TWI628231B - Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element - Google Patents

Abstract

The present invention provides a lateral electric field drive type liquid crystal display device capable of imparting alignment control ability with high efficiency and excellent afterimage characteristics. The present invention is a polymer composition that solves the above problems. The polymer composition contains: (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and (B) a polyimide and its At least one polymer selected from the group of precursors and (C) an organic solvent. In particular, the above-mentioned problems are solved by a manufacturing method of a substrate having a liquid crystal alignment film. The aforementioned manufacturing method obtains a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that is provided with alignment control energy by having the following steps: [I] 将A step of applying the composition on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] applying [II] A step of heating the obtained coating film.

Description

Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element

The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a liquid crystal display element driven in a lateral electric field. More specifically, it relates to a novel method for manufacturing a liquid crystal display element having excellent afterimage characteristics.

It is known that a liquid crystal display element is a lightweight, thin, and low power consumption display device. In recent years, it has been used in large-scale television applications and the like. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer on a transparent substrate with one of the electrodes. In addition, the liquid crystal display element makes a liquid crystal into a desired alignment state between substrates, and an organic film made of an organic material is used as the liquid crystal alignment film.

That is, the constituent member of the liquid crystal alignment film-based liquid crystal display element is formed on a surface in contact with the liquid crystal of the substrate holding the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. Furthermore, in addition to the role of the liquid crystal alignment film in a certain direction such as the direction in which the liquid crystal is aligned parallel to the substrate, the role of controlling the pretilt angle of the liquid crystal is sometimes required. The ability to control liquid crystal alignment in such a liquid crystal alignment film (hereinafter referred to as alignment Orientation control energy) is imparted by performing an alignment treatment on an organic film constituting a liquid crystal alignment film.

An alignment treatment method for imparting a liquid crystal alignment film that can be used for alignment control has been conventionally known as a rubbing method. The so-called rubbing method is to wipe (friction) the surface of the organic film such as polyvinyl alcohol, polyimide, or polyimide on the substrate with a cloth such as cotton, nylon, or polyester in a certain direction, so that the liquid crystal faces the wiping direction (friction Direction). Since this rubbing method can easily achieve a relatively stable alignment state of the liquid crystal, it is used in a conventional manufacturing process of a liquid crystal display element. In addition, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance or excellent electrical characteristics is mainly selected.

However, the rubbing method of wiping the surface of a liquid crystal alignment film made of polyimide or the like has a problem of generating dust or generating static electricity. In addition, in recent years, due to the high definition of the liquid crystal display element or the unevenness caused by the electrodes on the corresponding substrate or the active element for switching the liquid crystal drive, the liquid crystal alignment film cannot be uniformly wiped with a cloth. On the surface, uniform liquid crystal alignment sometimes cannot be achieved.

Therefore, the photo-alignment method is actively reviewed as another alignment processing method of the liquid crystal alignment film without rubbing.

There are various methods of photo-alignment, but anisotropy is formed in the organic film constituting the liquid crystal alignment film by linear polarized light or collimate light, and the liquid crystal is aligned according to the anisotropy.

As the main photo-alignment method, a decomposition-type photo-alignment method is known. This method, for example, irradiates a polyimide film with polarized ultraviolet light and uses molecular junctions The polarization dependence of the structure's ultraviolet absorption causes anisotropic decomposition. Then, the liquid crystal is aligned by using polyimide remaining without being decomposed (see, for example, Patent Document 1).

In addition, other photo-alignment methods, such as a photo-crosslinking type or a photo-isomerization type, are also known. For example, a photo-crosslinking type photo-alignment method, for example, using polyvinyl cinnamate and irradiating polarized ultraviolet rays, a dimerization reaction (cross-linking reaction) occurs at a double bond portion of two side chains parallel to the polarized light. The liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when the photo-isomerization type photo-alignment method uses a side-chain type polymer having azobenzene in a side chain, it is irradiated with polarized ultraviolet light, and an isomerization reaction occurs in an azobenzene portion of a side chain parallel to the polarization. , The liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 2).

As in the above example, the alignment processing method of the liquid crystal alignment film by the photo alignment method does not require friction, and there is no doubt that dust or static electricity is generated. In addition, even a substrate of a liquid crystal display element having an uneven surface can be subjected to an alignment treatment, which becomes an alignment treatment method of a liquid crystal alignment film suitable for an industrial production process.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

[Invention Summary]

As described above, the photo-alignment method, as an alignment processing method for a liquid crystal display element, has a great advantage because it does not require a rubbing step as compared with the conventional rubbing method used in industry. In addition, compared with a friction method that uses friction to make the alignment control energy approximately constant, the light alignment method can change the amount of polarized light irradiation to control the alignment control energy. However, when the photo-alignment method wants to achieve the same degree of alignment control ability as in the case of using the friction method, a large amount of polarized light irradiation is required, and sometimes a stable liquid crystal alignment cannot be achieved.

For example, in the decomposition-type light alignment method described in Patent Document 1, the polyimide film must be irradiated with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, etc., and a large amount of ultraviolet light must be irradiated for a long time. Moreover, in the case of the photo-alignment method of a dimerization type or a photo-isomerization type, it may be necessary to irradiate a large amount of ultraviolet rays of several J (Joules) to several tens J. Furthermore, in the photo-alignment method of the photo-crosslinking type or the photo-isomerization type, the liquid crystal alignment has poor thermal stability or photo-stability. Therefore, when it is used as a liquid crystal display element, there is a concern that a poor alignment or a residual image is displayed. Especially lateral electric field-driven liquid In the crystal display element, since liquid crystal molecules are switched in-plane, alignment of the liquid crystal is likely to be shifted after the liquid crystal is driven, so that an afterimage caused by AC driving becomes a large problem.

Therefore, the photo-alignment method requires high-efficiency or stable liquid crystal alignment for alignment processing, and requires a liquid crystal alignment film or liquid crystal alignment agent that can efficiently impart high alignment control ability to the liquid crystal alignment film.

An object of the present invention is to provide a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element capable of imparting alignment control ability with high efficiency and excellent afterimage characteristics, and a lateral electric field drive type liquid crystal display element having the substrate. In addition, an object of the present invention is to provide a liquid crystal alignment film and a method for manufacturing a substrate having the liquid crystal alignment film, which can expand a margin area of ultraviolet irradiation of the liquid crystal alignment film that can achieve good liquid crystal alignment.

The present inventors have actively reviewed the results in order to achieve the above-mentioned problems, and have found the following inventions.

<1> A polymer composition, particularly a polymer composition for manufacturing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, characterized in that it contains: (A) a photosensitive side chain exhibiting liquid crystallinity in a specific temperature range Polymer, (B) at least one polymer selected from the group consisting of polyimide and its precursor, and (C) an organic solvent.

<2> In the above <1>, the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement.

<3> In the above <1> or <2>, the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

<4> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (1) to (6):

In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted with halogen groups; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to The alicyclic hydrocarbon ring of 8 or the same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can each independently pass through -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, carbon 1 to 5 alkyl or 1 to 5 carbon oxy; Y ₂ is selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8 The alicyclic hydrocarbons, and the groups of these groups, and the hydrogen atoms to which they are bonded can also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or 1 to 5 carbons Alkyloxy substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in the Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, - CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; Cou means Coumarin -6-yl or coumarin-7-yl, and the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN , Halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q Each is independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, but X is When -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring, and when the number of P is 2 or more, P may be mutually The same or different, when the number of Q is 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0 ~ 2; when l1 and l2 are 0, when T is a single bond, A Also represents a single bond; when l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently A group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

<5> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (7) to (10):

In the formula, A, B, D, Y ₁ , X, Y ₂ and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1 and m2 represent integers from 1 to 3 ; N represents an integer from 0 to 12 (but when n = 0, B is a single bond).

