CN104136976A - Method for manufacturing liquid-crystal display element for use with in-plane switching - Google Patents

Abstract

The present invention is a method for manufacturing a liquid crystal display element for lateral electric field driving, characterized in that it includes the steps of coating a liquid crystal alignment agent on a substrate to form a liquid crystal alignment film and performing an alignment treatment, arranging a pair of substrates on which the liquid crystal alignment film has been formed facing each other according to conditions that make the liquid crystal alignment film face each other to form a liquid crystal cell, and then irradiating the liquid crystal cell with light to cause the liquid crystal to neutralize/or the photopolymerizable groups in the liquid crystal alignment film to react.

Description

Method for manufacturing liquid crystal display element for lateral electric field drive

technical field

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

Background technique

A liquid crystal display element used for a liquid crystal television, a liquid crystal display, etc. is normally provided with the liquid crystal aligning film for controlling the orientation state of a liquid crystal in an element.

At present, according to the most common method in the industry, the liquid crystal alignment film is made of polyamic acid and/or imidized polyamic acid formed on the electrode substrate by wiping in one direction with cloth such as cotton, nylon, polyester, etc. The surface of the film formed of imide is so-called friction treatment.

In the orientation process of a liquid crystal aligning film, the method of rubbing a film surface is a simple and industrially useful method excellent in productivity. However, the requirements for higher performance, higher definition, and larger size of liquid crystal display elements are increasing day by day. Damage to the surface of the liquid crystal alignment film caused by rubbing, dust, mechanical force or static electricity, and unevenness in the alignment treatment surface Various problems such as uniformity are becoming more and more obvious.

As a method instead of the rubbing treatment, there is known a photo-alignment method in which liquid crystal alignment ability is provided by irradiating polarized ultraviolet rays. As for the liquid crystal alignment treatment by the photo-alignment method, treatment by photoisomerization reaction, treatment by photodimerization, treatment by photolysis reaction, etc. have been proposed according to the mechanism (refer to Non-Patent Document 1).

For example, Patent Document 1 proposes a method of using a polyimide film having an alicyclic structure such as a cyclobutane ring on the main chain for the photo-alignment method. When using the polyimide film which adopted this photo-alignment method as a liquid crystal aligning film, since it has high heat resistance compared with another method, the usefulness can be expected.

Such a polyimide film having an alicyclic structure such as a cyclobutane ring exhibits high anisotropy by irradiating short-wavelength ultraviolet rays, especially polarized ultraviolet rays near 254 nm, to obtain a liquid crystal aligning film excellent in liquid crystal orientation. However, since the energy of ultraviolet light near 254 nm is high, a large amount of electric power is required for irradiation, and not only the cost for photo-alignment treatment is high, but also the load on the environment is large. In addition, in order to use short-wavelength ultraviolet rays with higher energy, there is a possibility of damaging electrodes or thin-film transistors (hereinafter also referred to as TFTs) formed on the substrate.

On the other hand, in the photo-alignment method utilizing photoisomerization or photodimerization, anisotropy can be imparted by irradiating polarized ultraviolet rays with a wavelength of 300 nm or more. However, the alignment regulation force of the liquid crystal aligning film obtained by the photo-alignment method of photoisomerization or photodimerization is weak, and when using it for a liquid crystal display element, there exists a problem that image sticking arises.

Here, there is known a liquid crystal display element of an in-plane electric field driving method (IPS: In-Plane Switching) in which an electric field is applied to a substrate in a horizontal direction (lateral direction) to drive liquid crystal molecules. This lateral electric field drive type liquid crystal display element is useful because of its wide viewing angle, but it has the problem of being particularly prone to image sticking as described above because it is easily affected by the alignment state of the liquid crystal.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 9-297313

non-patent literature

Non-Patent Document 1: "Liquid Crystal Photo-Alignment Film" Ri Kido, Ichimura Functional Materials, November 1997 Vol.17 No.1113-22

Contents of the invention

The technical problem to be solved by the invention

An object of the present invention is to provide a method of manufacturing a liquid crystal display element for lateral electric field driving, which can strengthen the alignment regulating force of liquid crystal and suppress the occurrence of afterimage.

Technical solutions adopted to solve technical problems

In order to achieve the above object, the present inventors found that the liquid crystal display element for lateral electric field driving obtained by the following method can achieve the above object when conducting serious research; The liquid crystal of the polymeric compound of the group, or use the liquid crystal aligning film obtained by the liquid crystal aligning agent that has the photopolymerizable group, utilize rubbing or photo-orientation method to carry out alignment treatment, after making the liquid crystal unit cell, by irradiating the light to make the existence A method of curing the liquid crystal in the part in contact with the liquid crystal aligning film by reacting the photopolymerizable group in the liquid crystal aligning film and the liquid crystal contact portion. In summary, the technical content of the present invention is as follows.

1. A method for manufacturing a liquid crystal display element driven by a transverse electric field, comprising coating a liquid crystal aligning agent on a substrate to form a liquid crystal aligning film and implementing alignment treatment, and then forming a liquid crystal aligning film through a liquid crystal Arranging the substrates facing each other so that the liquid crystal alignment film faces each other to produce a liquid crystal cell, and then irradiating the liquid crystal cell with light to react the photopolymerizable groups in the liquid crystal and/or in the liquid crystal alignment film process.

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

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

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

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

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

[chemical 1]

(In the formula, Me represents a methyl group.)

7. The method for manufacturing a liquid crystal display element for transverse electric field drive according to any one of 1 to 6, wherein the alignment treatment is performed by irradiation of polarized ultraviolet rays.

8. The method for manufacturing a liquid crystal display element driven by a transverse electric field as described in any one of 1 to 7, wherein, in the alignment treatment, a method selected from the following formulas (A-1) to (A-7) The photoreactive group of the structure reacts.

[Chem 2]

9. The method for manufacturing a liquid crystal display element driven by a transverse electric field as described in any one of 1 to 8, wherein the polymer contained in the liquid crystal aligning agent comprises polyimide precursors and At least one type of polyimide obtained by imidization.

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

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

The effect of the invention

If the present invention is adopted, it is possible to obtain a liquid crystal aligning film equipped with orientation treatment by rubbing or photo-alignment method, especially a liquid crystal alignment film that implements orientation treatment by photo-alignment. Liquid crystal display element.

Detailed ways

The present invention is a method for manufacturing a liquid crystal display element driven by a transverse electric field, which is characterized in that it includes coating a liquid crystal aligning agent on a substrate to form a liquid crystal aligning film and performing orientation treatment, and then forming the liquid crystal aligning film through a liquid crystal. A pair of substrates are arranged facing each other under the condition that the above-mentioned liquid crystal alignment film is opposed to produce a liquid crystal cell, and then the liquid crystal cell is irradiated with light to react the photopolymerizable group in the liquid crystal and/or in the liquid crystal alignment film. process. Hereinafter, each constituent requirement will be described in detail.

<Photopolymerizable group>

The liquid crystal aligning agent and/or liquid crystal used for the manufacturing method of this invention contain a photopolymerizable group. A photopolymerizable group-containing liquid crystal is obtained by adding a photopolymerizable group-containing compound (hereinafter also referred to as a polymerizable compound) to a liquid crystal. In addition, 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, and a photopolymerizable group may be introduced into a side chain of a polymer contained in the liquid crystal aligning agent, or It's both. The liquid crystal aligning film obtained using such a liquid crystal aligning agent contains a photopolymerizable group. When adding a polymeric compound to a liquid crystal, the addition ratio can be 0.1-30 (mass)% of a polymeric compound with respect to a liquid crystal, for example. Moreover, when adding a polymeric compound to a liquid crystal aligning agent, the addition ratio can be 0.1-30 (mass)% of a polymeric compound with respect to a liquid crystal aligning agent, for example.

When light such as ultraviolet light is irradiated to a liquid crystal display element containing a photopolymerizable group in the liquid crystal alignment film and/or liquid crystal, the photopolymerizable group located on the surface in contact with the liquid crystal alignment film and the liquid crystal reacts, and the The orientation of the liquid crystals on the surface of the film is cured. As a result, as shown in the examples described later, good liquid crystal orientation is obtained, and the orientation-regulating force of the liquid crystal is strengthened. As a result, the electrical characteristics such as image sticking caused by disordered liquid crystal orientation are improved. .

The photopolymerizable group is a group that undergoes a polymerization reaction by light such as ultraviolet rays, for example, as long as it is a group that is polymerized by light such as ultraviolet rays (hereinafter also referred to as a photopolymerizable group) or a photocrosslinking group (hereinafter (also referred to as a photocrosslinking group) is not particularly limited, but the structures shown below are preferably used.

[Chem 3]

(In the formula, Me represents a methyl group.)

