TWI476490B - Method for manufacturing liquid crystal display device for driving electric field - Google Patents

Description

Method for manufacturing liquid crystal display element for horizontal electric field driving

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

A liquid crystal display element used in a liquid crystal television, a liquid crystal display or the like is generally provided with a liquid crystal alignment film for controlling the arrangement state of liquid crystals.

According to the most popular method in the industry, the liquid crystal alignment film is produced by performing a so-called rubbing treatment by wiping the same on the electrode substrate in the same direction by using a cloth such as cotton, nylon or polyester. The surface of the film formed by polyamic acid and/or polyimine which is imidized with this hydrazine.

In the alignment process of the liquid crystal alignment film, the method of rubbing the film surface is an industrially useful method which is simple and excellent in productivity. However, there is an increasing demand for high performance, high definition, and large size of liquid crystal display elements, which are caused by damage, dust, mechanical force, or static electricity on the surface of the liquid crystal alignment film by rubbing treatment. In addition, various problems such as inhomogeneity in the orientation processing surface gradually appear.

As a method of replacing the rubbing treatment, a photo-alignment method of imparting directivity of a liquid crystal by irradiating ultraviolet rays after polarization is known. The liquid crystal alignment treatment by the photo-alignment method is proposed to use a photoisomerization reaction mechanism, a photodimerization, a photodegradation reaction, etc. (refer to a non-patent). Document 1).

For example, Patent Document 1 proposes a method in which a polyimine film having an alicyclic structure such as a cyclobutane ring in its main chain is used in a photo-alignment method. When a polyimide film having such a photo-alignment method is used for a liquid crystal alignment film, its usefulness can be expected because it has higher heat resistance than others.

Such a polyimine film having an alicyclic structure such as a cyclobutane ring is obtained by irradiating a short-wavelength ultraviolet ray, particularly a polarized ultraviolet ray near 254 nm, to exhibit high anisotropy and excellent liquid crystal orientation. Liquid crystal alignment film. However, since ultraviolet rays in the vicinity of 254 nm have high energy and require a large amount of electric power during irradiation, not only the cost required for the photo-alignment treatment but also the environmental load is large. Further, since a short-wavelength ultraviolet ray having a higher energy is used, it is considered to be likely to cause damage to an electrode formed on a substrate or a thin film transistor (hereinafter also referred to as a TFT).

On the other hand, a photo-alignment method using photoisomerization or photodimerization can impart anisotropy by irradiating a polarized ultraviolet ray having a wavelength of 300 nm or more. However, the liquid crystal alignment film obtained by the photo-alignment method using photoisomerization or photodimerization has a weak orientation inhibition force, and when used in a liquid crystal display element, a problem of occurrence of afterimage occurs.

Here, a liquid crystal display element of an IPS (In-Plane Switching) method in which an electric field is applied to a substrate in the horizontal direction (lateral direction) and liquid crystal molecules are switched is known. This horizontal electric field drive type liquid crystal display element is useful because of its wide viewing angle. However, it is a problem that it is easily affected by the orientation state of the liquid crystal, and thus it is particularly likely to generate an afterimage as described above.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-297313

[Non-patent literature]

[Non-Patent Document 1] "Liquid Crystal Light Orientation Film" Muto Association, Shimura Functional Materials, November 1997

Vol. 17 No. 11 13-22

An object of the present invention is to provide a method for producing a liquid crystal display element for lateral electric field driving which can enhance the orientation suppressing force of a liquid crystal and suppress the occurrence of afterimages.

In order to achieve the above object, the present inventors have made intensive studies and found that the liquid crystal display device for driving a horizontal electric field obtained by the following method can achieve the above object, and the present invention is completed by using photopolymerizable property. The liquid crystal of the polymerizable compound of the base or the liquid crystal alignment film obtained by the liquid crystal aligning agent having a photopolymerizable group is subjected to orientation treatment by rubbing or photo-alignment to form a liquid crystal cell, by The photopolymerizable group existing in the portion where the liquid crystal alignment film is in contact with the liquid crystal is reacted by irradiation with light, whereby the liquid crystal of the portion in contact with the liquid crystal alignment film is fixed. As such, the present invention is based on the following.

A method for producing a liquid crystal display device for driving a lateral electric field, characterized in that after a liquid crystal aligning agent is applied onto a substrate to form a liquid crystal alignment film and subjected to orientation treatment, a pair of substrates on which the liquid crystal alignment film is formed are formed After the liquid crystal alignment film is disposed opposite to each other so as to be opposed to the liquid crystal, the liquid crystal cell is formed, and the liquid crystal cell is irradiated with light to react the photopolymerizable group in the liquid crystal and/or the liquid crystal alignment film. step.

2. The method for producing a liquid crystal display device for driving a horizontal electric field, wherein the liquid crystal system contains a polymerizable compound having the photopolymerizable group.

3. The method for producing a liquid crystal display device for driving a lateral electric field according to 1 or 2, wherein the liquid crystal alignment agent contains the photopolymerizable group.

4. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of the first aspect, wherein the liquid crystal aligning agent contains a polymer having a photopolymerizable group in a side chain.

5. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of the first aspect, wherein the liquid crystal aligning agent contains a polymerizable compound having the photopolymerizable group.

6. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of the items 3 to 5, wherein the photopolymerizable group is a group selected from the group consisting of photopolymerizable groups shown below. (wherein Me represents a methyl group).

7. The method of producing a liquid crystal display device for driving a lateral electric field according to any one of 1 to 6, wherein the aligning treatment is performed by irradiation of polarized ultraviolet rays.

8. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of the preceding claims, wherein in the aligning treatment, the method is selected from the following formulas (A-1) to (A-7). Reaction of the photoreactive group of the structure

9. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of 1 to 8, wherein the polymer contained in the liquid crystal aligning agent comprises a polyimide precursor and is imidized. Polyimine At least one of the selected ones.

10. The method for producing a liquid crystal display device for driving a lateral electric field according to any one of claims 1 to 9, wherein the polymer contained in the liquid crystal aligning agent comprises a polyoxyalkylene.

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

According to the present invention, it is possible to obtain a liquid crystal display element for driving a lateral electric field, which is provided with an alignment treatment by a rubbing or photo-alignment method, in particular, a liquid crystal alignment film which is subjected to orientation treatment by light orientation, and can be The orientation inhibition force of the liquid crystal is strengthened and the occurrence of afterimage is suppressed.

The present invention relates to a method for producing a liquid crystal display device for driving a lateral electric field, which is characterized in that after a liquid crystal aligning agent is applied onto a substrate to form a liquid crystal alignment film and subjected to orientation treatment, a pair of substrates on which the liquid crystal alignment film is formed are formed. After the liquid crystal alignment film is disposed opposite to each other so as to be opposed to the liquid crystal, the liquid crystal cell is formed, and the liquid crystal cell is irradiated with light to react the photopolymerizable group in the liquid crystal and/or the liquid crystal alignment film. step. Hereinafter, the respective constituent elements will be described in detail.

<Photopolymerizable group>

The liquid crystal aligning agent and/or the liquid crystal system used in the manufacturing method of this invention contains a photopolymerizable group. The 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. Further, 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, or a photopolymerizable group may be introduced into a side chain of a polymer contained in the liquid crystal aligning agent, both of which may be used. . 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% by mass based on the liquid crystal. In addition, when the polymerizable compound is added to the liquid crystal aligning agent, the addition ratio may be, for example, 0.1 to 30% by mass based on the liquid crystal aligning agent.

When a liquid crystal display element containing a photopolymerizable group in the liquid crystal alignment film and/or the liquid crystal is irradiated with light such as ultraviolet rays, the photopolymerizable group located on the surface of the liquid crystal alignment film and the liquid crystal is reacted, and is positioned in the liquid crystal alignment film. The orientation of the liquid crystal on the surface is fixed. As a result, as shown in the examples to be described later, good liquid crystal directionality can be obtained, and the alignment suppressing force of the liquid crystal can be enhanced, and as a result, electrical characteristics such as afterimage phenomenon due to directional dispersion of the liquid crystal can be improved.