<6> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (11) to (13):

In the formula, A, X, 1, m, m1, and R have the same definitions as described above.

<7> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain represented by the following formula (14) or (15):

In the formula, A, Y ₁ , 1, m1 and m2 have the same definitions as above.

<8> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain represented by the following formula (16) or (17):

In the formula, A, X, l, and m have the same definitions as described above.

<9> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain represented by the following formula (18) or (19):

In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Oxygen.

<10> In any one of the above <1> to <3>, the component (A) has a photosensitive side chain represented by the following formula (20):

In the formula, A, Y ₁ , X, l, and m have the same definitions as above.

<11> In any one of the above <1> to <10>, the component (A) has any liquid crystal side chain selected from the group consisting of the following formulae (21) to (31):

In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and lipid having 5 to 8 carbon atoms. Cyclic hydrocarbons, and groups of groups thereof, and the hydrogen atoms to which they are bonded may also each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or carbon 1 to 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l represents 1 to 12 Integer, m represents an integer from 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, and in formulas (25) to (26), the total of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and Alicyclic hydrocarbons and alkyl or alkyloxy groups having 5 to 8 carbon atoms; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<12> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is given: [I] will be <1> The step of applying any one of the components of <11> to a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [ III] A step of heating the coating film obtained in [II].

<13> A substrate comprising a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by the method of the above <12>.

<14> A lateral electric field drive type liquid crystal display element, comprising the substrate according to <13>.

<15> A method for manufacturing a liquid crystal display element, which is characterized by obtaining a lateral electric field drive type liquid crystal display element by the following steps: a step of preparing the substrate (first substrate) of the above <13>; obtaining a first substrate having a liquid crystal alignment film The step of 2 substrates is to obtain a liquid crystal alignment film that imparts alignment control ability by having the following steps [I '] to [III']: [I '] coating a second substrate with the following components (A) ~ (C) A step of forming a coating film with a polymer composition: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a polyimide and its precursor At least one polymer selected from the group and (C) an organic solvent; [II '] a step of irradiating polarized ultraviolet rays on the coating film obtained by [I']; and [III '] obtained by [II'] A step of heating the coating film; and [IV] a step of obtaining a liquid crystal display element, in which the liquid crystal alignment films of the first and second substrates are opposed to each other through liquid crystal, and the first and second substrates are arranged to face each other.

<16> The method of the above <15>, wherein the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

<17> A lateral electric field drive type liquid crystal display element, characterized in that it is manufactured by the method of <15> or <16> above.

In addition, the following inventions were found.

<P1> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that imparts alignment control energy: [I] will contain (A), ( Steps of coating the polymer composition of B) and (C) on a substrate having a conductive film for lateral electric field driving to form a coating film: (A) Photosensitive side chain type exhibiting liquid crystallinity in a specific temperature range Molecule, (B) at least one polymer selected from the group consisting of polyimide and its precursor, and (C) an organic solvent.

[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [II].

<P2> In the above-mentioned <P1>, the component (A) may have a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement.

<P3> In the above-mentioned <P1> or <P2>, the polyimide precursor of the component (B) may be obtained by polymerizing a tetracarboxylic acid component and a diamine component.

<P4> In any one of the above <P1> to <P3>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (1) to (6):

In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms 12 alkyl groups, and the hydrogen atoms to which they are bonded may be substituted with halogen groups; Y ₁ represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and carbon number 5 ~ 8 alicyclic hydrocarbon rings, or the same or different 2 ~ 6 ring systems selected from these substituents are bonded through the bonding group B, and the hydrogen atom bonded to it can also be Each independently via -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen Group, 1 to 5 carbon atoms, or 1 to 5 alkyloxy groups; Y ₂ is selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon number The alicyclic hydrocarbons of 5 to 8 and the bases of a group composed of these, and the hydrogen atoms bonded thereto may also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or carbon The alkyl group having 1 to 5 substituents; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in the Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, Cou represents coumarin-6-yl or coumarin-7 -Groups, and the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, 1 to 5 carbon alkane Or an alkyloxy group with 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently selected from a single bond and a divalent A group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these, but X is -CH = CH-CO- When O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring, and H and I are each independently selected from a divalent benzene ring, naphthalene ring, and A benzene ring, a furan ring, a pyrrole ring, and a combination thereof.

<P5> In any one of the above-mentioned <P1> to <P3>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1 and m2 represent integers from 1 to 3 ; N represents an integer from 0 to 12 (but B is a single bond when n = 0).

<P6> In any one of the above <P1> to <P3>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

In the formula, A, X, 1, m and R have the same definitions as above.

<P7> In any one of <P1> to <P3>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , X, 1, m1 and m2 have the same definitions as above.

<P8> In any one of the above <P1> to <P3>, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l, and m have the same definitions as described above.

<P9> In any one of <P1> to <P3>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Oxygen.

<P10> In any one of <P1> to <P3>, the component (A) may have a photosensitive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, l, and m have the same definitions as above.

<P11> In any one of the above <P1> to <P10>, the (A) component may have any liquid crystal side chain selected from the group consisting of the following formulae (21) to (31).

In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and lipid having 5 to 8 carbon atoms. Cyclic hydrocarbons, and groups of groups of these, the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or carbon 1 to 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l represents 1 to 12 Integer, m represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 2 or more, and in formulas (27) to (28), the total of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and Alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<P12> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which is manufactured by any one of the above-mentioned <P1> to <P11>.

<P13> A lateral electric field drive type liquid crystal display device having the substrate of <P12>.

<P14> A method for manufacturing a liquid crystal display element, which is obtained by having the following steps to obtain a lateral electric field drive type liquid crystal display element: a step of preparing the substrate (first substrate) of the above <P12>; The step of obtaining a second substrate having a liquid crystal alignment film is to obtain a liquid crystal alignment film imparting alignment control ability by having the following steps [I '] to [III']: [I '] coating on the second substrate A step of forming a coating film with a polymer composition containing the following components (A), (B), and (C): (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, (B ) At least one polymer selected from the group consisting of polyimide and its precursor and (C) an organic solvent.

[II '] Step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; [III '] Step of heating the coating film obtained in [II']; and [IV] Step of obtaining a liquid crystal display element It is a method in which the liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal, and the first and second substrates are arranged to face each other.

<P15> A lateral electric field drive type liquid crystal display device manufactured by the aforementioned <P14>.

<P16> A composition for manufacturing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which contains the following components: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) At least one polymer selected from the group consisting of polyimide and its precursor and (C) an organic solvent.

<P17> In the above <P16>, the polyimide precursor of the component (B) may be obtained by polymerizing a tetracarboxylic acid component and a diamine component.

According to the present invention, a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element capable of imparting alignment control ability with high efficiency and excellent afterimage characteristics, and a lateral electric field drive type liquid crystal display element having the substrate can be provided.

The lateral electric field drive type liquid crystal display element manufactured by the method of the present invention can provide alignment control energy with high efficiency, so it does not damage the display characteristics even if it is continuously driven for a long time.

In the present invention, the polymer composition contains (B) at least one polymer selected from the group consisting of polyimide and its precursor, so that the liquid crystal alignment film can be expanded and realized. The area with sufficient liquid crystal alignment of the ultraviolet irradiation amount has a wide area, so the wider irradiation area can achieve the desired effect.

