The polyamic acid had a number average molecular weight of 19,000 and a weight average molecular weight of 28,000.

To 10.0 g of the liquid crystal aligning agent (E), 30 mg of RM1 (5% by mass based on the solid content) was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (E1).

(Synthesis Example 6)

MA1 (5.54 g, 16.0 mmol) was dissolved in NMP (51.1 g) and degassed for 6 minutes using a diagrammatic pump. AIBN (0.131 g, 0.8 mmol) was added and degassed again for 6 minutes. Thereafter, the reaction was carried out at 65 DEG C for 20 hours to obtain a polymer solution of methacrylate. BCS (37.8 g) was added to the polymer solution to dilute it to 6 mass% and stirred at room temperature for 5 hours to obtain liquid crystal aligning agent (F). This polymer had a number average molecular weight of 16,000 and a weight average molecular weight of 39000.

To 10.0 g of the liquid crystal aligning agent (F), 30 mg of RM1 (5% by mass based on the solid content) was added and dissolved by stirring at room temperature for 3 hours to prepare a liquid crystal aligning agent (F1).

&Lt; Production 2 of Liquid Crystal Cell &

(Example 3)

Using the liquid crystal aligning agent (C1) obtained in Synthesis Example 3, a liquid crystal cell was produced in the following order. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm and provided with a comb-shaped pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of <-like electrode elements bent at the center portion. The width of each electrode element in the short direction is 10 占 퐉, and the interval between the electrode elements is 20 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of <-like electrode elements bent at the center portion, the shape of each pixel is not a rectangle shape but a bold text Like shape. Each pixel is divided into upper and lower portions with the central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared with each other, the formation direction of the electrode elements of the pixel electrodes constituting the first region and the second region is different. That is, in the first region of the pixel, the electrode elements of the pixel electrode are formed so as to form an angle of + 15 degrees (clockwise direction) in the direction of alignment of the liquid crystal alignment film, Is formed at an angle (clockwise direction) of -15 degrees. That is, in the first region and the second region of each pixel, the direction of the rotation (inflation / switching) of the liquid crystal in the substrate plane caused by the application of the voltage between the pixel electrode and the counter electrode is reversed . The liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was spin-coated on the prepared substrate having the electrode. Subsequently, the substrate was dried with a hot plate at 80 DEG C for 90 seconds, and then fired in a hot air circulating oven at 160 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. Subsequently, a polarizing ultraviolet ray of 313 nm was irradiated (primary irradiation) at 50 mJ / cm 2 through the polarizing plate to the coated film surface to obtain a substrate with a liquid crystal alignment film attached. In addition, a liquid crystal aligning material (C1) was used to form a coating film on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, another substrate was adhered so that the liquid crystal alignment film surface faced and the alignment direction was 0 °, and then the sealant was cured to prepare empty cells. The liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method and the injection port was sealed to form an IPS (In-Plane Switching) mode liquid crystal display element To obtain a liquid crystal cell.

After the production of the liquid crystal cell, rearrangement treatment was performed in an oven at 120 캜 for 60 minutes. Thereafter, in a state in which the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, the liquid crystal cell was irradiated with ultraviolet light having passed through a 365 nm band-pass filter at 20 J / cm 2 (secondary irradiation).

(Residual image evaluation 2)

The liquid crystal cell for IPS mode prepared in Example 3 was provided between two polarizers arranged so that the polarization axes thereof were orthogonal to each other, the backlight was turned on in a voltage unapplied state, and the arrangement angle of the liquid crystal cells was adjusted Respectively. The rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the pixel is darkest to the angle at which the first area is darkest is calculated as the initial alignment azimuth angle. Subsequently, an alternating voltage of 16 V _PP was applied for 168 hours at a frequency of 30 Hz in an oven at 60 캜. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. After being left standing, the orientation azimuth was similarly measured, and the difference in orientation azimuth before and after the AC drive was calculated as an angle DELTA (deg.). Table 2 shows the results of the afterimage evaluation.