The photopolymerizable group is a group which causes a polymerization reaction by light such as ultraviolet rays, and is, for example, a group which is polymerized by light such as ultraviolet rays (hereinafter also referred to as a photopolymerization group) or a photocrosslinking group (hereinafter The term "photocrosslinking" is not particularly limited, but it is preferred to use a structure as shown below.

(wherein Me represents a methyl group).

Specific examples of the polymerizable compound include a compound having a photopolymerizable group at two terminals represented by the following formula (I), and a group represented by the following formula (II): having photopolymerization A compound having a terminal at the end of the group and a terminal having a photocrosslinking group, or a compound having a photocrosslinking group at each of two terminals represented by the following formula (III). Further, 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 may have a carbon number of 1 to 12 a divalent aromatic ring or a heterocyclic ring substituted with an alkoxy group, a Z ² alkyl group having 1 to 12 carbon atoms or a monovalent aromatic ring or a heterocyclic ring which may be substituted by an alkoxy group having 1 to 12 carbon atoms Q ¹ is a divalent organic group. Q ¹ is a ring structure having a stretching phenyl group (-C ₆ H ₄ -), a stretching phenyl group (-C ₆ H ₄ -C ₆ H ₄ -) or a cyclohexyl group (-C ₆ H ₁₀ -) It is better. It is because the interaction with the liquid crystal is likely to become large.

Specific examples of the polymerizable compound represented by the formula (I) include a polymerizable compound represented by the following formulas (I-1) to (I-5). In the following formula, V is a single bond or represented by -R ¹ O-, and R ¹ is a straight or branched alkyl group having 1 to 10 carbon atoms, preferably represented by -R ¹ O- and R ^A linear or branched alkyl group having 2 to 6 carbon atoms. Further, W is a single bond or represented by -OR ² -, and R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably represented by -OR ² - and R ² is linear or Branches have a carbon number of 2 to 6 alkyl groups. Further, although V and W may be the same structure, they may be different, but if they are the same, the synthesis is easy.

Further, the photopolymerizable group or the photocrosslinkable group is a polymerizable compound having an acrylate group or a methacrylate group even if it is not an α-methylene-γ-butyrolactone group, as long as the acrylate is used. The base or methacrylate group is a polymerizable compound having a structure bonded to a phenyl group via a spacer such as an alkyl group such as an oxygen-extension group, and has an α-methylene-γ-butyl group at both ends Similarly to the polymerizable compound of the ester group, the afterimage characteristics due to the AC stress can be greatly enhanced, that is, the afterimage generated by the application of the alternating current (AC) can be greatly suppressed. Further, as long as the acrylate group or the methacrylate group is a polymerizable compound having a structure in which a phenyl group is bonded via a spacer such as an alkyl group such as an alkyl group, it is possible to improve the stability to heat or to sufficiently withstand it. High temperature, for example, a calcination temperature of 200 ° C or higher.

Further, specific examples of the polymerizable compound represented by the formula (I) include a polymerizable compound of the following formula.

(wherein, R ¹² , V, and W are the same as defined above).

The method for producing the 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 above formula (I-1) can be synthesized by a combination of methods in organic synthetic chemistry. For example, SnCl ₂ can be used to make 2-(bromomethyl) by the method proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990), expressed by the following reaction formula. Acrylic acid (2-(bromomethyl)propenoic acid) is synthesized by reaction with an aldehyde or a ketone. Further, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm & Hass Co., Ltd., and THF is tetrahydrofuran.

(wherein R' represents a monovalent organic group).

Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al. in K. Ramarajan, K. Kamalingam, DJO'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56. -59 (1983) proposed method to synthesize.

In a specific synthesis example, when a polymerizable compound represented by the above formula (I-1) is synthesized by synthesizing a polymerizable compound represented by the above formula (I-1), wherein V is -R ¹ O- and W is -R ² O-, and R ¹ and R ^{2 are the} same, Two methods shown by the following reaction formulas.

In addition, when synthesizing the polymerizable compound represented by the above formula (1), in which R ¹ and R ^{2 are} different, a method represented by the following reaction formula is exemplified.

In the case where the polymerizable compound represented by the above formula (I-1) is synthesized in which V and W are a single bond, a method represented by the following reaction formula can be mentioned.

When the photopolymerizable group is introduced into the side chain of the polymer contained in the liquid crystal aligning agent, the effect of the present invention can be obtained even when the polymerizable compound in the liquid crystal or the liquid crystal aligning agent is small or absent. Of course, a polymerizable compound may be present in the liquid crystal or in the liquid crystal aligning agent, and further effects can be expected in this case. The introduction of a side chain having a photopolymerizable group (hereinafter also referred to as a photopolymerizable side chain) means containing a methacryl group, a propenyl group, a vinyl group, an allyl group, a styryl group, and an α-methylene group. a side chain of at least one selected from the group consisting of a γ-γ-butyrolactone group. As described above, a polymer such as at least one of a polyimine obtained by subjecting a polyimine precursor contained in a liquid crystal aligning agent and the polyimide precursor to ruthenium imidization can be used. a photopolymerizable side chain having at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group. Further, it is used in the liquid crystal aligning agent together with the above-mentioned polymerizable compound, and the afterimage characteristics due to AC stress or the like are remarkably improved as shown in the examples described later.

The photopolymerizable side chain may be directly bonded to a main chain of a polymer such as a polyimide precursor or a polyimide, or may be bonded via an appropriate bonding group. The side chain system of photopolymerization is, for example, represented by the following formula (b).

[R>15]-R ⁸ -R ⁹ -R ¹⁰ (b) (In the formula (b), R ⁸ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO- Any one of -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, and R ⁹ represents a single bond Or an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and the -CH ₂ - system of an alkyl group may be optionally substituted with -CF ₂ - or -CH=CH-, as described below. When the groups of any of the listed groups are not adjacent to each other, they may be substituted by such groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a carbocyclic ring and a divalent heterocyclic ring. R ¹⁰ represents a methacryl group, a propenyl group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group.

Further, although R ⁸ in the above formula (b) can be formed by a general organic synthesis method, from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO- -NH-, -CH ₂ O- is preferred.

Further, the carbon ring or the heterocyclic ring of the divalent carbocyclic ring or the divalent heterocyclic ring of any of -CH ₂ -, which is substituted for R ⁹ , may specifically be exemplified as follows, but is not limited thereto.

From the viewpoint of photopolymerizability, R ¹⁰ is preferably a methacryl group, a propenyl group, a vinyl group or an α-methylene-γ-butyrolactone group.

The photopolymerizable side chain is preferably present in a range in which a reaction can be carried out by irradiation with light such as ultraviolet rays to form a co-bonding to fix the orientation, and in order to improve the characteristics of the AC afterimage, it is not correct. Within the scope of other characteristics, as much as possible, the better.

This type of manufacture consists of having photopolymerization comprising at least one selected from the group consisting of methacryl, propylene, vinyl, allyl, styryl and α-methylene-γ-butyrolactone. The method of the polyimine precursor of the side chain and the polymer of at least one selected from the polyimine obtained by imidating the polyimine precursor is not particularly limited, but for example, In the method for obtaining polylysine by the reaction of a diamine and a tetracarboxylic dianhydride, the method further comprises containing a methacryl group, a propenyl group, a vinyl group, an allyl group, a styryl group, and an α- group. a diamine of a photopolymerizable side chain selected from at least one of methylene-γ-butyrolactone groups, or having a methacryl group, a propenyl group, a vinyl group, an allyl group, or a styryl group And α-methylene-γ- The photopolymerizable side chain tetracarboxylic dianhydride of at least one selected from the butyrolactone group is copolymerized.