1‧‧‧ side chain polymer film

2, 2a‧‧‧ side chain

3‧‧‧ side chain polymer film

4, 4a‧‧‧ side chain

5‧‧‧ side chain polymer film

6, 6a‧‧‧ side chain

7‧‧‧ side chain polymer film

8, 8a‧‧‧ side chain

[Fig. 1] A diagram schematically illustrating an example of anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. A crosslinkable organic group is used for a photosensitive side chain, and the introduced anisotropy is small. Of the situation.

[Fig. 2] Schematic illustration of the production of a liquid crystal alignment film used in the present invention An example of the anisotropic introduction process in the method. A crosslinked organic group is used for a photosensitive side chain, and the introduced anisotropy is large.

[Fig. 3] A diagram schematically illustrating an example of anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. An organic material that causes photo-Fries rearrangement or isomerization is used on a photosensitive side chain. Base, a diagram of the case where the introduced anisotropy is small.

[Fig. 4] A diagram schematically illustrating an example of anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. An organic material that causes photo-Fries rearrangement or isomerization is used on a photosensitive side chain. Base, a diagram of the case where the introduced anisotropy is large.

[Mode for Carrying Out the Invention]

As a result of active research by the present inventors, the following findings were obtained and the present invention has been completed.

The polymer composition used in the production method of the present invention has a photosensitive side chain polymer (hereinafter also simply referred to as a side chain polymer) that exhibits liquid crystallinity. The coating film obtained by using the polymer composition described above has A film of a photosensitive side chain polymer exhibiting liquid crystallinity. This coating film does not need to be subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. After the polarized light is irradiated, the side chain polymer film is heated to obtain a coating film (hereinafter, also referred to as a liquid crystal alignment film) to which alignment control ability is given. At this time, a slight anisotropy exhibited by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is effectively reorganized due to self-organization. to. As a result, a highly efficient alignment process as a liquid crystal alignment film can be realized, and a liquid crystal alignment film to which a high alignment control ability is given can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.

<Manufacturing method of substrate with liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>

The method for manufacturing a substrate with a liquid crystal alignment film of the present invention has the following steps: It obtains a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control energy is given by having the following steps: [I] will contain ( A) Photosensitive side-chain polymers exhibiting liquid crystallinity in a specific temperature range, (B) Polymerization of at least one polymer selected from the group consisting of polyimide and its precursor, and (C) polymerization of an organic solvent A step of applying a composition on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] applying [II] A step of heating the obtained coating film.

In addition to the substrate (first substrate) obtained above, a second substrate can be prepared to obtain a lateral electric field drive type liquid crystal display element.

The second substrate uses a substrate without a conductive film for lateral electric field drive instead of a substrate with a conductive film for lateral electric field drive, by using the above steps [I] to [III] Conductive film substrate, so for convenience, sometimes referred to as the step in this application Steps [I '] to [III']) can obtain a second substrate having a liquid crystal alignment film provided with alignment control ability.

A method for manufacturing a lateral electric field-driven liquid crystal display element has the following steps [IV]: [IV] a method of opposing the liquid crystal alignment films of the first and second substrates via liquid crystal, and causing the first and second substrate pairs obtained above to A step of arranging to obtain a liquid crystal display element. Thereby, a lateral electric field drive type liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] included in the manufacturing method of the present invention will be described.

<Step [I]>

Step [I] is a polymer containing at least one polymer selected from the group consisting of a photosensitive side chain polymer exhibiting liquid crystallinity, a polyimide, and a precursor thereof in a specific temperature range, and an organic solvent. The composition is applied on a substrate having a conductive film for driving a lateral electric field to form a coating film.

<Substrate>

The substrate is not particularly limited, but when the manufactured liquid crystal display element is a transmissive type, it is preferable to use a substrate with high transparency. In this case, there is no particular limitation, and a glass substrate, a plastic substrate such as an acrylic substrate, or a polycarbonate substrate can be used.

In addition, considering the application of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

<Conductive film for lateral electric field drive>

The substrate has a conductive film for driving a lateral electric field.

When the conductive film is of a transmissive type, the conductive film may be ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or the like, but is not limited thereto.

In the case of a reflective liquid crystal display element, the conductive film may be a material that reflects light, such as aluminum, but is not limited thereto.

As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<Polymer composition>

A polymer composition is coated on a substrate having a conductive film for driving a lateral electric field, especially a conductive film.

The polymer composition used in the manufacturing method of the present invention contains (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) a group of polyimide and its precursor A polymer selected from at least one of the above; and (C) an organic solvent.

<< (A) side chain polymer >>

The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range.

(A) The side-chain polymer needs to react with light in a wavelength range of 250 nm to 400 nm and display liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

(A) The side chain polymer is preferably a photosensitive side chain that reacts with light in a wavelength range of 250 nm to 400 nm.

(A) The side chain polymer system exhibits liquid crystallinity in a temperature range of 100 ° C to 300 ° C, and therefore it is preferable to have a mesogenic group.

(A) A side chain type polymer-based main chain is bonded to a photosensitive side chain, which causes a crosslinking reaction, an isomerization reaction, or a light Fryce rearrangement to be induced by light. The structure of the photosensitive side chain is not particularly limited, and it is preferably a structure that induces a cross-linking reaction or photo-Fries rearrangement by light induction, and more preferably a cross-linking reaction. At this time, even if exposed to external stress such as heat, the achieved alignment control performance can be stably maintained for a long time. The structure of the photosensitive side chain polymer film exhibiting liquid crystallinity is not particularly limited as long as it satisfies this characteristic, but it is preferred that it has a rigid liquid crystal component on the side chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

The structure of the polymer may be, for example, a main chain and a side chain bonded thereto, and the side chain has biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, etc. The liquid crystal component has a structure of a photosensitive group that is crosslinked or isomerized by light-sensing, which is bonded to the front end, or has a main chain and a side chain bonded thereto, and the side chain has a liquid crystal component. The structure of a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction.

A more specific example of the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is preferably one selected from the group consisting of hydrocarbons, (meth) acrylates, itaconates, fumarates, and horses. Lamate, α-Sub Free radical polymerizable groups such as methyl-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc., and a backbone composed of at least one of a group of siloxanes, Structure of a side chain formed by at least one of the following formulae (1) to (6).

In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms to which they are bonded may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted with halogen groups; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8 Alicyclic hydrocarbon rings, or the same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can also be independently passed through -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, carbon 1 to 5 alkyl or 1 to 5 carbon oxy; Y ₂ is selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8 Alicyclic hydrocarbons, and the groups of their combinations, and the hydrogen atoms to which they are bonded can also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH -CN, halo, alkyl having 1 to 5 carbons, or alkane having 1 to 5 carbons Substituent group; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or the same meanings as Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, - CH = CH- , -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; Cou means coumarin-6 -Groups or coumarin-7- groups, and the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo , 1 to 5 carbon alkyl groups, or 1 to 5 alkyloxy groups; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently A group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, but X is -CH = CH When -CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of P is 2 or more, P may be the same as or different from each other. When the number of Q is 2 or more, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer of 0 ~ 2; when l1 and l2 are 0, and A is a single bond when T is a single bond; When l1 is 1, B is also a single bond when T is a single bond; H and I are each independently selected from a divalent benzene ring and naphthalene , Biphenyl ring, a furan ring, a pyrrole ring, and a group of their portfolio.

The side chain may be any photosensitive side chain selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above; l represents an integer of 1 to 12; m represents an integer of 0 to 2; m1 and m2 represent 1 to 3; Integer; n represents an integer from 0 to 12 (but B is a single bond when n = 0).