As a specific example of a polymerizable compound, a compound represented by the following formula (I) having a photopolymerizable group at two terminals, a compound represented by the following formula (II) including a terminal having a photopolymerizable group and The terminal compound having a photocrosslinkable group is a compound represented by the following formula (III) having a photocrosslinkable group at each of its two terminals. In addition, in the following formulas (I) to (III), R ¹² is H or an alkyl group with 1 to 4 carbons, Z ¹ is an alkyl group with 1 to 12 carbons or an alkoxy group with 1 to 12 carbons Substituted divalent aromatic ring or heterocyclic ring, ^Z2 is a monovalent aromatic ring or heterocyclic ring that can be substituted by an alkyl group with 1 to 12 carbons or an alkoxy group with 1 to 12 carbons, ^Q1 is a divalent organic group group. Q ¹ preferably has a ring structure such as phenylene (-C ₆ H ₄ -), biphenylene (-C ₆ H ₄ -C ₆ H ₄ -) or cyclohexylene (-C ₆ H ₁₀ -). This is because the interaction with the liquid crystal tends to increase.

[chemical 4]

[chemical 5]

Specific examples of the polymerizable compound represented by the formula (I) include polymerizable compounds represented by the following formulas (I-1) to (I-5). In the following formula, V is a single bond or represented by -R ¹ O-, wherein R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by -R ¹ O-, wherein R ¹ is A linear or branched alkylene group having 2 to 6 carbon atoms. In addition, W is a single bond or represented by -OR ² -, wherein R ² is a linear or branched alkylene group having 1 to 10 carbons, preferably represented by -OR ² -, wherein R ² is linear or branched An alkylene group having 2 to 6 carbon atoms in the chain. In addition, V and W may have the same structure or different structures, and if they are the same, synthesis is easy.

[chemical 7]

In addition, even if it is a polymerizable compound that does not have an α-methylene-γ-butyrolactone group but has an acrylate group or a methacrylate group as a photopolymerizable group or a photocrosslinkable group, as long as it has The acrylate group or methacrylate group is a polymeric compound with a structure in which the phenylene group is bonded to the phenylene group through a spacer group such as an oxyalkylene group. Like the lactone-based polymerizable compound, it can greatly improve the image sticking property under AC stress, that is, it can significantly suppress the image sticking caused by the application of alternating current (AC). In addition, if it is a polymerizable compound having a structure in which an acrylate group or a methacrylate group is bonded to a phenylene group through a spacer group such as an oxyalkylene group, it may be sufficiently resistant to heat due to improved thermal stability. Subject to high temperature such as firing temperature above 200°C.

Moreover, as a specific example of the polymeric compound represented by formula (I), the polymeric compound of the following formula is also mentioned.

[chemical 8]

(In the formula, the definitions of R ¹² , V, and W are the same as above.)

The method for producing such a polymerizable compound is not particularly limited, and can be produced, for example, according to the synthesis examples described later. For example, a polymerizable compound represented by the above formula (I-1) can be synthesized by combining techniques in synthetic organic chemistry. For example, SnCl can be used by the method proposed by Talaga et al. P. Talaga, M. Schaeffer, C. Benezra and JLStampf in Synthesis ("Synthesis" magazine), 530 (1990) represented by the following reaction formula ₂ Synthesis is carried out by reacting 2-(bromomethyl)propenoic acid with aldehyde or ketone. In addition, Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas, and THF is tetrahydrofuran.

[chemical 9]

(In the formula, R' represents a monovalent organic group.)

In addition, 2-(bromomethyl)acrylic acid can be obtained by Ramarajan et al. K. Ramarajan, K.Kamalingam, D.J.O'Donnell and K.D.Berlin in OrganicSynthesis ("Organic Synthesis" magazine) represented by the following reaction formula , vol.61,56-59 (1983) in the proposed method to synthesize.

[chemical 10]

As a specific synthesis example, when synthesizing a polymerizable compound represented by the above formula (I-1) in which V is -R ¹ O-, W is -OR ² -, and R ¹ and R ² are the same, Two methods represented by the following reaction formula.

[chemical 11]

[chemical 12]

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 can be exemplified.

[chemical 13]

Moreover, when synthesizing the polymeric compound represented by the said formula (I-1) whose V and W are a single bond, the method represented by the following reaction formula is mentioned.

[chemical 14]

When a photopolymerizable group is introduced into the side chain of the polymer contained in the liquid crystal aligning agent, even when there is little or no polymerizable compound in the liquid crystal or in the liquid crystal aligning agent, the effect of the present invention can be obtained. Of course, a polymeric compound may exist in a liquid crystal or a liquid crystal aligning agent, and in this case, further effect can be expected. A side chain into which a photopolymerizable group is introduced (hereinafter also referred to as a photopolymerizable side chain) refers to a side chain containing a group selected from methacryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene A side chain of at least one of the group-γ-butyrolactone group. In this way, the polyimide precursor contained in the liquid crystal aligning agent and at least one of the polyimides obtained by imidizing the polyimide precursor are polymers containing Polymers with photopolymerizable side chains of at least one of acryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene-γ-butyrolactone groups, by combining with the above polymerizability When the compound is used in a liquid crystal aligning agent at the same time, as shown in the examples described later, image sticking characteristics such as AC stress can be significantly improved.

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

[chemical 15]

-R ⁸ -R ⁹ -R ¹⁰ (b)

(In formula (b), R ⁸ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N Any one of (CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-; R ⁹ represents a single bond, or an unsubstituted or fluorine-substituted alkylene with 1 to 20 carbons The -CH ₂ - of the alkylene group can be optionally substituted by -CF ₂ - or -CH=CH-, and any of the groups listed below can also be substituted by these groups when they are not adjacent to each other: -O -, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocyclic ring, divalent heterocyclic ring. R ¹⁰ represents methacryloyl, acryloyl, vinyl, allyl group, styryl group and α-methylene-γ-butyrolactone group.)

In addition, although it can be formed by a conventional organic synthesis technique, R ⁸ in the above formula (b) is preferably -CH ₂ -, -O-, -COO-, -NHCO-, -NH-, _-CH2O- .

In addition, as the carbocyclic or heterocyclic divalent carbocyclic or heterocyclic divalent ring that may be substituted for any -CH ₂ - of R ⁹ , specific examples include the following structures, but are not limited thereto.

[chemical 16]

R ¹⁰ is preferably a methacryloyl group, an acryloyl group, a vinyl group or an α-methylene-γ-butyrolactone group from the viewpoint of photopolymerization.

The amount of photopolymerizable side chains is preferably within a range in which the alignment can be cured by forming a covalent bond by reacting with irradiation of ultraviolet light, and within a range that does not affect other properties in order to further improve AC image sticking characteristics Preferably as many as possible.

In this way, for the production of photopolymerizable compounds having at least one selected from methacryloyl, acryloyl, vinyl, allyl, styryl and α-methylene-γ-butyrolactone groups The polyimide precursor of the side chain and the method of at least one polymer in the polyimide obtained by imidating the polyimide precursor are not particularly limited, for example, by diamine In the method for obtaining polyamic acid by reacting with tetracarboxylic dianhydride, diamine or tetracarboxylic dianhydride can be copolymerized, and the diamine or tetracarboxylic dianhydride have , a photopolymerizable side chain of at least one of a vinyl group, an allyl group, a styryl group, and an α-methylene-γ-butyrolactone group.

<polymer>

The polymer contained in the liquid crystal aligning agent used in the present invention is preferably polysiloxane or poly(meth)acrylic acid other than the polyimide precursor and the imidized polyimide. ester. Here, the polyimide precursor refers to polyamic acid (Polyamic acid, also called Polyamide acid) or polyamic acid ester. Moreover, these different polymers may be contained together in a liquid crystal aligning agent, and these content ratios can be selected variously according to the characteristic of a liquid crystal display element. It is preferable that the total amount of the polymer contained in a liquid crystal aligning agent is 0.1-20 (mass)%. In addition, polymers such as polyimide precursors, polyimides, polysiloxanes, and poly(meth)acrylates contained in the liquid crystal aligning agent of the present invention need to be soluble in the solvent contained in the liquid crystal aligning agent. .

<Photoreactive group>

In the step of alignment treatment in the production method of the present invention, when polarized ultraviolet rays are used, it is necessary to introduce a photoreactive group that exhibits liquid crystal alignment ability by utilization of polarized ultraviolet rays into the polymer contained in the liquid crystal aligning agent. Such a photoreactive group may be introduced into the main chain of the polymer or may be introduced into a side chain.

By irradiating polarized ultraviolet rays to a liquid crystal aligning film obtained from a liquid crystal aligning agent containing a polymer having a photoreactive group introduced, photoreaction is performed to impart anisotropy in the same direction as the polarization direction or in a direction perpendicular to the polarization direction , to align the liquid crystal. Photoreactions include photolysis, photodimerization, and photoisomerization. If specific examples are given, structures represented by the following formulas (A-3), (A-4), and (A-5) may be mentioned as structures that undergo a photodimerization reaction. As a structure which undergoes a photoisomerization reaction, the structure represented by following formula (A-6) and (A-7) is mentioned. As a structure which performs a photolysis reaction, the structure represented by following formula (A-1) and (A-2) is mentioned. In addition, the photoreactive group having a structure selected from the following formulas (A-1) to (A-7) means that after taking any number of H in the structures of these formulas (A-1) to (A-7) groups, groups where N is a bond in formulas (A-1) to (A-2), groups where O is a bond in formula (A-3), or these structures and other structures (such as alkylene, etc. ) combined groups.