<polymer>

The polymer contained in the liquid crystal aligning agent used in the present invention is preferably a polysiloxane or poly(poly) which is used in addition to a polyimide precursor and a polyimide obtained by imidization. Methyl) acrylate. Here, the polyimine precursor refers to polyamic acid (also known as polyamic acid) or polyphthalate. Further, the liquid crystal aligning agent may contain such different polymers at the same time, and the content ratios thereof may be variously selected in accordance with 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% by mass. Further, the polymer of the polyimine precursor, the polyimine, the polyoxyalkylene or the poly(meth)acrylate contained in the liquid crystal aligning agent of the present invention is required to be soluble in the liquid crystal aligning agent. Contained in the solvent.

<Photoreactive group>

In the step of the alignment treatment of the production method of the present invention, when a polarized ultraviolet ray is used, it is necessary to introduce a photoreactive group which exhibits the liquid crystal aligning energy by the use of polarized ultraviolet ray in the polymer contained in the liquid crystal aligning agent. . Such a photoreactive group can be introduced into the main chain of the polymer or can be introduced into the side chain.

The photoreaction is carried out by irradiating a polarized ultraviolet ray to a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polymer having a photoreactive group introduced therein. And attaching the same direction to the polarizing direction or perpendicular to the polarizing direction to orient the liquid crystal. In the photoreaction, there are photodecomposition, photodimerization, and photoisomerization. Specific examples of the structure in which the photodimerization reaction is carried out include the structures represented by the following formulas (A-3), (A-4), and (A-5). The structure which performs a photoisomerization reaction is a structure represented by following formula (A-6) and (A-7). The structure which performs a photodecomposition reaction is a structure represented by following formula (A-1) and (A-2). Further, the photoreactive group having a structure selected from the following formulas (A-1) to (A-7) means removal of the structures of the equations (A-1) to (A-7) a group after an arbitrary number H, a group in which N is a bond in the formula (A-1) to (A-2), a group in which O is a bond in the formula (A-3), or the like It is a group after bonding with other structures (for example, an alkyl group, etc.).

<Polyimide precursor and polyimine obtained by imidization of ruthenium>

The polyimine precursor contained in the liquid crystal aligning agent used in the present invention has, for example, a repeating unit represented by the following (1) (structure list) yuan).

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 hydrazine 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 are given by the following formulas (X-1) to (X-43). From the viewpoint of liquid crystal orientation, X ₂ is preferably (X-1) to (X-10), (X-26) to (X-28), (X-31) to (X-37). . Further, from the viewpoint of obtaining a liquid crystal alignment film which is more relaxed by the residual charge accumulated by the DC voltage, it is preferable to use a tetracarboxylic dianhydride having an aromatic ring structure as a raw material. The structure of X ₂ is preferably (X-26), (X-27), (X-28), (X-32), (X-35) or (X-37).

(In the formula (X-1), R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. Or an alkenyl group or a phenyl group. From the viewpoint of liquid crystal orientation, R ₂ , R ₃ , R ₄ and R ₅ are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, and a hydrogen atom or a methyl group. More preferably, it is more preferably at least one selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-2).

In the step of the alignment treatment of the production method of the present invention, when polarized ultraviolet rays are used, preferred structures of X _{2 are} (X1-1), (X1-2), (X-2), (X-). 3), (X-5), (X-7), (X-8), (X-9), (X-10), (X1-1), (X1-2), (X-6) ) is especially good.

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

(wherein Me represents a methyl group).

Organic solvents such as polyimine precursors or polyimines can be expected The solubility is improved, so it has (Y-8), (Y-20), (Y-21), (Y-22), (Y-28), (Y-29) or (Y-30) The structural unit of the structure is preferred.

The polyimine precursor contained in the liquid crystal aligning agent used in the present invention is a diamine component (for example, a diamine having a photopolymerizable side chain to be described later, or a diamine having a photoreactive group, etc.) The diamine) is obtained by a reaction with a tetracarboxylic dianhydride component (for example, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester described later). Specifically, polylysine is obtained by a reaction of a diamine component and a tetracarboxylic dianhydride. Polyphthalate by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base, or by reacting a tetracarboxylic acid diester with a diamine component in the presence of a suitable condensing agent or base Obtained by reaction. Further, the polyimine is obtained by dehydrating the polyamic acid or by heating the closed loop of the polyphthalate. Any of the polyamines, polyphthalates, and polyimides functions as a polymer for obtaining a liquid crystal alignment film.

<Diamine having photopolymerizable side chain>

a diamine having a photopolymerizable side chain comprising at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group For example, a diamine having a side chain represented by the above formula (b) can be mentioned. More specifically, for example, the diamine represented by the following general formula (2) is mentioned, but it is not limited to this.

(In the formula (2), R ⁸ , R ⁹ and R ^{10 are} as defined in the above formula (b)).

The bonding position of the two diamines (-NH ₂ ) in the formula (2) is not limited. Specifically, the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, and the position of 3, 4 with respect to the bonding group of the side chain are mentioned. Or 3,5 position. Among them, from the viewpoint of the reactivity in synthesizing polyamic acid, the position of 2, 4, 2, 5 or 3, 5 is preferred. If the ease of synthesizing the diamine is taken into consideration, the position of 2, 4 or 3, 5 is more preferable.

a diamine having a photopolymerizable side chain comprising at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group Specifically, a compound represented by the following is mentioned, but it is not limited to this.

(wherein X represents a single bond, or a bond selected by -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or is unsubstituted or substituted by a fluorine atom The alkyl group has a carbon number of 1 to 20).

The above having two photopolymerizable side chains comprising at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group The amine may be used in one type or in a mixture of two or more types depending on the liquid crystal directionality, the pretilt angle, the voltage holding property, the charge retention property, and the like, and the response speed of the liquid crystal when the liquid crystal display element is used.

Further, such a group has photopolymerizable properties including at least one selected from the group consisting of a methacryl group, a propylene group, a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group. The diamine of the side chain is preferably from 10 to 70 mol%, more preferably from 20 to 60 mol%, based on the total amount of the diamine component used for the synthesis of polylysine. It is 30~50% by mole.

<Diamine having photoreactive group>

In the step of the alignment treatment of the production method of the present invention, when a polarized ultraviolet ray is used, it is necessary to introduce a photoreactive group into the polymer contained in the liquid crystal aligning agent.

When the photodecomposition reaction is carried out by irradiation with polarized ultraviolet rays and an orientation treatment method of anisotropy is produced, the structures of the above formulas (A-1) and (A-2) are introduced into the polyimide precursor and the polycondensation. The main chain of quinone imine can be.

When a photodimerization reaction or a photoisomerization reaction is carried out by irradiation with polarized ultraviolet rays, and an orientation treatment method for generating anisotropy is used, the structures of the above formulas (A-3) to (A-7) are introduced into the polymerization. The main chain or side chain of the object can be.

When a polyimine precursor and a polyimine obtained by ruthenium imidation are used as a polymer contained in a liquid crystal aligning agent, it is used in the main chain or the side chain to contain the above formula (A-3). a method of using a tetracarboxylic dianhydride or a diamine having a structure of (A-7), but in view of easiness of synthesis, the above formula (A-3) to (A-7) are contained in a side chain. The structure of the diamine is preferred. Further, the side chain of the diamine means a structure branched from a structure in which two amine groups of a diamine are bonded. Specific examples of such a diamine include a compound represented by the following formula, but are not limited thereto.

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

<tetracarboxylic dianhydride component>

The tetracarboxylic dianhydride which reacts with the diamine component in order to obtain the polyphthalic acid contained in the liquid-crystal aligning agent used by this invention is not specifically limited. Specific examples thereof are listed below.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3. 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ',4,4'-Dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-di Alkene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.02,5]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride , six rings [6.6.0.12, 7.03, 6.19, 14.010, 13] hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dianhydride, 4-(2,5- Dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like.

Further, in addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, when aromatic tetracarboxylic dianhydride is used, liquid crystal directionality can be improved, and the accumulated charge of the liquid crystal cell can be reduced. good. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic acid. Acid dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride , 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,3,3',4-diphenyl ketone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc. .