The side chain may be any photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

In the formula, A, X, 1, m, m1, and R have the same definitions as described above.

The side chain may be a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , 1, m1 and m2 have the same definitions as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17):

In the formula, A, X, l, and m have the same definitions as described above.

The side chain may be a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1 and m2 have the same definitions as above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Oxygen.

The side chain may be a photosensitive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, l, and m have the same definitions as above.

In addition, the (A) side chain-type polymer may have any liquid crystal side chain selected from the group consisting of the following formulae (21) to (31).

In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and lipid having 5 to 8 carbon atoms. Cyclic hydrocarbons, and groups of groups of these, the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or carbon 1 to 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l represents 1 to 12 Integer, m represents an integer from 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, and in formulas (25) to (26), the total of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and Alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<< Method for manufacturing photosensitive side chain polymer >>

The said photosensitive side chain type polymer which can exhibit liquid crystallinity can be obtained by superposing | polymerizing the said photoreactive side chain monomer which has a photosensitive side chain, and a liquid crystal side chain monomer.

[Photoreactive side chain monomer]

The photoreactive side chain single system refers to a monomer that can form a polymer having a photosensitive side chain at a side chain portion of the polymer when the polymer is formed.

The photoreactive group in the side chain is preferably the following structure and its derivative.

More specific examples of the photoreactive side chain monomer include, for example, a compound selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, and α-methylene-γ-butane. Free radical polymerizable groups such as lactone, styrene, ethylene, maleimine, norbornene, and a polymerizable group composed of at least one group of siloxanes, and a polymerizable group composed of the above formula (1) ~ The photosensitive side chain formed by at least one of (6) is preferably, for example, a photosensitive side chain formed by at least one of the above formulae (7) to (10), and a photosensitive side chain formed by the above formulae (11) to (13). ), At least one of the photosensitive side chains, the photosensitive side chain represented by the above formula (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the above formula ( The structure of the photosensitive side chain represented by 18) or (19) and the photosensitive side chain represented by the above formula (20) is preferable.

This case is provided as a photoreactive and / or liquid crystalline side chain monomer, for example, novel compounds (1) to (11) represented by the following formulae (1) to (11); and represented by the following formulae (12) to (17) Compounds (12) to (17).

In the formula, R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; R ¹⁰ represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1; and Py Represents 2-pyridyl, 3-pyridyl, or 4-pyridyl; and v represents 1 or 2.

[Liquid crystal side chain monomer]

The so-called liquid crystal side chain single system means a polymer derived from the monomer exhibits liquid crystallinity, and the polymer can form a liquid crystal group (Mesogen) at the side chain portion.

The liquid crystal group in the side chain may be a group that becomes a liquid crystal group structure alone, such as biphenyl or phenyl benzoate, or a group such as benzoic acid, in which side chains are hydrogen bonded to each other to form a liquid crystal group structure. The liquid crystal group of the side chain preferably has the following structure.

More specific examples of the liquid crystalline side chain monomer are preferably those selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, and α-methylene-γ- Free-radically polymerizable groups such as butyrolactone, styrene, ethylene, maleimide, norbornene, and a polymerizable group composed of at least one group of siloxanes, and a polymerizable group composed of the above formula (21) The structure of the side chain formed by at least one of ~ (31) is preferable.

(A) The side chain type polymer can be obtained by the above-mentioned polymerization reaction of a photoreactive side chain monomer exhibiting liquid crystallinity. In addition, it is possible to copolymerize a photoreactive side chain monomer and a liquid crystalline side chain monomer that do not exhibit liquid crystallinity, or a copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity. And get. Furthermore, it can be copolymerized with other monomers within a range that does not impair liquid crystal display performance.

Other monomers are exemplified by freely polymerizable monomers which are commercially available.

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, Maleic anhydride, styrene compounds and ethylene compounds.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthryl methyl acrylate, phenyl acrylate, and 2,2,2-trifluoroacrylate Ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydroacrylic acid Furfuryl ester, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and acrylic acid 8-ethyl-8-tricyclodecyl ester and the like.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and anthryl methacrylate Methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methacrylic acid 2- Methoxyethyl, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, methyl 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl methacrylate- 8-tricyclodecyl ester and the like. It is also possible to use glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl) (meth) acrylate (Meth) acrylate compounds having a cyclic ether group such as 3-oxetanyl methyl ester.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The manufacturing method of the side chain polymer in this embodiment is not particularly limited, and a method widely used in industry can be used. Specifically, it can manufacture by cationic polymerization, radical polymerization, and anionic polymerization of the vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, a radical polymerization is particularly preferable from the viewpoint of easy reaction control.

As the polymerization initiator for the radical polymerization, conventional compounds such as a radical polymerization initiator, a reversible addition-broken chain transfer (RAFT) polymerization reagent, and the like can be used.

A radical thermal polymerization initiator is a compound that generates a radical by heating above a decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), and difluorenyl peroxides (ethyl fluorenyl peroxide) , Benzamyl peroxide, etc.), peroxides (hydrogen peroxide, third butyl peroxide, cumene peroxide, etc.), dialkyl peroxides (di- Third butyl peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (Peroxy neodecanoic acid third butyl ester, peroxy pivalic acid third butyl ester, peroxy 2-ethyl cyclohexanoic acid third pentyl ester, etc.), persulfates (potassium persulfate, Sodium sulfate, ammonium persulfate, etc.), azo-based compounds (azobisisobutyronitrile, and 2,2'-bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl Propyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4 ' -Cumyl acetone, 1-hydroxycyclohexylphenyl ketone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethyl Oxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1- Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4,4'-tri (third butylperoxycarbonyl) benzophenone, 2, 4,6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2, 6-bis (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (tri (Chloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylamino) Styryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5 , 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-(4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 ,, 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6- (Trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3 , 6-bis (2-methyl-2-morpholinylpropanyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone Bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4 , 4'-tetrakis (third butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (third hexylperoxycarbonyl) benzophenone, 3,3'- Bis (methoxycarbonyl) -4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4'-bis (methoxycarbonyl) -4,3'-bis (third butyl) Peroxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (third butylperoxycarbonyl) benzophenone, 2- (3-methyl -3H-benzothiazol-2-ylidene) -1-naphthyl-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -ylidene) -1- (2-benzylidene) ethanone and the like. These compounds can It can be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a block polymerization method, a solution polymerization method, and the like can be used.

The organic solvent used in the polymerization reaction of the photosensitive side chain polymer that can exhibit liquid crystallinity is not particularly limited as long as it can dissolve the produced polymer. Specific examples are listed below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone (Pyrrolidone), N-ethyl-2-pyrrolidone, N-methylcaprolactone Amine, dimethyl sulfene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl lysone, ethyl lysone, methyl lysone acetate , Ethyl lysinoacetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetic acid Ester monopropyl ether, 3-methyl-3-methoxybutylacetic acid , Tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, di Isobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane Alkane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propylene glycol acetate monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 -Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl 2-pentanone, 3-methoxy-N, N-dimethylpropylamine, 3-ethoxy-N, N-dimethylpropylamine, 3-butoxy-N, N- Dimethylpropanamide and so on.

These organic solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve the produced | generated polymer, in the range which the produced | generated polymer does not precipitate, it can mix and use in the said organic solvent.

In addition, in radical polymerization, oxygen in an organic solvent becomes a cause of hindering the polymerization reaction. Therefore, it is preferable that the organic solvent is degassed as much as possible.