[chemical 17]

<Polyimide precursor and polyimide obtained by imidating it>

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

[chemical 18]

In formula (1), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easiness of imidation 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. If specific examples are given, the following formulas (X-1) to (X-43) may be mentioned. From the viewpoint of liquid crystal orientation, _X2 is preferably (X-1) to (X-10), (X-26) to (X-28), and (X-31) to (X-37). In addition, from the viewpoint of obtaining a liquid crystal aligning film that relaxes the residual charge accumulated under the action of DC voltage, it is preferable to use tetracarboxylic dianhydride having an aromatic ring structure as a raw material, and as _X2 of the formula (1) structure, more preferably (X-26), (X-27), (X-28), (X-32), (X-35) or (X-37).

[chemical 19]

(In formula (X-1), R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbons, an alkenyl group with 2 to 6 carbons, a chain Alkenyl or phenyl. 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, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom or a methyl group. At least one of the structures represented by the following formulas (X1-1) to (X1-2).)

[chemical 20]

[chem 22]

[chem 23]

In the process of orientation treatment in the production method of the present invention, when polarized ultraviolet light is used, as a preferable structure of _X2 , (X1-1), (X1-2), (X-2), (X1-1), (X1-2), ( X-3), (X-5), (X-7), (X-8), (X-9), (X-10), particularly preferably (X1-1), (X1-2) and ( X-6).

In the above formula (1), Y ₂ is a divalent organic group, and its structure is not particularly limited. If specific examples of _Y2 are to be given, the following formulas (Y-1) to (Y-73) may be mentioned.

[chem 24]

[chem 25]

[chem 26]

[chem 27]

[chem 28]

[chem 29]

[chem 30]

[chem 31]

(In the formula, Me represents a methyl group.)

In order to expect the improvement of the solubility of polyimide precursors or polyimides to organic solvents, it is preferable to contain (Y-8), (Y-20), (Y-21), (Y-22) , (Y-28), (Y-29) or a structural unit of the structure of (Y-30).

The polyimide precursor contained in the liquid crystal aligning agent used in the present invention has diamines such as diamines having photopolymerizable side chains or diamines having photoreactive groups, etc. ) and a tetracarboxylic dianhydride component (for example, tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or tetracarboxylic diester described later) can be obtained by reaction. Specifically, polyamic acid is obtained by reaction of a diamine component and tetracarboxylic dianhydride. Polyamic acid ester is obtained by reacting diamine components and tetracarboxylic acid diester dichloride in the presence of alkali, or by reacting tetracarboxylic diester and diamine components in the presence of a suitable condensing agent and alkali . Moreover, a polyimide can be obtained by dehydrating and ring-closing this polyamic acid, or heating a polyamic acid ester, and ring-closing. As a polymer for obtaining a liquid crystal aligning film, any of the above-mentioned polyamic acid, polyamic acid ester, and polyimide is useful.

<Diamine having a photopolymerizable side chain>

Diamine having a photopolymerizable side chain containing at least one selected from methacryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene-γ-butyrolactone groups For example, a diamine having a side chain represented by the above formula (b) may be mentioned. More specifically, although diamine represented by following general formula (2) is mentioned, for example, it is not limited to this.

[chem 32]

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

The binding positions of the two amino groups (—NH ₂ ) in formula (2) are not limited. Specifically, the 2,3-position, 2,4-position, 2,5-position, 2,6-position, 3,4-position, and 3,5-position on the benzene ring of the binding group with respect to a side chain are mentioned. Among these, the 2,4-position, 2,5-position, or 3,5-position is preferable from a reactive viewpoint at the time of polyamic-acid synthesis. In consideration of ease of synthesis of diamine, 2,4-position or 3,5-position is more preferable.

Diamine having a photopolymerizable side chain containing at least one selected from methacryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene-γ-butyrolactone groups , specifically, the following compounds may be exemplified, but not limited thereto.

[chem 33]

(In the formula, X represents a single bond, or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or a non-substituted or fluorine atom-substituted carbon number of 1 to 20 alkylene.)

The aforementioned diamine having a photoreactive side chain comprising at least one selected from methacryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene-γ-butyrolactone groups Depending on properties such as liquid crystal orientation when forming a liquid crystal alignment film, pretilt angle, voltage retention characteristics, and accumulated charge, and liquid crystal response speed when forming a liquid crystal display element, you can use one or a mixture of two or more.

In addition, such a photopolymerizable side chain having at least one selected from methacryloyl, acryloyl, vinyl, allyl, styryl, and α-methylene-γ-butyrolactone groups The diamine is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 50 mol%, based on the total amount of diamine components used in the synthesis of polyamic acid.

<Diamine having a photoreactive group>

In the process of the orientation treatment in the manufacturing method of this invention, when polarized ultraviolet-ray is used, it is necessary to introduce a photoreactive group into the polymer contained in a liquid crystal aligning agent.

In the case of using an orientation treatment method in which anisotropy is generated by photodecomposition reaction by irradiation of polarized ultraviolet rays, the structures of the above formulas (A-1), (A-2) can be introduced into the polyimide precursor and The main chain of polyimide.

In the case of using an orientation treatment method in which anisotropy is generated by photodimerization or photoisomerization reaction by irradiation of polarized ultraviolet rays, the structures of the above formulas (A-3) and (A-7) can be introduced into polymerization The main chain or side chain of the substance.

As the polymer contained in the liquid crystal aligning agent, in the case of using a polyimide precursor and a polyimide obtained by imidizing it, there are those containing the above formula in the main chain or side chain (A-3)～(A-7) The method of the tetracarboxylic dianhydride or diamine of the structure, but from the viewpoint of the ease of synthesis, it is preferable to use the side chain containing the above-mentioned formula (A-3) A diamine having a structure of -(A-7). In addition, the side chain of a diamine means the structure branched from the structure which connected the two amino groups of a diamine. As a specific example of such diamine, the compound represented by the following formula is mentioned, However, It is not limited to these.

[chem 34]

(In the formula, X represents a single bond, or a bonding group selected from -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or a non-substituted or fluorine atom-substituted carbon number of 1 to An alkylene group of 20. R represents a hydrogen atom, or an unsubstituted or fluorine atom-substituted alkyl or alkyl ether group with 1 to 5 carbons.)

<Tetracarboxylic dianhydride component>

In order to obtain the polyamic acid contained in the liquid crystal aligning agent used for this invention, the tetracarboxylic dianhydride which reacts with a diamine component is not specifically limited. Specific examples thereof will be given below.

As the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 ,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-Cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic 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-tricarboxycyclopentylacetic dianhydride, cis-3,7-dibutylcyclooct-1,5-diene- 1,2,5,6-Tetracarboxylic dianhydride, Tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dianhydride, Hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-di anhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, etc.

Also, if an aromatic tetracarboxylic dianhydride is used in addition to the above-mentioned tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, the liquid crystal orientation is improved, and the accumulated charge of the liquid crystal cell can be reduced, so it is preferred . Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic Carboxylic acid dianhydride, 2,3,3',4-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4- Benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic Acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, etc.

Tetracarboxylic dianhydride may be used alone or in combination of two or more depending on properties such as liquid crystal orientation when forming a liquid crystal aligning film, voltage retention, and accumulated charge.

In order to obtain the polyamic acid ester contained in the liquid crystal aligning agent used for this invention, the tetracarboxylic-acid dialkyl ester which reacts with a diamine component is not specifically limited. Specific examples thereof will be given below.

Specific examples of aliphatic tetracarboxylic acid diesters include dialkyl 1,2,3,4-cyclobutanetetracarboxylate, 1,2-dimethyl-1,2,3,4- Dialkyl cyclobutane tetracarboxylate, 1,3-dimethyl-1,2,3,4-dialkyl cyclobutane tetracarboxylate, 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 Dialkyl esters, dialkyl 1,2,4,5-cyclohexanetetracarboxylate, dialkyl 3,4-dicarboxy-1-cyclohexylsuccinate, 3,4-dicarboxy-1 ,Dialkyl 2,3,4-tetrahydro-1-naphthalene succinate, dialkyl 1,2,3,4-butane tetracarboxylate, bicyclo[3,3,0]octane- Dialkyl 2,4,6,8-tetracarboxylate, Dialkyl 3,3',4,4'dicyclohexyltetracarboxylate, Dialkyl 2,3,5-tricarboxycyclopentyl acetate dialkyl ester, cis-3,7-dibutylcyclooct-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]nonane-3 ,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl ester, hexacyclic [6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ] ten Hexa-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3 , 4-Tetralin-1,2-dicarboxylic acid dialkyl ester, etc.