The tetracarboxylic dianhydride is used in combination with one or two or more types depending on the characteristics of the liquid crystal orientation, the voltage holding property, and the accumulated charge when the liquid crystal alignment film is formed.

The dicarboxylic acid dialkyl ester which is reacted with the diamine component in order to obtain the polyphthalate contained in the liquid crystal aligning agent used in the present invention is not particularly limited. Specific examples thereof are listed below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-ring. Dialkyl butane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Alkyl ester, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexyl succinate, 3,4-dicarboxy-1, Dialkyl 2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butanetetracarboxylate, bicyclo[3,3,0]octane-2, Dialkyl 4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxycyclopentylacetate Ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.02,5]decane -3,4,7,8-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-yl -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid dialkyl ester, and the like.

Examples of the aromatic tetracarboxylic acid dialkyl esters include dialkyl pyromellitic acid, dialkyl 3,3',4,4'-biphenyltetracarboxylate, and 2,2',3,3. '-Biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-diphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-diphenyl ketone tetracarboxylic acid dialkyl Base ester, dialkyl 2,3,3',4-diphenyl ketone tetracarboxylate, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxybenzene) Dialkyl dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, and the like.

<Method for producing polylysine>

The polyamic acid which is a polyimide precursor can be synthesized by the method shown below.

Specifically, it is preferred to react the tetracarboxylic dianhydride and the diamine 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 It can be synthesized in 1~12 hours.

The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone depending on the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. The concentration of the polymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily causing precipitation of the polymer and easily obtaining a high molecular weight body.

The polyamic acid obtained by the above method can be recovered by injecting a poor solvent while properly stirring the reaction solution to precipitate the polymer. In addition, after several times of precipitation and washing with a poor solvent, it is available. A powder of poly-proline which is purified by heating or drying at room temperature. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl sarbuta, acetone, and toluene.

<Method for producing polyamidomate>

The polyglycolate which is a polyimide precursor can be synthesized by the methods (1) to (3) shown below.

(1) When synthesized from polyaminic acid

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

Specifically, it is preferred to react the polyamic acid with the esterifying agent 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 It can be synthesized in 1~4 hours.

The esterifying agent is preferably one which can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl condensate. Aldehyde, N,N-dimethylformamide isopropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide di-t - butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine chloride or the like. The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents based on the repeating unit 1 molar of the polyglycolic acid.

The solvent used in the above reaction is based on the solubility of the polymer, and is N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone. For this reason, one type or a mixture of two or more types may be used. The concentration at the time of the synthesis is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass, from the viewpoint of easily causing precipitation of the polymer and easily obtaining a high molecular weight body.

(2) When synthesized by the reaction of a tetracarboxylic acid diester dichloride with a diamine

Polyammonium esters can be synthesized from tetracarboxylic acid diester dichlorides and diamines.

Specifically, the tetracarboxylic acid diester dichloride and the diamine can be 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. It is synthesized in 24 hours, preferably 1 to 4 hours.

Although pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used as the base, pyridine is preferred in order to stabilize the reaction. The amount of the base to be added is preferably an amount which is easily removed, and from the viewpoint of easily obtaining a high molecular weight body, it is preferably 2 to 4 moles per mole of the tetracarboxylic acid diester dichloride.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone depending on the solubility of the monomer and the polymer, and one type or a mixture of two types may be used. the above. The concentration of the polymer at the time of synthesis is less likely to cause precipitation of the polymer, and from the viewpoint of easily obtaining a high molecular weight body, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyglycolate is preferably as far as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere.

(3) When synthesizing poly-proline from tetracarboxylic acid diester and diamine

Polyammonium esters can be synthesized by polycondensation of a tetracarboxylic acid diester with a diamine.

Specifically, the tetracarboxylic acid diester and the diamine can be 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. It is synthesized in an hour, preferably from 3 to 15 hours.

As the condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-three Methylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl) -N,N,N',N'-tetramethylurea hexafluorophosphate, (2,3-dihydro-2-thio-3-benzo Triazolyl) phosphonic acid diphenyl and the like. The amount of the condensing agent added is preferably 2 to 3 moles per mole of the tetracarboxylic acid diester.

As the base system, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is preferably from 2 to 4 times the molar amount of the diamine component from the viewpoint of easily obtaining a high molecular weight body.

Further, in the above reaction, the reaction is efficiently carried out by adding Lewis acid as an additive. The Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The addition amount of Lewis acid is preferably from 0 to 1.0 times the molar amount of the diamine component.

In the synthesis method of the above three polyglycolates, in order to obtain a polymer The amount of the polyglycolate is particularly preferably the synthesis method of the above (1) or (2).

The solution of the polyglycolate obtained by the above method can be precipitated by injecting a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, it is possible to obtain a powder of a polyphthalate which is purified at a constant temperature or by heating and drying. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl sarbuta, acetone, and toluene.

<Method for Producing Soluble Polyimine>

The above polyimine can be produced by imidating the above polyamic acid or polyamine. When the polyimine is produced from a polyphthalate, the chemistry of adding a basic catalyst to the polyamine solvent solution obtained by dissolving the polyphthalate solution or the polyamidolate powder in an organic solvent is added. Sexual imidization is simple. The chemical hydrazine imidization is preferred because the ruthenium imidization reaction is carried out at a relatively low temperature and the molecular weight of the polymer is not easily lowered during the imidization.

The chemical hydrazine imidization can be carried out by stirring the polyamidated ester which is imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferred because it has sufficient alkalinity in carrying out the reaction.

The temperature at which the hydrazine imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C ~ 100 ° C, the reaction time can be carried out within 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 phthalate group. The ruthenium imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time. In the solution after the imidization reaction, since the added catalyst or the like remains, the obtained quinone imidized polymer is recovered by the means described below, and re-dissolved in an organic solvent. It is better to be a liquid crystal director.

When the polyimine is produced from polyamic acid, it is convenient to imidize the chemical hydrazine in the polyamic acid solution obtained by the reaction of the diamine component and the tetracarboxylic dianhydride. The chemical hydrazine imidization is preferred because the ruthenium imidization reaction is carried out at a relatively low temperature, and the molecular weight of the polymer is less likely to be lowered during the imidization.

The chemical hydrazine 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, the solvent used in the above polymerization reaction can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, the pyridine is preferred because it has a moderate basicity in the progress of the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after the completion of the reaction becomes easy, and it is preferable.

The temperature at which the ruthenium imidization reaction is carried out is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be carried out within 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The ruthenium imidization ratio of the obtained polymer can be controlled by adjusting the amount of the catalyst, the temperature, and the reaction time.

In the solution after the imidization reaction of polyglycolate or polylysine, since the added catalyst or the like remains, the obtained oxime is imidized by the means set forth below. The polymer is recovered and re-dissolved in an organic solvent to form a liquid crystal aligning agent of the present invention.

The solution of the polyimine obtained by the above method can be precipitated by injecting a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, it is possible to obtain a powder of a polyphthalate which is purified at a constant temperature or by heating and drying.

The poor solvent is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

<Method for producing polyoxyalkylene oxide>

The method for obtaining the polyoxyalkylene used in the present invention is not particularly limited, and for example, it is obtained by condensing an alkoxydecane in an organic solvent. In general, a polyoxyalkylene is obtained by polycondensing the above alkoxysilane to obtain a solution which is uniformly dissolved in an organic solvent.

The method of polycondensing the alkoxysilane is, for example, a method of hydrolyzing and condensing the alkoxysilane in a solvent such as an alcohol or a diol.

In this case, the hydrolysis or condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, in theory, as long as it is 0.5 times mole of water of the total alkoxy group in the alkoxysilane, it is generally It is preferred to add water in an excess of more than 0.5 times mole.

In the present invention, the amount of water used in the above reaction may be appropriately selected as required, but it is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxysilane.