The polymerization temperature at the time of radical polymerization may be selected from any temperature of 30 ° C to 150 ° C, but is preferably in the range of 50 ° C to 100 ° C. In addition, the reaction can be performed at any concentration, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high to be uniformly stirred. Therefore, the monomer concentration is preferably 1% by mass ~ 50 mass%, more preferably 5 mass% to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is larger than that of the monomer, the molecular weight of the obtained polymer becomes smaller, and when the ratio is smaller, the molecular weight of the obtained polymer becomes larger. The ratio is preferably 0.1 mol% to 10 mol% relative to the monomer to be polymerized. Gather again Various monomer components, solvents, initiators, etc. may be added at the time.

[Recycling of polymers]

When the polymer produced is recovered from the reaction solution of the photosensitive side-chain polymer exhibiting liquid crystallinity obtained by the above reaction, the reaction solution may be put into a weak solvent to precipitate these polymers. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, heptane, butylcellolysin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl alcohol Ethyl ether, water, etc. The precipitated polymer is put into a weak solvent, and after filtering and recovering, the polymer can be dried under normal pressure or reduced pressure at normal temperature or under heating. In addition, when the polymer recovered by precipitation is re-dissolved in an organic solvent, and the operation of re-precipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the weak solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more weak solvents selected from these are used, it is preferable to improve the purification efficiency.

When the molecular weight of the (A) side chain polymer of the present invention takes into consideration the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film, the weight average molecular weight measured by GPC (gel permeation chromatography) method It is preferably 2,000 to 1,000,000, and more preferably 5,000 to 100,000.

[Modulation of polymer composition]

The polymer composition used in the present invention is preferably a coating liquid suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is in the form of a solution in which a resin component for forming a resin film is dissolved in an organic solvent State modulation is better. Here, this resin component is a resin component containing the photosensitive side chain type polymer which can demonstrate liquid crystallinity demonstrated previously. At this time, the content of the resin component is preferably 1% to 20% by mass, more preferably 3% to 15% by mass, and particularly preferably 3% to 10% by mass.

In the polymer composition of this embodiment, all of the aforementioned resin components may be photosensitive side-chain polymers capable of exhibiting liquid crystallinity, but they may be mixed within a range that does not impair liquid crystal display performance and photosensitivity. Other polymers than. At this time, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, and preferably 1% by mass to 50% by mass.

Examples of such other polymers include polymers composed of poly (meth) acrylate, polyamic acid, and the like, which are not photosensitive side chain polymers that exhibit liquid crystallinity.

<< (B) ingredients >>

The component (B) of the polymer composition used in the present invention is a polymer having at least one selected from the group consisting of polyimide and its precursor. The component (B) is preferably a polyimide precursor obtained by polymerizing a tetracarboxylic acid component and a diamine component, and a polyimide obtained by subjecting the polyimide precursor to fluorination. An amine selected from at least one polymer. Polyimide precursors include, for example, polyamidic acid (also known as POLYAMIDE ACID) or polyamidate.

<<< tetracarboxylic acid component >>>

(B) The tetracarboxylic acid component of the raw material of the component includes, for example, the following tetracarboxylic acids Dianhydride.

Tetracarboxylic dianhydrides having an alicyclic structure or an aliphatic structure, such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 -Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic 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-cyclohexyl succinic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, bicyclic [3,3 , 0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic dianhydride, cis-3,7-dibutylcyclooctane-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, hexacyclic [6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ] Alkane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalene-succinic acid di Anhydride, etc.

Aromatic tetracarboxylic dianhydrides, such as pyromelite dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetrahydride Carboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3 ' , 4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The characteristics of liquid crystal alignment, voltage holding characteristics, and stored charge of the liquid crystal alignment film formed by the above-mentioned tetracarboxylic dianhydride-based compounding may be 1 type or 2 or more types may be used in combination.

The tetracarboxylic acid component as the raw material of the (B) component can be used. Tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl diester dichloride. When the tetracarboxylic acid component contains such a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyfluorene imide precursor, that is, a polyamidate. The dialkyl dicarboxylic acid that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.

Specific examples are as follows.

Specific examples of the aliphatic tetracarboxylic acid diesters include, for example, 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl esters, and 1,2-dimethyl-1,2,3,4-cyclobutane Alkane tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1, Dialkyl 2,3,4-cyclobutane tetracarboxylic acid, dialkyl 1,2,3,4-cyclopentane tetracarboxylic acid, dialkyl 2,3,4,5-tetrahydrofuran tetracarboxylic acid Ester, 1,2,4,5-cyclohexane tetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl dialkyl succinate, 3,4-dicarboxyl-1,2 , 3,4-tetrahydro-1-naphthalene succinate dialkyl, 1,2,3,4-butane dicarboxylic acid dialkyl, bicyclic [3,3,0] octane-2,4 Dialkyl 6,6,8-tetracarboxylic acid, dialkyl 3,3 ', 4,4'-dicyclohexyl tetracarboxylic acid, dialkyl 2,3,5-tricarboxycyclopentylacetate Cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclic [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 ] Hexane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dialkyl ester, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalene- Succinic dianhydride.

Aromatic dialkyl dicarboxylic acid esters, specifically, for example, dialkyl pyromelite, 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl, 2,2', 3, 3'-biphenyltetracarboxylic acid dialkyl, 2,3,3 ', 4'-biphenyltetracarboxylic acid dialkyl Ester, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3', 4'-benzophenone tetracarboxylic acid dialkyl ester, bis (3, 4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) fluorene dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3 , 6,7-naphthalene tetracarboxylic acid dialkyl and the like.

<<< diamine content >>>

The diamine component as a raw material of the component (B) includes, for example, the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines, and diamines containing urea bonds.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4 ' -Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like.

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, and 3,5- Diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5- Diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino- 2,2'-dimethylbiphenyl (Bibenzyl), 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylphosphonium, 3, 3'-diaminodiphenylphosphonium, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy) benzene, 1,4-bis (4-aminophenoxy) Phenyl) benzene, 3,5-bis (4-aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [(4-amino Phenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (4-aminophenoxy) phenyl] fluorene, 1,1-bis (4-amine Phenyl) cyclohexane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2, 2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-di Amino diphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminofluorene, 1,6-diamine Hydrazone, 1,8-diaminofluorene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisilaxane, benzidine, 2,2'- Dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) Butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane , 1,8-bis (4-aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1 , 7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, bis (4-aminophenyl) propane-1,3-dioate, bis (4-aminophenyl) butane -1,4-Diester, bis (4-aminophenyl) pentane-1,5-diester, bis (4-aminophenyl) hexane-1,6-diester, di (4-Aminophenyl) heptane-1,7-diacid Ester, bis (4-aminophenyl) octane-1,8-diester, bis (4-aminophenyl) nonane-1,9-diester, bis (4-aminophenyl) ) Decane-1,10-diester, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminophenoxy (Yl) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) Phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy Yl] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] Decane and so on.

Examples of the aromatic-aliphatic diamine include a diamine represented by the following formula [DAM].

(In the formula [DAM], Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group.)

Specific examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-ylbenzylamine, 3-amino-N-methylbenzylamine, and 4-amino-N-formyl Benzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methylaminebutyl) aniline, 3- (5 -Aminepentyl) aniline, 4- (5-Aminopentyl) benzene Amine, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthalene Group) methylamine, 2- (6-aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine, and the like.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, and 2,7- Diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-amine Phenyl) -1,3,4-oxadiazole and the like.

Examples of the aliphatic diamine include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1 , 3-Diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane Alkane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylnonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethane, and the like.

Examples of the diamine containing a urea bond include N, N'-bis (4-aminophenethyl) urea and the like.