Examples of aromatic tetracarboxylic acid dialkyl esters include pyromellitic acid dialkyl esters, 3,3',4,4'-biphenyl tetracarboxylic acid dialkyl esters, 2,2',3, Dialkyl 3'-Biphenyl Tetracarboxylate, Dialkyl 2,3,3',4-Biphenyl Tetracarboxylate, Dialkyl 3,3',4,4'-Benzophenone Tetracarboxylate Dialkyl ester, 2,3,3',4-benzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) ) dialkyl sulfone ester, dialkyl 1,2,5,6-naphthalene tetracarboxylate, dialkyl 2,3,6,7-naphthalene tetracarboxylate, etc.

<Manufacturing method of polyamic acid>

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

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

The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, and γ-butyrolactone from the solubility of monomers and polymers, and these can be used 1 or a mixture of two or more. The concentration of the polymer is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer does not easily occur and a high molecular weight body is easily obtained.

The polyamic acid produced in this way can deposit and collect|recover a polymer by pouring into a poor solvent, fully stirring a reaction solution. Moreover, the powder of the purified polyamic acid can be obtained by normal temperature or heat drying after carrying out precipitation several times and washing|cleaning with a poor solvent. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Manufacturing method of polyamic acid ester>

The polyamic acid ester which is a polyimide precursor can be compounded by the method of (1)-(3) shown below.

(1) When synthesized from polyamic acid

Polyamic acid ester can be compounded by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.

Specifically, it can be synthesized by reacting polyamic acid and an esterifying agent at -20°C to 150°C, preferably 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 to 4 hours, in the presence of an organic solvent.

The esterifying agent is preferably one that can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide di-neopentyl butyl acetal, N,N-dimethylformamide di-tert-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 salt etc. The addition amount of the esterification agent is preferably 2 to 6 molar equivalents with respect to 1 mole of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the polymer, and one or more of these solvents can be used. Use 2 or more types in combination. The concentration at the time of synthesis is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer does not easily occur and that a high molecular weight body is easily obtained.

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

Polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine.

Specifically, tetracarboxylic acid diester dichloride and diamine can be reacted at -20 to 150°C, preferably 0 to 50°C, for 30 minutes to 24 hours, preferably 1 to 4 hours, in the presence of a base and an organic solvent. to synthesize.

As the above-mentioned base, pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used, and pyridine is preferable in order to make the reaction proceed mildly. It is preferable that the addition amount of a base is 2-4 times mole with respect to a tetracarboxylic-acid diester diacid chloride from the viewpoint that it is easy to remove the quantity and obtain a high molecular weight body.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone and γ-butyrolactone from the viewpoint of monomer and polymer solubility, and these can be used alone or in combination of two or more. The polymer concentration during synthesis is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer does not easily occur and that a high molecular weight body is easily obtained. In addition, in order to prevent the hydrolysis of tetracarboxylic acid diester diacid chloride, the solvent used in the synthesis of polyamic acid ester is preferably in a dehydrated state as much as possible, and it is preferably performed in a nitrogen atmosphere to prevent the mixing of foreign gases.

(3) Synthesis of polyamic acid from tetracarboxylic acid diester and diamine

Polyamic acid ester can be compounded by polycondensing tetracarboxylic-acid diester and diamine.

Specifically, tetracarboxylic acid diester and diamine can be reacted at 0°C to 150°C, preferably 0°C to 100°C, for 30 minutes to 24 hours, preferably 3 to 24 hours, in the presence of a condensing agent, a base, and an organic solvent. 15 hours to synthesize.

As the above-mentioned condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N' -Carbonyldiimidazole, Dimethoxy-1,3,5-triazinemethylmorpholine, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea Tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea Hexafluorophosphate, (2,3-dihydro-2-thio-3-benzo Azolyl) diphenyl phosphonate, etc. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to a tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. It is preferable that the addition amount of a base is 2-4 times mole with respect to a diamine component from the viewpoint of the quantity which can be removed easily and a high molecular weight body easily.

In addition, in the above reaction, adding a Lewis acid as an additive enables the reaction to proceed efficiently. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. It is preferable that the addition amount of a Lewis' acid is 0-1.0 times mole with respect to a diamine component.

Among the synthetic methods of the above three kinds of polyamic acid esters, the synthetic method of the above (1) or the above (2) is particularly preferable in order to obtain a high molecular weight polyamic acid ester.

The solution of the polyamic acid ester obtained above can deposit a polymer by pouring into a poor solvent, fully stirring a reaction solution. After performing precipitation several times and washing|cleaning with a poor solvent, it can obtain the powder of the purified polyamic acid ester at normal temperature or heat drying. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Manufacturing method of soluble polyimide>

The said polyimide can be manufactured by imidating the said polyamic acid or polyamic acid ester. In the case of producing polyimide from polyamic acid ester, chemical imidization is convenient, and this chemical imidation is to dissolve the above-mentioned polyamic acid ester solution or polyamic acid ester powder in an organic solvent, and A basic catalyst is added to the obtained polyamic acid solution. Chemical imidization is preferred because the imidization reaction is carried out at a relatively low temperature, and the molecular weight of the polymer is less likely to decrease during the imidization process.

The chemical imidation can be performed by stirring the polyamic acid ester to be imidized in an organic solvent under the presence of a basic catalyst. As the organic solvent, the solvents used in the above-mentioned polymerization reaction can be used. As a basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned. Among them, triethylamine is preferred because it has sufficient basicity to allow the reaction to proceed.

The temperature during the imidization reaction may be -20°C to 140°C, preferably 0°C to 100°C, and the reaction time may be 1 to 100 hours. The quantity of basic catalyst is 0.5-30 mole times of amic acid ester group, Preferably it is 2-20 mole times. The imidization rate of the obtained polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time. Since the added catalyst etc. remain in the solution after imidation reaction, it is preferable to use as a liquid crystal aligning agent after recovering the obtained imidation polymer by the following method and redissolving it in an organic solvent.

In the case of producing polyimide from polyamic acid, chemical imidization is conveniently performed by reacting the above-mentioned polyamic acid produced by diamine component and tetracarboxylic dianhydride. A catalyst is added to the solution. The chemical imidization is to carry out the imidization reaction at a relatively low temperature, and the reduction of the molecular weight of the polymer is unlikely to occur during the imidization process, so it is preferred.

Chemical imidization can be performed 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 solvents used in the above-mentioned polymerization reaction can be used. As a basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned. Of these, pyridine is preferred because it has a suitable basicity to allow the reaction to proceed. Moreover, as an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned, Among them, when using acetic anhydride, it is easy to perform purification after completion|finish of reaction, and it is preferable.

The temperature during the imidization reaction may be -20°C to 140°C, preferably 0°C to 100°C, and the reaction time may be 1 to 100 hours. The amount of basic catalyst is 0.5-30 mole times of amic acid group, preferably 2-20 mole times, and the amount of acid anhydride is 1-50 mole times of amic acid group, preferably 3-30 mole times. The imidization rate of the obtained polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.

In the solution after the imidation reaction of polyamic acid ester or polyamic acid, the added catalyst etc. remain, so it is preferable to recover the imidated polymer obtained by the following method and redissolve it with an organic solvent, then use As a liquid crystal aligning agent of the present invention.

A polymer can be precipitated by pouring the solution of the polyimide produced above into a poor solvent, stirring well. After performing precipitation several times and washing|cleaning with a poor solvent, it can obtain the powder of the purified polyamic acid ester at normal temperature or heat drying.

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

<Production method of polysiloxane>

The method of obtaining the polysiloxane used in the present invention is not particularly limited, for example, it can be obtained by condensing an alkoxysilane in an organic solvent. Usually, polysiloxane can be obtained as the solution which melt|dissolved uniformly in the organic solvent after polycondensing the said alkoxysilane.

As a method of polycondensing an alkoxysilane, the method of hydrolyzing and condensing an alkoxysilane in solvents, such as alcohol and diol, is mentioned, for example.

At this time, the hydrolytic condensation reaction may be any of partial hydrolysis and complete hydrolysis. For complete hydrolysis, it is sufficient to add 0.5 times the mole of water of all the alkoxy groups in the alkoxysilane in theory, but it is usually preferable to add water in an amount exceeding 0.5 times the mole.

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

In addition, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine, etc. are usually used for the purpose of promoting hydrolysis and condensation reactions. Catalysts such as alkalis, metal salts of hydrochloric acid, sulfuric acid, nitric acid, etc. In addition, generally, the solution in which the alkoxysilane is dissolved is heated to further promote the hydrolysis and condensation reactions. At this time, the heating temperature and heating time can be appropriately selected as necessary. For example, the method of heating and stirring at 50 degreeC for 24 hours, the method of heating and stirring under reflux for 1 hour, etc. are mentioned.