Further, generally, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid is used for the purpose of promoting hydrolysis and condensation reaction; ammonia, methylamine, ethylamine, ethanolamine, A base such as triethylamine; a catalyst such as a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. In addition to this, in general, hydrolysis and condensation reactions are further promoted by heating a solution in which alkoxysilane is dissolved. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating and stirring at 50 ° C for 24 hours, a method of heating and stirring for 1 hour under reflux, and the like can be mentioned.

Further, as another method, for example, a method in which a mixture of alkoxysilane, a solvent, and oxalic acid is heated and polycondensed can be mentioned. Specifically, a method in which oxalic acid is added to an alcohol solution of an oxalic acid in an alcohol, and then the alkoxysilane is mixed in a state in which the solution is heated. In this case, the amount of oxalic acid to be used is preferably 0.2 to 2 moles per mole 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. It is preferably a method of heating under reflux for several tens of minutes to several ten hours in order to avoid evaporation or volatilization of the liquid.

When polyoxyalkylene is obtained, when a plurality of alkoxysilanes are used, they may be mixed as a mixture in which alkoxysilane is previously mixed, or a plurality of alkoxysilanes may be sequentially mixed.

The alkoxysilane used to obtain the polyoxyalkylene can be exemplified by the compounds described below.

Examples of the alkoxysilane compound having a photopolymerizable group in the side chain include 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, and methacrylonitrile. Trimethoxyoxane, methacryloyloxymethyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, propyleneoxyethyltrimethoxydecane, propylene Ethoxyethyl triethoxy decane, styrylethyl trimethoxy decane, styrylethyl triethoxy decane, 3-(N-styrylmethyl-2-amine ethylamino)propyl trimethyl Oxy decane, ethylene phenethyl trimethoxy decane, vinyl phenethyl triethoxy decane, ethylene trimethoxy decane, and the like.

Other alkoxy decane compounds include methyltrimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, and A. Tripropoxydecane, 3-aminopropyltrimethoxyoxane, 3-aminopropyltriethoxyoxane, N-2 (aminoethyl) 3-aminopropyltriethoxyoxane, N-2 ( Aminoethyl) 3-aminopropyltrimethoxy decane, 3-(2-aminoethylaminopropyl)trimethoxy decane, 3-(2-aminoethylaminopropyl)triethoxy decane, 2-amine Ethylamine methyltrimethoxy decane, 2-(2-aminoethylthioethyl)triethoxy decane, 3-mercaptopropyltriethoxy decane, decylmethyltrimethoxy decane, ethylene triethoxy decane, 3 - isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, bromopropyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, dimethyl diethoxy decane, Dimethyltrimethoxy decane, diethyldiethoxy decane, diethyltrimethoxy decane, diphenyltrimethoxy decane, diphenyldiethoxy oxime Alkane, 3-aminopropylmethyldiethoxy decane, 3-aminopropyldimethylethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, γ-ureidopropyl triethoxy decane , γ-ureidopropyltrimethoxyoxane, γ-ureidopropyltripropoxydecane, and the like.

The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxydecane is not particularly limited as long as the alkoxysilane is dissolved. Further, even when the alkoxysilane is not dissolved, it may be dissolved as long as the polycondensation reaction with the alkoxysilane is carried out. In general, since an alcohol is produced by a polycondensation reaction of an alkoxysilane, an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with an alcohol is used.

Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3- Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, a diol such as 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol or the like; 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 II Methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol a glycol ether such as monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether, N -methyl-2-pyrrolidine Ketone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethylurea, hexamethylphosphonium triamine, m - cresol and the like.

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

<Method for producing poly(meth) acrylate>

The method for obtaining the poly(meth)acrylate used in the present invention is not particularly limited. By using a monomer such as an acrylate compound or a methacrylate compound, a monomer having a photopolymerizable group or a photoreactive group as required, and a polymerization initiator as required, in a solvent It is obtained by polymerization at a temperature of 50 ° C to 110 ° C. The solvent to be used at this time is not particularly limited as long as the monomer and the obtained polymer are dissolved.

Examples of the acrylate compound include methacrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, and phenyl acrylate. , 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-Ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate , 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and mercaptomethyl. Acrylate, 蒽methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl Acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2- Ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-gold Alkyl methacrylate, 8-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 stilbene acetate, ethyl stilbene acetate, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxyl Methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate , ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidine Ketones, etc.

The solution of the polymer obtained as described above is poured into methanol, ethanol, water or the like under stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then subjected to normal temperature or under normal pressure or reduced pressure. It is dried by heating to become the desired polymer powder. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the polymer can be removed, and as a result, the purified polymer powder can be obtained. When it cannot be fully purified in one operation, The obtained powder is redissolved in a solvent, and the above operation may be repeated.

<Liquid Crystal Orienting Agent>

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

When polysiloxane is used as the polymer contained in the liquid crystal aligning agent, the molecular weight of the polyoxyalkylene is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, still more preferably 10,000 to 100,000, in terms of weight average molecular weight. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 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, preferably 5,000 to 300,000, more preferably 5,000 to 300,000, more preferably Good is 10,000~100,000. Further, the number average molecular weight is preferably from 1,000 to 250,000, more preferably from 2,500 to 150,000, still more preferably from 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 or polymerizable compound contained in the liquid crystal aligning agent is uniformly dissolved. Polyamines are used if specific examples are listed When the precursor or polyimine is used as the polymer, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N- Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl azine , dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and the like. Further, examples of the polyphenylene oxide as the polymer include a polyol compound such as ethylene glycol or 1,2-propylene glycol, N-methylformamide, N,N-dimethylformamide, and the like. Amidoxime compound or the like. Further, examples of the use of the poly(meth)acrylate as the polymer include an alcohol compound, a ketone compound, a guanamine compound or an ester compound, or other aprotic compounds. These may be used alone or in combination of two or more. In addition, even if it is a solvent which cannot melt|dissolve a polymer or a polymeric compound uniformly, it can mix with the above-mentioned organic solvent in the range which does not isolate|separate a polymer or a polymeric 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. As the solvent, generally, a solvent having a lower surface tension than the above organic solvent can be used. Specific examples thereof include ethyl celecoxib, butyl siroli, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate Ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl racesu acetate, dipropylene glycol, 2-(2-B Oxypropoxy)propanol, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more types.

In the liquid crystal aligning agent used in the present invention, in addition to the above, a dielectric constant or conductivity of a polymer other than the above polymer, a liquid crystal alignment film may be added as long as the effect of the present invention is not impaired. A dielectric or conductive substance for the purpose of changing the electrical properties of the liquid crystal; a decane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate; for the purpose of improving the hardness or density of the film when the liquid crystal alignment film is formed Further, the cross-linking compound is a ruthenium-imiding accelerator for the purpose of efficiently imidating the ruthenium of the polyimide precursor in the case of calcining the coating film.

<Manufacture of liquid crystal alignment film>

The liquid crystal alignment film used in the production method of the present invention is obtained by applying the liquid crystal alignment agent to a substrate, drying it as needed, and then subjecting the surface of the coating film obtained by calcination to orientation treatment.

The substrate to which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used, and the process can be simplified. From the viewpoint of the use, it is preferred to use a substrate on which an indium tin oxide (ITO) electrode or the like for driving a liquid crystal is formed. Further, in the reflective liquid crystal display device, even if it is a single-sided substrate, it can be used as an opaque substrate such as a germanium wafer. In this case, a material such as aluminum that reflects light can be used. The coating method of the liquid crystal aligning agent of the present invention is a spin coating method, a printing method, an inkjet method, or the like.

The drying and calcining steps after coating the liquid crystal aligning agent can be selected at any temperature and time. Generally, in order to sufficiently remove the organic solvent contained, it is preferably at 50 ° C to 120 ° C and preferably dried for 1 minute to 10 minutes, and then preferably at 150 ° C to 300 ° C and preferably calcined. 5 minutes to 120 minutes. The thickness of the coating film after the calcination is not particularly limited. However, if the thickness of the liquid crystal display device is too small, the thickness of the coating film is preferably from 5 to 300 nm, more preferably from 10 to 200 nm.