In addition, in the component (B), the diamine component which is polymerized with the tetracarboxylic acid component is within a range that does not impair the effect of the present invention. A diamine having a side chain for vertical alignment may be contained.

The diamine component in the component (B) may contain the following diamines.

(In the formula, m and n are each an integer from 1 to 11, m + n is an integer from 2 to 12, h is an integer from 1 to 3, and j is an integer from 0 to 3.)

The introduction of these diamines can contribute to a higher voltage retention rate (also referred to as VHR) of a liquid crystal display element using a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention. These diamines are preferable from the viewpoint that the accumulated charge reduction effect of such a liquid crystal display element is excellent.

The diamine component in the component (B) includes, for example, a diaminosiloxane represented by the following formula.

(Where m is an integer from 1 to 10.)

Among these (B) components, the diamine component has characteristics such as liquid crystal alignment, voltage holding characteristics, and charge accumulation when used as a liquid crystal alignment film. You can use 1 type or 2 or more types in combination. The mixing ratio at this time is not limited.

When the molecular weight of the polymer (polyimide precursor, polyimide) of the component (B) is taken into consideration, the strength of the obtained liquid crystal alignment film, the workability when the liquid crystal alignment film is formed, and the uniformity of the liquid crystal alignment film, The weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

When a polymer of the component (B) is obtained by a polymerization reaction of a tetracarboxylic acid component and a diamine component of the respective raw materials, a known synthetic method can be used. In general, a method of reacting a tetracarboxylic acid component and a diamine component in an organic solvent. The reaction between the tetracarboxylic acid component and the diamine component is relatively easy to proceed in an organic solvent and does not generate by-products, so it is preferred.

The organic solvent used for the reaction between the tetracarboxylic acid component and the diamine component is not particularly limited as long as it is a polyamine acid produced by dissolution.

Specific examples are as follows.

Organic solvents that can be used here include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylmethylene, tetramethylurea, pyridine, dimethylfluorene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, Ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve B Ester, ethyl cellosolve acetate, butyl carbid Alcohol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether Propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, Butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, di Ethyl ether, cyclohexanone, ethylene carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, acetone Methyl ester, ethyl pyruvate , Methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 -Propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N- Dimethylpropionamine, 3-ethoxy-N, N-dimethylpropionamine, 3-butoxy-N, N-dimethylpropionamine and the like. These can be used alone or in combination. Moreover, even if it is a solvent which does not dissolve a polyamic acid, in the range which does not precipitate the produced polyamic acid, you may mix and use it with the said solvent.

In addition, the moisture in the organic solvent will hinder the polymerization reaction and cause the generated polyamic acid to hydrolyze. Therefore, it is preferable to use a dehydrated organic solvent.

When the tetracarboxylic acid component and the diamine component are reacted in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly or dispersed or dissolved in an organic solvent and added. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like may be used. In addition, when the tetracarboxylic acid component or the diamine component is composed of a plurality of compounds, the reaction may be performed in a mixed state in advance, or the reactions may be sequentially performed individually, or the low-molecular-weight bodies of the respective reactions may be mixed and reacted as High molecular weight body.

The polymerization temperature at this time may be selected from any temperature of -20 to 150 ° C, and is preferably in the range of -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration, but when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction solution will be too high and it is difficult to stir uniformly. Therefore, the total concentration in the reaction solution of the tetracarboxylic acid component and the diamine component is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is performed at a high concentration in the initial stage, and an organic solvent may be added thereafter.

In the polymerization reaction of polyamic acid, the ratio of the total molar number of the tetracarboxylic acid component to the total molar number of the diamine component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer this mole ratio is to 1.0, the larger the molecular weight of the polyamidic acid produced.

<<< Polyimide >>>

Polyimide is obtained by dehydrating and closing the polyimide precursor of the aforementioned polyamic acid or polyamic acid ester. Dehydration of the amino acid group in polyimide The ring rate (imidization rate) does not have to be 100%, and it can be adjusted arbitrarily according to the purpose or purpose within the range of 0% to 100%.

The method for subjecting a polyimide precursor to ammonium imidization includes, for example, hot ammonization which heats a solution of a polyacrylic acid or a polyacrylic acid ester in a solution state, or a polyimide or a polyamic acid The catalyst is added to the solution of the ester.

The temperature at which the polyamidic acid or polyamidate is subjected to thermal sulfidation in a solution is 100 to 400 ° C, preferably 120 to 250 ° C. The water generated by the fluoridation reaction is aside It is preferable to discharge to the outside of the reaction system.

Catalysts for polyamidic acid or polyamidate. Imidization is based on polyamidic acid or polyamidate solution. Add alkaline catalyst and acid anhydride, preferably -20 ~ 250 ℃. It is performed by stirring at 0 to 180 ° C. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amino acid group, preferably 3 to 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is also preferred because it has a moderate alkalinity that allows the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. When acetic anhydride is used, purification at the end of the reaction is facilitated, and therefore, it is preferable. The rate of imidization through the catalyst imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

A method for synthesizing polyphosphonate is, for example, a tetracarboxylic acid diester obtained by reacting the tetracarboxylic acid diester with a halogenating agent such as thionyl chloride, thionium dichloride, ethylene dichloride, and phosphorus oxychloride. Contrast between ester dichloride and diamine Or a method in which a tetracarboxylic acid diester and a diamine component are reacted in the presence of a suitable condensing agent or a base. Alternatively, it can be obtained by polymerizing polyamidic acid in advance and esterifying a carboxylic acid in the polyamino acid by a polymer reaction.

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

As the base, pyridine, triethylamine, 4-dimethylaminopyridine, and the like can be used, but from the viewpoint of stable reaction progress, pyridine is preferred. The addition amount of the alkali is an amount that is easily removed and a high-molecular-weight body is easily obtained, and is preferably 2 to 4 times mole compared to the tetracarboxylic acid diester dichloride.

When the condensation reaction is performed in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodifluoride can be used as the condensing agent. Imine hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethylurea cation tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N', N'-tetramethylurea cation hexafluorophosphate , (2,3-dihydro-2-thio (keto) yl-3-benzoxazolyl) phosphonic acid diphenyl ester, 4- (4,6-dimethoxy-1,3,5-tri (Azin-2-yl) 4-methoxymorpholinium chloride n-hydrate and the like.

Moreover, in the method using the said condensing agent, reaction can be performed efficiently using a Lewis acid as an additive. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of the Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the tetracarboxylic acid diester.

The solvent used in the above reaction may be a solvent used in the polymerization of the polyamic acid shown above, but in terms of the solubility of the monomer and the polymer, N-methyl-2-pyrrolidone, γ- Butyrolactone may be used singly or in combination of two or more kinds. The concentration at the time of synthesis is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that it is not easy to cause precipitation of a polymer and it is easy to obtain a high molecular weight body. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the synthesis of the polyurethane is preferably dehydrated as much as possible, and the reaction is in a nitrogen atmosphere to prevent outside air from mixing. good.

Polyimide precursors such as polyamic acid and polyimide, polyimide precursors such as polyamic acid and polyimide, which are recovered from the reaction solution of polyimide, In the case of polyimide, it is sufficient to add the reaction solution to a weak solvent and cause it to precipitate. Examples of the weak solvent for Shendian include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer which is put into a weak solvent to precipitate it can be dried after filtering and recovering, at normal pressure or reduced pressure, at normal temperature or after heating. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the weak solvent at this time include alcohols, ketones, and hydrocarbons. When three or more types of weak solvents selected from these are used, the efficiency of purification can be further improved, which is preferable.