Moreover, as another method, the method of heating and polycondensing the mixture of an alkoxysilane, a solvent, and oxalic acid is mentioned, for example. Specifically, it is a method of adding oxalic acid to alcohol in advance to form an alcohol solution of oxalic acid, and then mixing the alkoxysilane with the solution heated. In this case, the amount of oxalic acid used is preferably 0.2 to 2 moles relative to 1 mole of all the alkoxy groups contained in the alkoxysilane. The heating in this method can be performed at a liquid temperature of 50 to 180°C. In order to avoid evaporation, volatilization, etc. of the liquid, a method of heating under reflux for several tens of minutes to ten hours is preferable.

When using several types of alkoxysilanes at the time of polysiloxane manufacture, alkoxysilanes may be mixed as the mixture previously mixed, and several types of alkoxysilanes may be mixed sequentially.

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

Examples of the alkoxysilane compound having a photopolymerizable group on the side chain include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, Methacryloxymethyltrimethoxysilane, Methacryloxymethyltriethoxysilane, 3-Acryloxypropyltrimethoxysilane, 3-Acryloxypropyl Triethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styreneethyltrimethoxysilane, styreneethyltriethoxysilane, 3- (N-Styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, Vinylphenylethyltrimethoxysilane, Vinylphenylethyltriethoxysilane, Vinyltrimethoxy Silane etc.

Examples of other alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyl Triethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2(aminoethyl) 3-aminopropyltriethyl Oxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, 3-(2-aminoethylaminopropyl)trimethoxysilane, 3-(2-aminoethylaminopropyl ) Triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2-(2-aminoethylthioethyl)triethoxysilane, 3-mercaptopropyltriethoxysilane, Mercaptomethyltrimethoxysilane, Vinyltriethoxysilane, 3-Isocyanatopropyltriethoxysilane, Trifluoropropyltrimethoxysilane, Chloropropyltriethoxysilane, Bromopropyltriethoxysilane Ethoxysilane, 3-Mercaptopropyltrimethoxysilane, Dimethyldiethoxysilane, Dimethyldimethoxysilane, Diethyldiethoxysilane, Diethyldimethoxysilane , diphenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane silane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane and γ-ureidopropyltripropoxysilane, etc.

The solvent used for the polycondensation of alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane. Moreover, even when alkoxysilane does not dissolve, what is necessary is just to dissolve simultaneously with the polycondensation reaction of alkoxysilane. Generally, alcohols, glycols, glycol ethers, or organic solvents with good compatibility with alcohols are used because alcohols are produced by the polycondensation reaction of alkoxysilanes.

Specific examples of the above-mentioned 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, 1 , 4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol and other glycols; Ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethyl Diol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether , propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and other glycol ethers; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethyl Acetamide, γ-butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, m-cresol, etc.

In the present invention, the above-mentioned polymerization solvents may be used in combination of multiple types.

<Manufacturing method of poly(meth)acrylate>

There is no particular limitation on the method of obtaining the poly(meth)acrylate used in the present invention. It can be obtained by making a monomer such as an acrylate compound or a methacrylate compound, a monomer having a photopolymerizable group or a photoreactive group used as needed, and a polymerization initiator used as needed, etc. in a solvent. Obtained by polymerizing at a temperature of 50°C to 110°C. The solvent used at this time is not particularly limited as long as it dissolves the monomer and the obtained polymer.

Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenylmethyl acrylate, phenyl acrylate, acrylic acid 2,2,2 - Trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-acrylate Tricyclodecanyl and 8-ethyl-8-tricyclodecanyl acrylate, etc.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, methyl Anthracenylmethyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl 2-methoxyethyl acrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate ester, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate and methacrylic acid 8-Ethyl-8-tricyclodecanyl ester, etc.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone , cyclohexanone, 2-pentanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, 2 -Hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate ester, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N- Methylpyrrolidone, etc.

Put the polymer solution obtained above into methanol, ethanol, water, etc. under stirring for reprecipitation, filter and wash the resulting precipitate, and dry it at normal temperature or under reduced pressure to produce the desired product. polymer powder. By such an operation, the polymerization initiator or unreacted monomer coexisting with the polymer can be removed, and as a result, a purified polymer powder can be obtained. In the case that one operation cannot sufficiently purify, the obtained powder can be dissolved in a solvent again, and the above operation can be repeated.

<Liquid crystal aligning agent>

When using a polyimide precursor or a polyimide as a polymer contained in a liquid crystal aligning agent, the molecular weight of a polyimide precursor or a polyimide is preferably 2000-500000 by weight average molecular weight, More preferably, it is 5,000 to 300,000, and still more preferably, it is 10,000 to 100,000. In addition, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

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

When poly(meth)acrylate is used as the polymer contained in the liquid crystal aligning agent, the molecular weight of the poly(meth)acrylate is preferably 2,000 to 500,000 in weight average molecular weight, more preferably 5,000 to 300,000, still more preferably 10000～100000. In addition, the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

The organic solvent contained in the liquid crystal aligning agent used for this invention will not be specifically limited if it can melt|dissolve the said polymer or polymeric compound contained in a liquid crystal aligning agent uniformly. Specific examples thereof include N,N-dimethylformamide and N,N-diethylformamide when polyimide precursors or polyimides are used as polymers. , N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl Sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolinone, 3-methoxy-N,N-dimethylpropionamide, etc. In addition, when polysiloxane is used as a polymer, for example, polyol compounds such as ethylene glycol and 1,2-propylene glycol, N-methylformamide, N,N-dimethylformamide, etc. amide compounds, etc. Moreover, when using poly(meth)acrylate as a polymer, an alcohol compound, a ketone compound, an amide compound, or an ester compound, or other aprotic compounds etc. are mentioned, for example. These solvents may be used alone or in combination of two or more. In addition, even a solvent that cannot uniformly dissolve the polymer or polymerizable compound alone may be mixed with the above-mentioned organic solvent as long as the polymer or polymerizable compound does not precipitate.

The liquid crystal aligning agent of this invention may contain the solvent aimed at improving the uniformity of the coating film when apply|coating a liquid crystal aligning agent to a board|substrate other than the organic solvent for the purpose of dissolving a polymer or a polymeric compound. As the solvent, generally, a solvent having a lower surface tension than the above-mentioned organic solvents is used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, 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, Propylene Glycol-1-Monomethyl Ether-2-Acetate, Propylene Glycol-1-Monoethyl Ether-2-Acetate, Butyl Cellosolve Acetate, Dipropylene Glycol, 2-(2-Ethoxypropoxy) Propylene Glycol alcohol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, etc. These solvents may use 2 or more types together.

In the liquid crystal alignment agent used in the present invention, in addition to the above-mentioned components, as long as the effects of the present invention are not impaired, polymers other than the above-mentioned polymers may be added to change the dielectric constant or conductivity of the liquid crystal alignment film. Dielectric or conductive substances for the purpose of isoelectric properties, silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, crosslinking for the purpose of improving the hardness or density of the film when it is made into a liquid crystal alignment film Active compounds, and imidization accelerators for the purpose of efficiently advancing the imidization of the polyimide precursor when firing the coating film, and the like.

<Manufacture of Liquid Crystal Alignment Film>

The liquid crystal aligning film used in the manufacturing method of this invention applies|coats the said liquid crystal aligning agent on a board|substrate, bakes after drying as needed, and is obtained by orientation-processing the obtained coating film surface.

The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate with high transparency, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. From the viewpoint of simplifying the production process From this point of view, it is preferable to use a substrate on which ITO (Indium TinOxide) electrodes or the like for liquid crystal driving are formed. In addition, opaque materials such as silicon wafers can be used in reflective liquid crystal display elements, but only on one side of the substrate, and the electrodes at this time can also use reflective materials such as aluminum. As a coating method of the liquid crystal aligning agent described in this invention, a spin coating method, a printing method, an inkjet method, etc. are mentioned.

Any temperature and time can be selected for the drying and firing steps after applying the liquid crystal aligning agent. Usually, in order to fully remove the contained organic solvent, it is preferably dried at 50°C to 120°C for 1 minute to 10 minutes, and then preferably fired at 150°C to 300°C for 5 minutes to 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when it is too thin, 5-300 nm is preferable, and 10-200 nm is more preferable.

<Orientation processing>

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

As a preferred specific example of the alignment treatment by the photo-alignment method, irradiation of ultraviolet rays polarized in a certain direction including ultraviolet rays having a wavelength of 200 nm to 400 nm, preferably 210 nm to 380 nm, for example, 300 nm to 350 nm, is exemplified on the surface of the above-mentioned coating film. , Depending on the situation, further heat-treating at a temperature of 150 to 250° C. is a method of imparting liquid crystal orientation ability. Moreover, in order to improve liquid-crystal orientation, you may irradiate an ultraviolet-ray, heating a coating-film board|substrate at 50-250 degreeC. The irradiation amount of the above-mentioned ultraviolet rays is preferably in the range of 1 to 10000 mJ/cm ² , particularly preferably in the range of 1 to 2000 mJ/cm ² .