<Targeting Processing>

The orientation treatment used in the production method of the present invention is an orientation treatment by rubbing, and an orientation treatment by irradiation of polarized ultraviolet light, that is, a so-called photo-alignment method.

A preferred embodiment of the alignment treatment by the photo-alignment method is to irradiate the surface of the coating film with a wavelength of 200 nm or more and 400 nm or less, preferably 210 nm or more and 380 nm or less, and for example, ultraviolet rays of 300 nm or more and 350 nm or less. A method of imparting directivity to the liquid crystal by subjecting the ultraviolet rays polarized in a certain direction to heat treatment at a temperature of 150 to 250 ° C as the case may be. Further, in order to improve the liquid crystal orientation, the coated substrate may be heated at 50 to 250 ° C while irradiating ultraviolet rays. The irradiation amount of the ultraviolet system to 1 ~ 10,000mJ / cm ² by the range of preferably to 1 ~ 2,000mJ / cm ² by the range of the particularly preferred.

Further, the film after the above-described polarized ultraviolet light irradiation may be subjected to a contact treatment by water or a specific organic solvent. The organic solvent described above is not particularly limited, and examples thereof include water, methanol, and ethanol. 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl sirlo, ethyl lactate, lactate Ester, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among the above solvents, from the viewpoint of high anisotropy and easy to obtain a uniform liquid crystal alignment film, 1-methoxy-2-propanol and 1-methoxy-2-propanol acetate are used. , butyl 赛路苏, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate It is preferable to select at least one of the group formed. In particular, it is preferred to select at least one selected from the group consisting of 1-methoxy-2-propanol and ethyl lactate.

The contact treatment of the ultraviolet ray film after the irradiation with the polarized light and the solution containing the organic solvent is carried out by a treatment in which the film or the liquid such as the immersion treatment or the spray (spray) treatment is preferably sufficiently contacted. Among them, the method of immersing the film in a solution containing an organic solvent is preferably from 10 seconds to 1 hour, more preferably from 1 minute to 30 minutes. The contact treatment may be carried out at room temperature, but it is preferably carried out at 10 to 80 ° C, more preferably 20 to 50 ° C. In addition, a means of improving contact such as ultrasonic waves may be applied as needed.

After the above contact treatment, washing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone may be carried out for the purpose of removing the organic solvent in the used solution. Either (washed) or dried, or both. The temperature at the time of drying is preferably from 80 to 250 ° C, more preferably from 80 to 150 ° C.

The liquid crystal alignment film obtained as described above can stabilize the liquid crystal molecules Oriented in a certain direction.

<Method of Manufacturing Liquid Crystal Display Element for Driving Horizontal Waves>

In the liquid crystal display device for driving a horizontal electric field manufactured by the method of the present invention, after the substrate having the liquid crystal alignment film described above is obtained, a liquid crystal cell for driving a horizontal electric field is produced by a known method, and the horizontal electric field is driven by the transverse electric field. A liquid crystal cell for transverse electric field driving is produced by using a liquid crystal cell. In addition, the liquid crystal display element of the IPS (In-Plane Switching) system is a liquid crystal display element in which an electric field is applied to the substrate in the horizontal direction (lateral direction) and liquid crystal molecules are switched.

A liquid crystal display device having a passive matrix structure will be described as an example of a method of fabricating a liquid crystal display device for driving a lateral electric field. Further, a liquid crystal display element for horizontal electric field driving of an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display may be used.

The substrate used for the liquid crystal display device for driving a horizontal electric field to be used in the present invention is not particularly limited as long as it is a substrate having high transparency, but a substrate for forming a transparent electrode for driving a liquid crystal is generally formed on the substrate. Specific examples are the same as those described in the production of the liquid crystal alignment film.

Further, the liquid crystal alignment film is obtained by applying the liquid crystal aligning agent onto the substrate, and then calcining it, and if necessary, it is formed by rubbing treatment or irradiation with radiation such as polarized ultraviolet rays. Next, the other substrate is superposed on one of the substrates such that the liquid crystal alignment films of the liquid crystal alignment films are opposed to each other, and the periphery is adhered by a sealing material. In order to control the substrate gap, the spacer is generally Mix in the sealant. Further, it is preferable that the spacer for controlling the gap of the substrate is dispersed in the in-plane portion where the sealing member is not provided. An opening portion capable of filling the liquid crystal from the outside is provided in a part of the sealing material.

Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material by being provided in the opening of the sealing material. The liquid crystal material is, for example, liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.). Thereafter, the opening is sealed with an adhesive. For the injection, a vacuum injection method or a method of utilizing a capillary phenomenon in the atmosphere may be used. Thereby, a liquid crystal cell for driving a lateral electric field is produced.

Next, the liquid crystal cell for driving the horizontal electric field is irradiated with light such as ultraviolet rays. Here, the irradiation amount of the ultraviolet ray is, for example, 1 to 60 J, preferably 40 J or less, and the amount of ultraviolet ray irradiation is small, and it is possible to suppress the decrease in reliability due to breakage of the member constituting the liquid crystal display element, and to illuminate the ultraviolet ray. Time reduction is more suitable for improving manufacturing efficiency. The wavelength of the ultraviolet ray to be irradiated is, for example, 200 nm to 400 nm.

When such a liquid crystal cell is irradiated with light such as ultraviolet rays, that is, when the liquid crystal alignment film or the liquid crystal is irradiated with light such as ultraviolet rays, the photopolymerizable group located on the surface of the liquid crystal alignment film and the liquid crystal is reacted, and the liquid crystal alignment film is located. The orientation of the liquid crystal on the surface is fixed. As a result, as shown in the examples to be described later, the alignment suppressing force of the liquid crystal can be enhanced, and as a result, the liquid crystal display element for lateral electric field drive which improves the electrical characteristics such as the afterimage phenomenon due to the directional dispersion of the liquid crystal is obtained.

Next, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates are attached to the surface of the two substrates opposite to the liquid crystal layer. By going through In the step, a liquid crystal display element for driving a lateral electric field is obtained.

In the horizontal electric field driving liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device for driving a horizontal electric field according to the present invention, since the liquid crystal alignment suppressing power is strong and the generation of afterimages can be suppressed, it can be suitably used for a large screen and high. Fine LCD TVs, etc.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

<Modulation of Liquid Crystal Directing Agent>

The code used for the preparation of the liquid crystal aligning agent described below is as follows.

(tetracarboxylic dianhydride)

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

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

(diamine)

p-PDA: p-phenylenediamine

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

DA-2: a diamine compound represented by the following formula

DA-3: a diamine compound represented by the following formula

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

(methacrylic monomer)

MA1: a methacrylic monomer represented by the following formula

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

(radical polymerization initiator)

AIBN: 2,2'-azobisisobutyronitrile

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cyrus

(polymerizable compound)

RM1: 5,5'(4,4'-(bisphenyl-4,4'-diylbis(oxy)) bis(butane-4,1-diyl) bis represented by the following formula 3-extended methyldihydrofuran-2(3H)-one)

RM2: a polymerizable compound represented by the following formula

RM3: a polymerizable compound represented by the following formula

Further, the molecular weight measurement conditions of the polymer (polyperide, polyimine) are as follows.

Device: manufactured by Senshu Scientific co., Ltd. Normal temperature gel permeation chromatography (GPC) device (SSC-7200), Column: Shodex pipe column (KD-803, KD-805)

Column temperature: 50 ° C

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH CORPORATION, and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd.

(Synthesis Example 1)

After adding NNP (22.0 g) to DA-1 (5.10 g, 14.0 mmol), and stirring at room temperature to completely dissolve, CBDA (2.66 g, 13.6 mmol) and NMP (22.0 g) were added at room temperature. The reaction was carried out for 10 hours to obtain a polyaminic acid solution. To the polyamic acid solution (40 g), NMP (40.0 g) and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A1). The polyamine has a number average molecular weight of 6,500 and a weight average molecular weight of 26,000.