(Example 4)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (C2) was used in place of the liquid crystal aligning agent (C1), and the residual image was evaluated.

(Example 5)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (C3) was used in place of the liquid crystal aligning agent (C1), and the residual image was evaluated.

(Example 6)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (D1) was used in place of the liquid crystal aligning agent (C1) and the irradiation amount of the polarized ultraviolet ray was set to 500 mJ / cm2.

(Example 7)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (E1) was used in place of the liquid crystal aligning agent (C1), and the residual image was evaluated.

(Example 8)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (F1) was used in place of the liquid crystal aligning agent (C1) and the irradiation amount of the polarized ultraviolet ray was set to 500 mJ / cm2.

(Example 9)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (C) was used in place of the liquid crystal aligning agent (C1), and the residual image was evaluated.

(Comparative Example 4)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (C) was used instead of the liquid crystal aligning agent (C1) and the secondary irradiation was not performed, and the residual image was evaluated.

(Comparative Example 5)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (D) was used in place of the liquid crystal aligning agent (C1), the irradiation amount of the polarized ultraviolet ray was set to 500 mJ / , And the residual image was evaluated.

(Comparative Example 6)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (E) was used instead of the liquid crystal aligning agent (C1) and the secondary irradiation was not carried out, and the residual image was evaluated.

(Comparative Example 7)

A liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (F) was used in place of the liquid crystal aligning agent (C1), the irradiation amount of the polarized ultraviolet ray was set to 500 mJ / , And the residual image was evaluated.

From the results shown in Table 2, all of Comparative Examples 4 to 7, in which no polymerizable compound was added, were greatly deviated in orientation azimuth angle after AC driving, but the polymerizable compound was added, ), It was confirmed that even after AC driving, the orientation azimuth angle was not substantially shifted as compared with Comparative Examples 4 to 7. [ As compared with Comparative Example 4 in which a polymer having a photopolymerizable group in a side chain was contained and the UV irradiation (secondary irradiation) was conducted after the production of the liquid crystal cell, the orientation azimuth angle Is small. In Examples 3 to 9, since the photopolymerizable group of the polymerizable compound or polymer is polymerized at the interface of the alignment film by the secondary irradiation, and the surface of the liquid crystal alignment film is fixed, it is presumed that the deviation of the orientation azimuth is very small.

Claims

A liquid crystal aligning agent is applied to a substrate to form a liquid crystal alignment film and subjected to alignment treatment. Thereafter, a pair of substrates having the liquid crystal alignment film formed thereon are disposed opposite to each other via a liquid crystal so that the liquid crystal alignment film is opposed, Irradiating the liquid crystal cell with light, and reacting the photopolymerizable group in the liquid crystal and / or the liquid crystal alignment film,
Wherein the photopolymerizable group is a group selected from the following photopolymerizable groups.

The method according to claim 1,
Wherein the liquid crystal contains the polymerizable compound having the photopolymerizable group.

3. The method according to claim 1 or 2,
Wherein the liquid crystal aligning agent contains the photopolymerizable group.

3. The method according to claim 1 or 2,
Wherein the liquid crystal aligning agent contains a polymer having the photopolymerizable group in a side chain thereof.

3. The method according to claim 1 or 2,
Wherein the liquid crystal aligning agent contains the polymerizable compound having the photopolymerizable group.

3. The method according to claim 1 or 2,
Wherein the alignment treatment is carried out by irradiation with polarized ultraviolet light.

3. The method according to claim 1 or 2,
Wherein the photo-reactive group having a structure selected from the following formulas (A-1) to (A-7) is reacted in the alignment treatment.

3. The method according to claim 1 or 2,
Wherein the polymer contained in the liquid crystal aligning agent contains at least one selected from a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.

3. The method according to claim 1 or 2,
Wherein the polymer contained in the liquid crystal aligning agent contains a polysiloxane.

3. The method according to claim 1 or 2,
Wherein the polymer contained in the liquid crystal aligning agent contains poly (meth) acrylate.

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