The polyimide precursor obtained by polymerizing the tetracarboxylic acid component and the diamine component is, for example, a polymer having a repeating unit represented by the following formula [a]. In addition, the polyimide precursors having such repeating units The dehydrated closed-loop is polyimide.

(In the formula [a], R ₁₁ is a tetravalent organic group derived from a tetracarboxylic acid component (the following formula (c)) of the raw material, and R ₁₂ is 2 of a diamine component (the following formula (b)) derived from the raw material Valence organic groups, A ₁₁ and A ₁₂ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, each of which may be the same or different, and j represents a positive integer.)

In the above formula [a], R ₁₁ and R ₁₂ are each one kind and may be polymers having the same repeating unit, and R ₁₁ or R ₁₂ are plural kinds and may be polymers having repeating units of different structures.

The above formula [a] in, R ₁₁ system radical derived from the tetracarboxylic acid component of the starting material, thus component (A) and (B) R Juxi component ₁₁ of the imine precursor structure represented by the above formula (4) of . And, R ₁₂ system radical derived from a diamine component of raw materials, thus R polyimide component (A) of the precursor ₁₂ having _{^{-P 1 - (Q 1) P}} - (Q 2) q - (Q 3 ) The side chain represented by _r -P ² and the main chain of R ₁₂ of the polyimide precursor of the component (B) has -CR ²¹ _2- .

(In formula [b] and formula [c], R ₁₁ and R ₁₂ are the same as those defined in formula [a].)

<< (C) Organic solvent >>

The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves a resin component. Specific examples are listed below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfene, tetramethylurea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, 3-methoxy-N, N-dimethylpropane Pyridamine, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolinone, ethyl Pentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl acetate, propylene carbonate, diglyme Ether, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol Alcohol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether , Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These can be used alone or in combination.

The polymer composition used in the present invention may contain components other than the components (A), (B), and (C) described above. Examples include solvents or compounds that improve film thickness uniformity or surface smoothness when coating a polymer composition, compounds that improve adhesion between a liquid crystal alignment film and a substrate, and the like, but are not limited thereto.

Specific examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness are listed below.

For example, isopropanol, methoxymethylpentanol, methyl lysin, ethyl lysin, butyl lysin, methyl lysin acetate, ethyl lysin acetate, butyl card Alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane , N-pentane, n-octane , Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, malonate Alcohol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 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, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate , N-butyl lactate, isoamyl lactate and other solvents with low surface tension.

These weak solvents may be used singly or in combination. When using a solvent as described above, avoiding a significant decrease in the solubility of the solvent contained in the polymer composition as a whole, preferably 5 to 80% by mass of the entire solvent, and more preferably 20 to 60% by mass.

Compounds that improve the uniformity of the film thickness or surface smoothness include, for example, fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants.

More specifically, there are EF TOP (registered trademark) EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (Sumitomo 3M Company), ASAHI GUARD (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical), and the like. These surfactants are used in proportions relative to the polymer composition. 100 parts by mass of the contained resin component is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include, for example, the following compounds containing a functional silane.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropane Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, acetic acid 9-triethoxysilyl-3,6-diazanonyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxy Silyl, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethyl) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) ) -3-aminopropyl triethoxy silane-like.

In addition, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, in order to prevent the decrease in electrical characteristics caused by the backlight when constituting a liquid crystal display element, the polymer composition may contain a phenoplast system such as the following Or additives to epoxy-containing compounds. Although the specific phenolic plastic additive is shown below, it is not limited to this structure.

Specific epoxy-containing compounds include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl ether Glyceryl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Group) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When using a compound that improves the adhesion to the substrate, the amount used is 100 parts by mass relative to the resin component contained in the polymer composition, preferably 0.1 to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass. When the amount is less than 0.1 parts by mass, the effect of improving adhesion cannot be expected, and when the amount is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

Additives can also use photosensitizers. Colorless sensitizers and triplet sensitizers are preferred.

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, and carbonyl Dicoumarin, aromatic 2-hydroxy ketone, and aromatic substituted by amine 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, Benzoanthone, thiazoline (2-benzylidene methylene-3-methyl-β-naphthothiazoline, 2- (β-naphthoyl methylene) -3-methyl Benzothiazoline, 2- (α-naphthylidenemethylene) -3-methylbenzothiazoline, 2- (4-biphenoxymethylene) -3-methylbenzothiazoline , 2- (β-naphthyridinemethylene) -3-methyl-β-naphthylthiazoline, 2- (4-Biphenoyl methylene) -3-methyl-β- Naphthylthiazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthylthiazoline), oxazoline (2-benzylidenemethylene-3-methyl) -Β-naphthyloxazoline, 2- (β-naphthylmethylene) -3-methylbenzooxazoline, 2- (α-naphthylmethylene) -3- Methylbenzoxazoline, 2- (4-bisphenolylmethylene) -3-methylbenzoxazoline, 2- (β-naphthylidenemethylene) -3-methyl- β-naphthoxazoline, 2- (4-biphenoxymethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylidenemethylene) -3 -Methyl-β-naphthoxazoline), benzothiazole, nitrobenzene Amine (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitropinene (5-nitropinene), (2-[(m-hydroxy-p-methoxy ) Styrenyl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindole, furanocoumarin, and the like.

Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone and acetophenone. ketone.

In addition to the above, in the polymer composition, as long as the range of the effect of the present invention is not impaired, a dielectric body or a conductive material may be added to change the electrical properties such as the permittivity or conductivity of the liquid crystal alignment film. The cross-linking compound is used to improve the film hardness or density when forming a liquid crystal alignment film.

The method of applying the polymer composition to a substrate having a conductive film for lateral electric field driving is not particularly limited.

The coating method is generally industrially performed by screen printing, lithography, flexographic printing, or inkjet. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), or a spray method, and these can be used depending on the purpose.

After the polymer composition is coated on a substrate having a conductive film for lateral electric field drive, heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven can be used at 50 to 200 ° C, preferably 50 The coating film was obtained by evaporating the solvent at ~ 150 ° C. The drying temperature at this time is preferably lower than the liquid crystal phase development temperature of the side chain polymer.

When the thickness of the coating film is too thick, the power consumption of the liquid crystal display element becomes unfavorable. When the thickness is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm.

After the step [I], and before the step [II], a step of cooling the substrate on which the coating film is formed to room temperature may be provided.

<Step (II)>

Step [II] is irradiating the coating film obtained in step [I] with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, The polarized plate is irradiated with polarized ultraviolet rays in a direction. The ultraviolet rays used can be ultraviolet rays with a wavelength ranging from 100nm to 400nm. It is preferable to select the most appropriate wavelength according to the type of coating film used, the transparent filter, and the like. In addition, for example, ultraviolet light in a range of 290 nm to 400 nm can be selected to selectively induce a photo-crosslinking reaction. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized ultraviolet radiation depends on the coating film used. The irradiation amount is 1 of the amount of polarized ultraviolet rays in which the difference between the absorbance of ultraviolet rays in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction is the maximum value of ΔA (hereinafter also referred to as ΔAmax). A range of% to 70% is preferable, and a range of 1% to 50% is more preferable.

<Step [III]>

Step [III] is to heat the coating film irradiated with polarized ultraviolet rays in step [II]. By heating, an alignment control ability can be given to a coating film.