In addition, 60 mg (10% by mass based on the solid content) of the polymerizable compound RM1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal aligning agent. (A2).

(Synthesis Example 2)

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

In addition, 60 mg (10% by mass based on the solid content) of the polymerizable compound RM1 was added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture was stirred at room temperature for 3 hours to be dissolved to prepare a liquid crystal orientation. Agent (B2).

<Production of Liquid Crystal Cell 1> (Comparative Example 1)

The liquid crystal cell was produced in the order shown below using the liquid crystal aligning agent (A2) obtained in Synthesis Example 1. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film was used. The pixel electrode has a comb-like shape in which the electrode elements which are bent in the central portion and have a U-shaped shape are arranged in plural. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. The pixel electrode in which each pixel is formed is formed by arranging the electrode elements having a U-shaped bent portion in the central portion as a plurality of columns. Therefore, the shape of each pixel is not rectangular, but is provided in the central portion in the same manner as the electrode elements. Bending is similar to the shape of a bold figure. Further, each pixel is divided into upper and lower sides by a curved portion at the center thereof, and has a first region on the upper side of the curved portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +10° (clockwise) in the first region of the pixel, and is in the second region of the pixel. In the middle, the electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). In other words, the first region and the second region of each pixel are configured to be rotated in the substrate surface by the application of a voltage between the pixel electrode and the counter electrode (in-plane, The switching directions are opposite to each other. The liquid crystal aligning agent (A2) obtained in Synthesis Example 1 was spin-coated on the prepared substrate of the above-mentioned electrode. Subsequently, the film was dried on a hot plate at 90 ° C for 60 seconds, and then calcined in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Thereafter, the coating film surface was irradiated with ultraviolet rays of 313 nm at 20 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, as the counter substrate, even if the glass substrate having the columnar spacer having a height of 4 μm in which the electrode was not formed was formed, the coating film was formed in the same manner using the liquid crystal aligning agent (A2), and the alignment treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Next, the other substrate is bonded so that the orientation direction of the liquid crystal alignment film becomes 0°, and then the sealant is cured to produce a hollow cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the hollow cell by a vacuum injection method, and the injection port was sealed to obtain an IPS (In-Plane Switching) mode liquid crystal display element (horizontal electric field drive) The liquid crystal cell of the structure of the liquid crystal display element).

(Example 1)

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

(Comparative Example 2)

In addition to using liquid crystal aligning agent (B2) instead of liquid crystal aligning agent (A2) The same operation as in Comparative Example 1 was carried out, and the liquid crystal cell of Comparative Example 2 was obtained.

(Example 2)

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

(Comparative Example 3)

The same operation as in Comparative Example 1 was carried out except that the liquid crystal aligning agent (A1) was used instead of the liquid crystal aligning agent (A2), and the liquid crystal cell of Comparative Example 3 was obtained.

(afterimage evaluation 1)

The liquid crystal cells of the IPS mode prepared in each of Examples 1 to 2 and Comparative Examples 1 to 3 were placed between two polarizing plates arranged such that the polarization axis was perpendicular, and no voltage was applied. The backlight is turned on to adjust the arrangement angle of the liquid crystal cells so that the brightness of the transmitted light is minimized. Next, the rotation angle at which the liquid crystal cell is rotated from the second region of the pixel to the darkest angle to the darkest angle of the first region is calculated as the initial positioning azimuth. Then, an alternating voltage of 8 V _PP was applied at a frequency of 30 Hz for 24 hours at room temperature. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were short-circuited, and they were allowed to stand at room temperature for 1 hour. After the placement, the orientation azimuth angle was measured in the same manner, and the difference in the azimuth angles before and after the AC drive was calculated as the angle Δ (deg.).

As a result, as shown in Table 1, the polymerizable compound was added, and the liquid crystal cells were irradiated with UV after the production of Examples 1 and 2, and no UV irradiation was observed after the liquid crystal cell was produced. In Comparative Example 3 (second irradiation) or Comparative Examples 1 and 2 in which UV was not irradiated after the liquid crystal cell was produced, the difference in orientation azimuth between before and after AC driving was extremely small. Therefore, in Examples 1 and 2, it can be said that the orientation suppressing power is strong and the afterimage characteristics are extremely excellent. This is considered to be because the liquid crystal cell is irradiated with UV from the outside, and the added photopolymerizable compound forms a polymerization layer on the surface of the alignment film, so that the orientation is fixed. Further, in the first embodiment and the second embodiment, since the difference in the orientation azimuth between the two before and after the AC driving is zero, it is difficult to compare, but the comparative example 2 in which the polymer having the photopolymerizable BEM-S is used is used. Since the difference in orientation azimuth between the front and rear of the AC drive was smaller than that of Comparative Example 1, it was confirmed that the afterimage characteristics were further improved by using the polymer introduced by the photopolymerizable BEM-S.

(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 the mixture was reacted at room temperature for 10 hours to obtain a polyaminic acid solution. NMP (32.1 g) and BCS (42.9 g) were added to the polyamic acid solution (32.1 g) to be diluted to 6 wt%, and then stirred at room temperature for 10 hours to obtain a liquid crystal director (C). . The polyamine has a number average molecular weight of 13,000 and a weight average molecular weight of 19,000.

In addition, 30 mg (5% by mass based on the solid content) of the polymerizable compound RM1 was added to 10.0 g of the liquid crystal aligning agent (C), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal aligning agent (C1). ).

In addition, 30 mg (5% by mass based on the solid content) of the polymerizable compound RM2 was added to 10.0 g of the liquid crystal aligning agent (C), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal aligning agent (C2). ).

In addition, 30 mg (5% by mass based on the solid content) of the polymerizable compound RM3 was added to 10.0 g of the liquid crystal aligning agent (C), and the mixture was stirred at room temperature for 3 hours to dissolve the 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 after reacting at 80 ° C for 5 hours, CBDA (1.92 g, 10.0 mmol) and NMP ( 14.1 g), reacting at 40 ° C for 10 hours to obtain a polyaminic acid solution. Add NMP (70.4g) and BCS to this polyaminic acid solution (70.4g) After 93.8 g) was diluted to 6 wt%, the mixture was stirred at room temperature for 10 hours to obtain a liquid crystal director (D). The polyamine had a number average molecular weight of 12,000 and a weight average molecular weight of 21,000.

In addition, 30 mg (5% by mass based on the solid content) of the polymerizable compound RM1 was added to 10.0 g of the liquid crystal aligning agent (D), and the mixture was stirred at room temperature for 3 hours to dissolve the liquid crystal aligning agent (D1). ).

(Synthesis Example 5)

CBDA (1.92 g, 10.0 mmol), p-PDA (0.54 g, 5.0 mmol), 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 Polylysine solution. NMP (23.6 g) and BCS (31.5 g) were added to the polyamic acid solution (23.6 g) to be diluted to 6 wt%, and then stirred at room temperature for 10 hours to obtain a liquid crystal aligning agent (E). . The polyamine has a number average molecular weight of 19,000 and a weight average molecular weight of 28,000.

In addition, 30 mg (5% by mass based on the solid content) of RM1 was added to 10.0 g of the liquid crystal aligning agent (E), and the mixture was stirred at room temperature for 3 hours to be dissolved 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 by a diaphragm pump for 6 minutes, and then AIBN (0.131 g, 0.8 mmol) was added and degassed for 6 minutes. Thereafter, the reaction was carried out at 65 ° C for 20 hours to obtain a polymer solution of methacrylate. Polymer solution BCS (37.8 g) was added and diluted to 6 mass%, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal director (F). The polymer had a number average molecular weight of 16,000 and a weight average molecular weight of 39,000.