Furthermore, the above-mentioned film irradiated with polarized ultraviolet rays may be subsequently subjected to a contact treatment with water or a solution containing a specific organic solvent. There are no particular limitations on the above-mentioned organic solvents, and examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanone, 1-methoxy-2- Propyl acetate, Butyl cellosolve, Ethyl lactate, Methyl lactate, Diacetone alcohol, Methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Propyl acetate, Butyl acetate, and cyclohexyl acetate etc. Among the above-mentioned solvents, those selected from 1-methoxy-2-propanol and 1-methoxy-2-propanol acetate are preferred from the viewpoint of easily obtaining a liquid crystal aligning film with high anisotropy and no unevenness. , butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate and cyclohexyl acetate At least 1 species. Particularly preferred is at least one selected from 1-methoxy-2-propanol and ethyl lactate.

The contact treatment of the film irradiated with polarized ultraviolet rays with a solution containing an organic solvent is preferably performed by a treatment such as immersion treatment, spray treatment, or the like to sufficiently contact the film with the liquid. Among them, a method of immersing the film in a solution containing an organic solvent for 10 seconds to 1 hour, more preferably 1 to 30 minutes, is preferred. The contact treatment may be performed at normal temperature or under heating, but it is preferably performed at 10 to 80°C, more preferably at 20 to 50°C. In addition, methods of enhancing contact, such as ultrasonic waves, may be performed as needed.

After the above-mentioned contact treatment, in order to remove the organic solvent in the solution used, either washing (rinsing) or drying with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, etc. or both. As temperature at the time of drying, 80-250 degreeC is preferable, and 80-150 degreeC is more preferable.

The liquid crystal aligning film obtained above can orient liquid crystal molecules stably in a certain direction.

<Manufacturing method of liquid crystal display element for lateral electric field drive>

The liquid crystal display element for lateral electric field driving manufactured by the manufacturing method of the present invention is to manufacture a liquid crystal unit cell for lateral electric field driving by a known method after obtaining the above-mentioned substrate with a liquid crystal alignment film, and use the liquid crystal for lateral electric field driving. The unit cell is made into a liquid crystal display element driven by a transverse electric field. In addition, an in-plane switching (IPS: In-Plane Switching) liquid crystal display element refers to a liquid crystal display element in which an electric field is applied to a substrate in a horizontal direction (lateral direction) to drive liquid crystal molecules.

As an example of a method of manufacturing a liquid crystal display element for lateral electric field driving, a liquid crystal display element having a passive matrix structure will be described as an example. Alternatively, it may be a liquid crystal display element for lateral electric field drive with an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting image display.

The substrate used in the liquid crystal display element for transverse electric field driving manufactured by the present invention is not particularly limited as long as it is highly transparent, and is usually a substrate on which transparent electrodes for driving liquid crystals are formed. As a specific example, the board|substrate similar to the board|substrate described in manufacture of the said liquid crystal aligning film is mentioned.

In addition, the liquid crystal aligning film is formed by applying the above-mentioned liquid crystal aligning agent on the substrate, firing, rubbing or irradiating radiation such as polarized ultraviolet rays as needed. Next, the other board|substrate was laminated|stacked on one board|substrate so that the mutual liquid crystal aligning film surface might face, and the periphery was bonded with the sealing material. In order to control the substrate gap, spacers are usually pre-mixed in the sealing material. In addition, it is preferable to spread a spacer for controlling the substrate gap also in the in-plane portion where no sealing material is provided. An opening that can be filled with liquid crystal from the outside is provided in advance in a part of the sealing material.

Next, a liquid crystal material is injected into the space surrounded by the two substrates and the sealing material through the opening provided in the sealing material. The liquid crystal material may, for example, be liquid crystal MLC-2041 (manufactured by Merck & Co., Ltd.). Then, this opening is sealed with an adhesive. For the injection, a vacuum injection method may be used, or a method utilizing capillarity in the atmosphere may be used. In this way, a liquid crystal cell for lateral electric field driving was produced.

Next, light, such as an ultraviolet-ray, is irradiated to this liquid crystal cell for transverse electric field drive. Here, the irradiation amount of ultraviolet rays is, for example, 1 to 60J, preferably less than 40J. A small amount of ultraviolet irradiation can suppress the decrease in reliability caused by the destruction of the members constituting the liquid crystal display element, and reduce the irradiation time of ultraviolet rays can improve manufacturing efficiency, so it is suitable . The wavelength of the ultraviolet rays to be irradiated is, for example, 200 nm to 400 nm.

When light such as ultraviolet rays is irradiated to the liquid crystal cell obtained above, that is, light such as ultraviolet rays is irradiated to the liquid crystal alignment film or liquid crystal, the photopolymerizable group located on the surface that is in contact with the liquid crystal alignment film and the liquid crystal reacts, and the The orientation of the liquid crystal on the surface of the liquid crystal aligning film is hardened. As a result, as shown in the examples described below, the alignment-regulating force of the liquid crystal is strengthened, and as a result, a liquid crystal display for lateral electric field drive with improved electrical characteristics such as image sticking caused by disordered alignment of the liquid crystal is obtained. element.

Next, setting of the polarizing plate is performed. Specifically, a pair of polarizing plates were attached to the surface of the two substrates on the side opposite to the liquid crystal layer. Through the above steps, a liquid crystal display element for lateral electric field driving can be obtained.

The liquid crystal display element for lateral electric field drive manufactured by the method for manufacturing a liquid crystal display element for lateral electric field drive of the present invention as described above is an element in which the alignment restriction force of liquid crystal is strong and image sticking is suppressed, so it can be favorably It is used for large-screen and high-definition LCD TVs, etc.

Example

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

<Preparation of liquid crystal aligning agent>

The abbreviation used for preparation of the following liquid crystal aligning agent is as follows.

(tetracarboxylic dianhydride)

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

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

(diamine)

p-PDA: p-phenylenediamine

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

[chem 35]

DA-2: Diamine compound represented by the following formula

[chem 36]

DA-3: Diamine compound represented by the following formula

[chem 37]

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

[chem 38]

(Methacrylic acid monomer)

MA1: Methacrylic acid monomer represented by the following formula

[chem 39]

MA1 was 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 Cellosolve

(polymeric compound)

RM1: 5,5'(4,4'-(biphenyl-4,4'-diylbis(oxyl))bis(butane-4,1-diyl))bis( 3-Methylenedihydrofuran-2(3H)-one)

[chemical 40]

RM2: A polymeric compound represented by the following formula

[chem 41]

RM3: A polymeric compound represented by the following formula

[chem 42]

In addition, the molecular weight measurement conditions of a polymer (polyamic acid, polyimide) are as follows.

Apparatus: Normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Morihide Scientific Co., Ltd.

Column: Showa Denko Co., Ltd. (Shodex) column (KD803, KD805)

Column temperature: 50°C

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

Flow rate: 1.0ml/min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation (Tosoh Corporation) and polyethylene oxide manufactured by Polymer Laboratories Corporation Alcohol (molecular weight is about 12000, 4000, 1000).

(Synthesis Example 1)

Add NMP (22.0g) in DA-1 (5.10g, 14.0mmol), stir at room temperature to make it dissolve completely, add CBDA (2.66g, 13.6mmol) and NMP (22.0g), at room temperature The reaction was carried out for 10 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic-acid solution (40g), and it obtained liquid crystal aligning agent (A1) by stirring at room temperature for 5 hours. The polyamic acid had a number average molecular weight of 6,500 and a weight average molecular weight of 26,000.

Moreover, polymerizable compound RM1 of 60 mg (10 mass % with respect to solid content) was added with respect to the said liquid crystal aligning agent (A1) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared liquid crystal aligning agent (A2).

(Synthesis Example 2)

Add NMP (20.8g) to DA-1 (3.57g, 9.8mmol) and BEM-S (1.11g, 4.2mmol), stir at room temperature to dissolve completely, add CBDA (2.66g, 13.6mM mol) and NMP (20.8g), reacted at room temperature for 10 hours to obtain a polyamic acid solution. NMP (40.0g) and BCS (20.0g) were added to this polyamic-acid solution (40g), and it obtained liquid crystal aligning agent (B1) by stirring at room temperature for 5 hours. The polyamic acid had a number average molecular weight of 7,500 and a weight average molecular weight of 25,000.

Moreover, polymeric compound RM1 of 60 mg (10 mass % with respect to solid content) was added with respect to the said liquid crystal aligning agent (B1) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared liquid crystal aligning agent (B2).

<Production of liquid crystal cell 1>

(comparative example 1)

Using the liquid crystal aligning agent (A2) obtained in the synthesis example 1, manufacture of a liquid crystal cell was performed by the procedure shown below. The substrate was a glass substrate with a size of 30 mm×40 mm and a thickness of 0.7 mm, and a substrate on which a pixel electrode in the shape of a grate tooth formed by patterning an ITO film was arranged was used. The pixel electrode has a grate-like shape formed by arranging a plurality of “く”-shaped electrode elements bent at the center. The short-side width of each electrode element was 3 μm, and the interval between electrode elements was 6 μm. The pixel electrode forming each pixel is formed by arranging a plurality of "く"-shaped electrode elements with curved central parts. Therefore, the shape of each pixel is not rectangular, but has a thick image with a curved central part like the electrode elements. The shape of the "く" character. Then, each pixel is divided up and down with the curved portion in the center as a boundary, and has a first area above the curved portion and a second area below the curved portion. When the first region and the second region of each pixel are compared, it is found that the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is taken as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (clockwise direction), and the first region of the pixel In the region 2, the electrode elements of the pixel electrodes are formed at an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation movement (in-plane switching) of the liquid crystal excited by the voltage application between the pixel electrode and the counter electrode in the substrate plane are opposite to each other. The way the direction is composed. The liquid crystal aligning agent (A2) obtained in the synthesis example 1 was spin-coated on the prepared said board|substrate with an electrode. Next, after drying on a 90 degreeC hot plate for 60 second, it baked in the hot-air circulation furnace of 200 degreeC for 30 minutes, and formed the liquid crystal aligning film of film thickness 100nm. Then, 20 mJ/cm ^<2> of ultraviolet rays of 313 nm were irradiated to the coating film surface through a polarizing plate, and the board|substrate with a liquid crystal aligning film was obtained. In addition, a liquid crystal aligning agent (A2) was used to form a coating film in the same manner on a glass substrate having a columnar spacer with a height of 4 μm in which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd. (Kyoritsu Chemical)) was printed on the liquid crystal aligning film of one substrate. Next, after bonding together the other side board|substrate so that the relative orientation direction of a liquid crystal aligning film may become 0 degree, the sealing agent was hardened, and the empty cell was produced. Liquid crystal MLC-2041 (manufactured by Merck & Co., Ltd.) was injected into the empty unit cell by a depressurized injection method, and the injection port was sealed to obtain an IPS (In-Plane Switching) mode liquid crystal display element (a liquid crystal display element of a lateral electric field drive method) structure of liquid crystal cells.

(Example 1)

About the liquid crystal cell manufactured by the operation similar to the comparative example 1, the ultraviolet ray 20J/cm ^<2> of 365nm was irradiated from the outside of the liquid crystal cell (irradiation twice), and the liquid crystal cell of Example 1 was obtained.

(comparative example 2)

Except having used a liquid crystal aligning agent (B2) instead of a liquid crystal aligning agent (A2), the operation similar to the comparative example 1 was performed, and the liquid crystal cell of the comparative example 2 was obtained.

(Example 2)

About the liquid crystal cell manufactured by the operation similar to the comparative example 2, the ultraviolet ray 20J/cm ^<2> of 365nm was irradiated from the outside of the liquid crystal cell (irradiation twice), and the liquid crystal cell of Example 2 was obtained.

(comparative example 3)

Except having used a liquid crystal aligning agent (A1) instead of a liquid crystal aligning agent (A2), the operation similar to the comparative example 1 was performed, and the liquid crystal cell of the comparative example 3 was obtained.

(afterimage evaluation 1)

The IPS mode liquid crystal cells prepared in each of Examples 1-2 and Comparative Examples 1-3 were placed between two polarizers arranged so that the polarization axes were perpendicular to each other, and the backlight was turned on in a state where no voltage was applied. To emit light, the arrangement angle of the liquid crystal cell is adjusted under the condition that the brightness of the transmitted light is minimized. Next, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the pixel becomes darkest to the angle at which the first region becomes darkest is calculated as an initial orientation azimuth angle. Next, an AC voltage of 8 V _PP was applied at a frequency of 30 Hz for 24 hours in a room temperature environment. Then, between the pixel electrode and the counter electrode of the liquid crystal cell was short-circuited, and it was left to stand at room temperature for 1 hour in this state. After standing, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuth before and after AC driving was calculated as an angle Δ (deg.).

[Table 1]

The results are shown in Table 1. Examples 1 and 2, in which a polymerizable compound was added or UV was irradiated after liquid crystal cell production, were compared with those in Examples 1 and 2, which did not add a polymerizable compound and were not irradiated with UV after liquid crystal cell production (two irradiations). Compared with comparative example 3 or comparative example 1 and 2 which did not irradiate with UV after preparation of a liquid crystal cell, the difference of the orientation azimuth angle before and after AC driving was very small. However, it can be considered that Examples 1 and 2 have a strong orientation-regulating force and are very excellent in image sticking characteristics. This is considered to be because the added photopolymerizable compound forms a polymerized layer on the surface of the alignment film by irradiating UV from the outside after the liquid crystal cell production, thereby hardening the alignment. In addition, since the difference in orientation azimuth angle before and after AC driving of both Example 1 and Example 2 is zero, it is difficult to compare, but from Comparative Example 2 using a polymer introduced with photopolymerizable BEM-S It was confirmed that the difference in orientation azimuth angle before and after driving was smaller than in Comparative Example 1, and it was confirmed that the image sticking characteristics could be further improved by using a polymer into which photopolymerizable BEM-S was introduced.

(Synthesis Example 3)

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

Moreover, polymerizable compound RM1 of 30 mg (5 mass % with respect to solid content) was added to the liquid crystal aligning agent (C) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared liquid crystal aligning agent (C1).

Moreover, polymeric compound RM2 of 30 mg (5 mass % with respect to solid content) was added to the liquid crystal aligning agent (C) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared a liquid crystal aligning agent (C2).

Moreover, polymerizable compound RM3 of 30 mg (5 mass % with respect to solid content) was added to the liquid crystal aligning agent (C) of 10.0g, and it stirred and melt|dissolved at room temperature for 3 hours, and prepared a liquid crystal aligning agent (C3).

(Synthesis Example 4)

BODA (2.50g, 10.0 mmol), DA-3 (9.65g, 20.0 mmol) were mixed in NMP (42.3g), and after reacting at 80°C for 5 hours, CBDA (1.92g, 10.0 mmol) and NMP (14.1 g) was reacted at 40° C. for 10 hours to obtain a polyamic acid solution. After adding NMP (70.4g) and BCS (93.8g) to this polyamic-acid solution (70.4g) and diluting to 6 weight%, it stirred at room temperature for 10 hours, and obtained the liquid crystal aligning agent (D). The polyamic acid had a number average molecular weight of 12,000 and a weight average molecular weight of 21,000.

Moreover, polymerizable compound RM1 of 30 mg (5 mass % with respect to solid content) was added to the liquid crystal aligning agent (D) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared liquid crystal aligning agent (D1).

(Synthesis Example 5)

Mix CBDA (1.92g, 10.0mmol), p-PDA (0.54g, 5.0mmol), DA-2 (2.24g, 5.0mmol) in NMP (18.9g) and react at room temperature for 10 hours to obtain Polyamic acid solution. After adding NMP (23.6g) and BCS (31.5g) to this polyamic-acid solution (23.6g) and diluting to 6 weight%, it stirred at room temperature for 10 hours, and obtained the liquid crystal aligning agent (E). The polyamic acid had a number average molecular weight of 19,000 and a weight average molecular weight of 28,000.

Moreover, polymerizable compound RM1 of 30 mg (5 mass % with respect to solid content) was added to 10.0 g of liquid crystal aligning agents (E), and it stirred and melt|dissolved at room temperature for 3 hours, and prepared liquid crystal aligning agent (E1).

(Synthesis Example 6)

MA1 (5.54 g, 16.0 mmol) was dissolved in NMP (51.1 g), and after degassing with a diaphragm pump for 6 minutes, AIBN (0.131 g, 0.8 mmol) was added and degassed again for 6 minutes. Then, it was made to react at 65 degreeC for 20 hours, and the methacrylate polymer solution was obtained. BCS (37.8g) was added to this polymer solution, it diluted to 6 mass %, and it obtained the liquid crystal aligning agent (F) by stirring at room temperature for 5 hours. The polymer had a number average molecular weight of 16,000 and a weight average molecular weight of 39,000.

Moreover, polymerizable compound RM1 of 30 mg (5 mass % with respect to solid content) was added to the liquid crystal aligning agent (F) of 10.0g, it stirred and melt|dissolved at room temperature for 3 hours, and prepared a liquid crystal aligning agent (F1).