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

<Production of Liquid Crystal Cell 2> (Example 3)

The liquid crystal cell was produced in the order shown below using the liquid crystal aligning agent (C1) obtained in Synthesis Example 3. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film was used. The pixel electrode has a comb-like shape in which the electrode elements which are bent in the central portion and have a U-shaped shape are arranged in plural. The width of each electrode element in the short-side direction was 10 μm, and the interval between the electrode elements was 20 μm. The pixel electrode in which each pixel is formed is formed by arranging the electrode elements having a U-shaped bent portion in the central portion as a plurality of columns. Therefore, the shape of each pixel is not rectangular, but is provided in the central portion in the same manner as the electrode elements. Bending is similar to the shape of a bold figure. Further, each pixel is divided into upper and lower sides by a curved portion at the center thereof, and has a first region on the upper side of the curved portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise) in the first region of the pixel, and is in the second region of the pixel. In the middle, the electrode elements of the pixel electrode are formed at an angle of -15 (clockwise). In other words, the first region and the second region of each pixel are configured to be rotated in the substrate surface by the application of a voltage between the pixel electrode and the counter electrode (in-plane, The switching directions are opposite to each other. The liquid crystal aligning agent (C1) obtained in Synthesis Example 3 was spin-coated on the prepared substrate of the above-mentioned electrode. Subsequently, the film was dried on a hot plate at 80 ° C for 90 seconds, and then calcined in a hot air circulating oven at 160 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. Thereafter, the coating film surface was irradiated with a polarizing ultraviolet ray of 313 nm at 50 mJ/cm ² through a polarizing plate to obtain a substrate with a liquid crystal alignment film. Further, as the counter substrate, even if the glass substrate having the columnar spacer having a height of 4 μm in which the electrode was not formed was formed, the coating film was formed in the same manner using the liquid crystal aligning agent (C1), and the alignment treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Next, the other substrate is bonded so that the orientation direction of the liquid crystal alignment film becomes 0°, and then the sealant is cured to produce a hollow cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the hollow cell by a vacuum injection method, and the injection port was sealed to obtain an IPS (In-Plane Switching) mode liquid crystal display element (horizontal electric field drive) The liquid crystal cell of the structure of the liquid crystal display element).

After making liquid crystal cells, the orientation treatment was carried out in an oven at 120 ° C for 60 minutes. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were short-circuited, and the liquid crystal cell was irradiated with 20 J/cm ² (second exposure) through the ultraviolet light of the 365 nm band pass filter.

(afterimage evaluation 2)

The IPS mode liquid crystal cell prepared in each of the third embodiments is placed between two polarizing plates arranged such that the polarization axis is perpendicular, and the backlight is turned on without applying a voltage to transmit light. The brightness becomes the smallest way to adjust the configuration angle of the liquid crystal cells. Next, the rotation angle at which the liquid crystal cell is rotated from the second region of the pixel to the darkest angle to the darkest angle of the first region is calculated as the initial positioning azimuth. Then, an alternating voltage of 16 V _PP was applied at a frequency of 30 Hz in an oven at 60 ° C for 168 hours. Thereafter, the pixel electrode of the liquid crystal cell and the counter electrode were short-circuited, and they were allowed to stand at room temperature for 1 hour. After the placement, the orientation azimuth angle was measured in the same manner, and the difference in the azimuth angles before and after the AC drive was calculated as the angle Δ (deg.). The afterimage evaluation results are shown in Table 2.

(Example 4)

After the liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (C2) was used instead of the liquid crystal aligning agent (C1), afterimage evaluation was performed.

(Example 5)

A liquid crystal cell was produced in the same order as in Example 3 except that the liquid crystal aligning agent (C3) was used instead of the liquid crystal aligning agent (C1), and afterimage was performed. Evaluation.

(Example 6)

After the liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (D1) was used instead of the liquid crystal aligning agent (C1), and the amount of the polarized ultraviolet ray was changed to 500 mJ/cm ² , the afterimage evaluation was performed.

(Example 7)

After the liquid crystal cell was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (E1) was used instead of the liquid crystal aligning agent (C1), afterimage evaluation was performed.

(Example 8)

After the liquid crystal cell was produced in the same order as in Example 3 except that the liquid crystal aligning agent (F1) was used instead of the liquid crystal aligning agent (C1), and the amount of the polarized ultraviolet ray was changed to 500 mJ/cm ² , the afterimage evaluation was performed.

(Example 9)

After the 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), afterimage evaluation was performed.

(Comparative Example 4)

In addition to using a liquid crystal aligning agent (C) in place of the liquid crystal aligning agent (C1), After the liquid crystal cells were produced in the same order as in Example 3 except that the irradiation was not performed twice, the afterimage evaluation was performed.

(Comparative Example 5)

A liquid crystal was produced in the same order as in Example 3 except that the liquid crystal aligning agent (D) was used instead of the liquid crystal aligning agent (C1), and the amount of the polarized ultraviolet ray was changed to 500 mJ/cm ² , and the irradiation was not performed twice. After the cell, the afterimage evaluation was performed.

(Comparative Example 6)

After the 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), the afterimage evaluation was performed.

(Comparative Example 7)

A liquid crystal was produced in the same manner as in Example 3 except that the liquid crystal aligning agent (F) was used instead of the liquid crystal aligning agent (C1), and the amount of the polarized ultraviolet ray was changed to 500 mJ/cm ² , and the irradiation was not performed twice. After the cell, the afterimage evaluation was performed.

From the results of Table 2, it was confirmed that in Comparative Examples 4 to 7 in which the polymerizable compound was not added, the orientation azimuth angle was largely deviated after AC driving, but the polymerizable compound was added, and the liquid crystal cell was UV-produced. In Examples 3 to 8 of irradiation (2 shots), the orientation azimuth angle after AC driving was hardly deviated as compared with Comparative Examples 4 to 7. Next, in Example 9, in which the polymer having a photopolymerizable group in the side chain and the liquid crystal cell were subjected to UV irradiation (second irradiation), the deviation of the orientation azimuth was compared with the case where the irradiation was not performed twice. Example 4 is smaller. In the third to the ninth embodiments, since the surface of the liquid crystal alignment film is fixed by the polymerization of the polymerizable compound or the photopolymerizable group of the polymer by the secondary irradiation, the deviation of the orientation azimuth can be estimated. very small.

Claims (11)

A method for producing a liquid crystal display device for driving a lateral electric field, characterized in that after a liquid crystal aligning agent is applied onto a substrate to form a liquid crystal alignment film and subjected to orientation treatment, a pair of substrates on which the liquid crystal alignment film is formed are formed The liquid crystal alignment film is disposed opposite to each other so as to form a liquid crystal cell, and the liquid crystal cell is irradiated with light to react the photopolymerizable group in the liquid crystal and/or the liquid crystal alignment film. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the liquid crystal system contains a polymerizable compound having the photopolymerizable group. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the liquid crystal aligning agent contains the photopolymerizable group. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the liquid crystal aligning agent contains a polymer having a photopolymerizable group in a side chain. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the liquid crystal aligning agent contains a polymerizable compound having the photopolymerizable group. The method for producing a liquid crystal display device for driving a horizontal electric field according to any one of claims 3 to 5, wherein the photopolymerizable group is selected from the group consisting of photopolymerizable groups shown below. base, (wherein Me represents a methyl group). The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the aligning treatment is performed by irradiation of polarized ultraviolet rays. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the alignment treatment has a structure selected from the following formulas (A-1) to (A-7). Photoreactive group to carry out the reaction The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the polymer contained in the liquid crystal aligning agent comprises a polyimine precursor and a polycondensation obtained by imidating the polymer. At least one selected from the group consisting of quinone imines. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the polymer contained in the liquid crystal aligning agent comprises a polyoxyalkylene. The method for producing a liquid crystal display device for driving a horizontal electric field according to the first aspect of the invention, wherein the polymer contained in the liquid crystal aligning agent comprises a poly(meth)acrylate.