<Production of liquid crystal cell 2>

(Example 3)

Using the liquid crystal aligning agent (C1) obtained in the synthesis example 3, manufacture of a liquid crystal cell was performed by the procedure shown below. The substrate was a glass substrate with a size of 30 mm×40 mm and a thickness of 0.7 mm, and a substrate on which a pixel electrode in the shape of a grate tooth formed by patterning an ITO film was arranged was used. The pixel electrode has a grate-like shape formed by arranging a plurality of “く”-shaped electrode elements bent at the center. The short-side width of each electrode element was 10 μm, and the interval between electrode elements was 20 μm. The pixel electrode forming each pixel is formed by arranging a plurality of "く"-shaped electrode elements with curved central parts. Therefore, the shape of each pixel is not rectangular, but has a thick image with a curved central part like the electrode elements. The shape of the "く" character. Then, each pixel is divided up and down with the curved portion in the center as a boundary, and has a first area above the curved portion and a second area below the curved portion. When the first region and the second region of each pixel are compared, it is found that the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the alignment treatment direction of the liquid crystal alignment film described later is taken as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +15° (clockwise direction), and the first region of the pixel In the 2 region, the electrode elements of the pixel electrodes are formed at an angle of -15° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation motion (in-plane switching) of the liquid crystal excited by the voltage application between the pixel electrode and the counter electrode in the substrate plane are opposite to each other. The way the direction is composed. The liquid crystal aligning agent (C1) obtained in the synthesis example 3 was spin-coated on the prepared said board|substrate with an electrode. Next, after drying on an 80 degreeC hot plate for 90 seconds, it baked in the hot-air circulation furnace of 160 degreeC for 30 minutes, and formed the liquid crystal aligning film of film thickness 100nm. Then, 50 mJ/cm ^<2> of polarized ultraviolet rays of 313 nm were irradiated to the coating film surface through a polarizing plate (1 time irradiation), and the board|substrate with a liquid crystal aligning film was obtained. In addition, a liquid crystal aligning agent (C1) was used to form a coating film in the same manner on a glass substrate having a columnar spacer with a height of 4 μm in which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal aligning film of one substrate. Next, after bonding together the other side board|substrate so that the relative orientation direction of a liquid crystal aligning film may become 0 degree, the sealing agent was hardened, and the empty cell was produced. Liquid crystal MLC-2041 (manufactured by Merck & Co., Ltd.) was injected into the empty unit cell by a depressurized injection method, and the injection port was sealed to obtain an IPS (In-Plane Switching) mode liquid crystal display element (a liquid crystal display element of a lateral electric field drive method) structure of liquid crystal cells.

After manufacturing the liquid crystal cell, reorientation treatment was performed for 60 minutes in an oven at 120°C. Thereafter, between the pixel electrode and the counter electrode of the liquid crystal cell was short-circuited, and 20 J/cm ² of ultraviolet rays passing through a 365 nm bandpass filter were irradiated to the liquid crystal cell (2 irradiations).

(afterimage evaluation 2)

The liquid crystal unit cell for IPS mode prepared in Example 3 is arranged between two polarizers arranged in a manner that the polarization axes are perpendicular to each other, and the backlight is illuminated in a state where no voltage is applied, so that the brightness of the transmitted light reaches The minimum condition adjusts the arrangement angle of the liquid crystal cell. Next, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the pixel becomes darkest to the angle at which the first region becomes darkest is calculated as an initial orientation azimuth angle. Next, in a 60° C. oven, an AC voltage of 16 V _PP was applied at a frequency of 30 Hz for 168 hours. Then, between the pixel electrode and the counter electrode of the liquid crystal cell was short-circuited, and it was left to stand at room temperature for 1 hour in this state. After standing, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuth before and after AC driving was calculated as an angle Δ (deg.). Table 2 shows the image sticking evaluation results.

(Example 4)

After producing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (C2) instead of a liquid crystal aligning agent (C1), image sticking evaluation was performed.

(Example 5)

After producing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (C3) instead of a liquid crystal aligning agent (C1), image sticking evaluation was performed.

(Example 6)

After manufacturing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (D1) instead of a liquid crystal aligning agent (C1), and having made the irradiation amount of the polarized ultraviolet-ray into 500mJ/ ^cm2 , image sticking evaluation was performed.

(Example 7)

After producing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (E1) instead of a liquid crystal aligning agent (C1), image sticking evaluation was performed.

(Embodiment 8)

After manufacturing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (F1) instead of a liquid crystal aligning agent (C1), and making the irradiation amount of polarized ultraviolet-ray into 500mJ/ ^cm2 , image sticking evaluation was performed.

(Example 9)

After producing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (C) instead of a liquid crystal aligning agent (C1), image sticking evaluation was performed.

(comparative example 4)

After manufacturing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (C) instead of a liquid crystal aligning agent (C1), and not performing twice irradiation, image sticking evaluation was performed.

(comparative example 5)

After using the liquid crystal aligning agent (D) instead of the liquid crystal aligning agent (C1), the irradiation amount of the polarized ultraviolet rays was set to 500mJ/cm ² , and the irradiation was not performed twice, after the liquid crystal cell was produced in the same steps as in Example 3, Perform afterimage evaluation.

(comparative example 6)

After manufacturing a liquid crystal cell by the procedure similar to Example 3 except having used a liquid crystal aligning agent (E) instead of a liquid crystal aligning agent (C1), and not performing 2 times of irradiation, image sticking evaluation was performed.

(comparative example 7)

After using the liquid crystal aligning agent (F) instead of the liquid crystal aligning agent (C1), the irradiation amount of the polarized ultraviolet rays was set to 500mJ/cm ² , and the irradiation was not performed twice, after the liquid crystal cell was produced in the same steps as in Example 3, Perform afterimage evaluation.

[Table 2]

From the results in Table 2, it was confirmed that in any of Comparative Examples 4 to 7 without adding a polymerizable compound, the orientation azimuth angle was greatly deviated after AC driving, but after adding a polymerizable compound and performing UV irradiation after liquid crystal cell production (2 Sub-irradiation) Examples 3 to 8 showed almost no deviation in orientation azimuth angles compared with Comparative Examples 4 to 7 even after AC driving. In addition, it can be seen that Example 9, which contains a polymer having a photopolymerizable group on the side chain and is subjected to UV irradiation (2 irradiations) after liquid crystal cell production, is more aligned than Comparative Example 4 which does not perform 2 irradiations. The deviation in azimuth is small. The reason is presumed as follows: in Examples 3 to 9, the polymerizable compound or the photopolymerizable group of the polymer polymerized on the interface of the alignment film was irradiated twice, and the surface of the liquid crystal alignment film was cured, so the deviation of the alignment azimuth angle was very small.

Claims (11)

1. A method for manufacturing a liquid crystal display element driven by a transverse electric field, comprising coating a liquid crystal aligning agent on a substrate to form a liquid crystal aligning film and implementing alignment treatment, and then forming a liquid crystal aligning film through a liquid crystal Arranging the substrates facing each other so that the liquid crystal alignment film faces each other to produce a liquid crystal cell, and then irradiating the liquid crystal cell with light to react the photopolymerizable groups in the liquid crystal and/or in the liquid crystal alignment film process. 2. The method of manufacturing a liquid crystal display element for transverse electric field driving according to claim 1, wherein the liquid crystal contains a polymerizable compound having the photopolymerizable group. 3. The method for producing a liquid crystal display element for lateral electric field drive according to claim 1 or 2, wherein the liquid crystal aligning agent contains the photopolymerizable group. 4. The method for producing a liquid crystal display element driven by a transverse electric field according to any one of claims 1 to 3, wherein the liquid crystal aligning agent contains a polymer having the photopolymerizable group on the side chain. things. The said liquid crystal aligning agent contains the polymeric compound which has the said photopolymerizable group, The manufacturing method of the liquid crystal display element for transverse electric field drives in any one of Claims 1-4 characterized by the above-mentioned. 6. The method for producing a liquid crystal display element driven by a transverse electric field according to any one of claims 3 to 5, wherein the photopolymerizable group is selected from the photopolymerizable groups shown below group; [chemical 1] In the formula, Me represents a methyl group. 7. The method for manufacturing a liquid crystal display element for transverse electric field drive according to any one of claims 1 to 6, wherein the alignment treatment is performed by irradiation of polarized ultraviolet rays. 8. The method for manufacturing a liquid crystal display element driven by a transverse electric field as claimed in any one of claims 1 to 7, wherein, in the alignment treatment, the following formula (A-1) to (A- 7) The photoreactive group of the structure reacts, [Chem 2] 9. The method for manufacturing a liquid crystal display element driven by a transverse electric field as claimed in any one of claims 1 to 8, wherein the polymer contained in the liquid crystal alignment agent contains polyimide precursors and At least one kind of polyimide obtained by imidating this. The polymer contained in the said liquid crystal aligning agent contains polysiloxane, The manufacturing method of the liquid crystal display element for transverse electric field drives in any one of Claims 1-9 characterized by the above-mentioned. The polymer contained in the said liquid crystal aligning agent contains poly(meth)acrylate, The manufacturing method of the liquid crystal display element for transverse electric field drives in any one of Claims 1-10 characterized by the above-mentioned.