For heating, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the coating film used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range of a temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as a liquid crystal exhibiting temperature). For example, when the film surface of the coating film is used, the liquid crystal display temperature of the coating film surface is estimated to be lower than the liquid crystal display temperature of the photosensitive side chain polymer that exhibits liquid crystal properties as a whole. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature on the surface of the coating film. That is, the temperature range of the heating temperature after the irradiation of polarized ultraviolet light is a temperature range that is higher than the liquid crystal display temperature of the side chain polymer used. A temperature lower than the lower limit of 10 ° C is set as the lower limit, and a temperature lower than the upper limit of the liquid crystal temperature range by 10 ° C is set as the upper limit. When the heating temperature is lower than the above temperature range, there is a tendency that the effect of anisotropic amplification by heat in the coating film is insufficient, and when the heating temperature is too higher than the above temperature range, the state of the coating film is close to isotropic. The liquid state (isotropic phase) tends to be difficult to align in one direction by self-organization.

The liquid crystal display temperature refers to a glass transition temperature (Tg) or higher when the side chain polymer or coating film surface is transferred from the solid phase phase to the liquid crystal phase, and the liquid crystal phase transition occurs from the liquid crystal phase phase to the isotropic phase ( Isotropic phase) The temperature below the isotropic phase transfer temperature (Tiso).

By having the above steps, the manufacturing method of the present invention can achieve an efficient introduction of anisotropy into a coating film. Moreover, a substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<Step [IV]>

[IV] Step is to obtain the substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving obtained in [III] in the same manner as obtained in [I '] to [III'] above. The substrate (second substrate) with a liquid crystal alignment film without a conductive film is arranged in an opposite manner through the liquid crystal alignment film of the two, and a liquid crystal cell is produced by a conventional method, and a lateral electric field-driven liquid crystal display is produced. Element steps. In addition, steps [I '] to [III'] are similar to step [I] except that a substrate without the conductive film for lateral electric field driving is used instead of the substrate with a conductive film for lateral electric field driving in step [I]. ] ~ [III] Do the same. Differences between steps [I] ~ [III] and steps [I ’] ~ [III’] The point is only the presence or absence of the above-mentioned conductive film, so the description of steps [I '] to [III'] is omitted.

To give an example of the production of a liquid crystal cell or a liquid crystal display element, prepare the first and second substrates described above, and spread the spacers on the liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes the inner side, and attach another A method of sealing a substrate by injecting liquid crystal under reduced pressure, or a method of attaching a substrate and sealing after dropping liquid crystal on a liquid crystal alignment film surface on which a spacer is dispersed. At this time, one of the substrates is preferably a substrate using an electrode having a comb-like structure for driving a lateral electric field. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The method for producing a substrate with a coating film of the present invention is to apply a polymer composition on a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, introduction of an anisotropy into the side-chain polymer film with high efficiency is achieved by heating, and a substrate with a liquid crystal alignment film having alignment control ability of liquid crystal is manufactured.

The coating film used in the present invention utilizes the principle of molecular realignment caused by the photoreaction based on side chains and the self-organization of liquid crystallinity to achieve the introduction of high-efficiency anisotropy to the coating film. In the manufacturing method of the present invention, when the side chain polymer has a photo-crosslinkable group structure as a photoreactive group, the side chain polymer is used to form a coating film on a substrate, and then irradiated with polarized ultraviolet rays, followed by heating Production of a liquid crystal display device.

The following description uses photocrosslinking having a photoreactive group. An embodiment of a side chain polymer having a basic structure is called a first embodiment, and a side chain polymer having a structure that has a light Fries rearrangement group that is a photoreactive group or a base that causes isomerization is used. The embodiment is called a second embodiment.

FIG. 1 schematically illustrates anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film using a side-linked polymer having a structure having a photo-crosslinkable group as a photoreactive group in the first aspect of the present invention. Illustration of an example. FIG. 1 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, and FIG. 1 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, FIG. 1 (c ) Is a diagram schematically showing the state of the side chain polymer film after heating, especially when the anisotropy introduced is small, that is, in the first aspect of the present invention, the amount of ultraviolet radiation in step [II] is △ A is a schematic diagram when the maximum ultraviolet exposure is within the range of 1% to 15%.

FIG. 2 schematically illustrates anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film using a side chain polymer having a structure having a photo-crosslinkable group as a photoreactive group in the first aspect of the present invention. Illustration of an example. FIG. 2 (a) is a diagram schematically showing a state of a side chain type polymer film before polarized light irradiation, FIG. 2 (b) is a diagram schematically showing a state of a side chain type polymer film after polarized light irradiation, and FIG. 2 (c ) Is a diagram schematically showing the state of the side chain polymer film after heating, especially when the anisotropy introduced is large, that is, in the first aspect of the present invention, the amount of ultraviolet radiation in step [II] is △ A is a schematic diagram when the range of 15% to 70% of the maximum ultraviolet irradiation amount.

Fig. 3 is a schematic illustration of a second aspect of the present invention, in which Anisotropy in a method for manufacturing a liquid crystal alignment film of a side chain polymer using a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) as a photoreactive group An example of import processing. FIG. 3 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, FIG. 3 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, and FIG. 3 (c ) Is a diagram schematically showing the state of the side chain polymer film after heating, especially when the anisotropy introduced is small, that is, in the second aspect of the present invention, the amount of ultraviolet radiation in the step [II] is △ A is a schematic diagram when the maximum ultraviolet irradiation amount is within a range of 1% to 70%.

FIG. 4 schematically illustrates the manufacture of a liquid crystal alignment film using a side chain polymer having a structure having a light Fries rearrangement group represented by the above formula (19) as a photoreactive group in the second aspect of the present invention. An example of anisotropic import processing in the method. FIG. 4 (a) is a diagram schematically showing a state of a side chain type polymer film before polarized light irradiation, FIG. 4 (b) is a diagram schematically showing a state of a side chain type polymer film after polarized light irradiation, and FIG. 4 (c ) Is a diagram schematically showing the state of the side chain polymer film after heating, especially when the anisotropy introduced is large, that is, in the second aspect of the present invention, the amount of ultraviolet radiation in the step [II] is △ A is a schematic diagram when the maximum ultraviolet irradiation amount is within a range of 1% to 70%.

In the first aspect of the present invention, in the anisotropic introduction treatment of the coating film, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount, △ A, first, A coating film 1 is formed on the substrate. As shown in FIG. 1 (a), the coating film 1 formed on the substrate has a structure in which side chains 2 are randomly arranged. According to the random arrangement of the side chain 2 of the coating film 1, the side The liquid crystal component and the photosensitive group of the chain 2 are also randomly aligned, and the coating film 1 is isotropic.

In the first aspect of the present invention, in the anisotropic introduction process for the coating film, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, △ A is first set at A coating film 3 is formed on the substrate. As shown in FIG. 2 (a), the coating film 3 formed on the substrate has a structure in which side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the liquid crystal components and photosensitive groups of the side chains 4 are also randomly aligned, and the coating film 2 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction process for the coating film, a side chain using a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) is used. In the case of the liquid crystal alignment film of the polymer type, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the maximum ultraviolet irradiation amount, first, a coating film 5 is formed on the substrate. As shown in FIG. 3 (a), the coating film 5 formed on the substrate has a structure in which side chains 6 are randomly arranged. According to the random arrangement of the side chains 6 of the coating film 5, the liquid crystal components and the photosensitive groups of the side chains 6 are also randomly aligned, and the side chain polymer film 5 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction process for the coating film, when a liquid crystal alignment film using a side chain polymer having a structure having a light Fries rearrangement group represented by the above formula (19) is used In the case where the ultraviolet irradiation amount in the step [II] is in a range of 1% to 70% of the maximum ultraviolet irradiation amount ΔA, first, a coating film 7 is formed on the substrate. As shown in FIG. 4 (a), the coating film 7 formed on the substrate has a structure in which side chains 8 are randomly arranged. According to the random arrangement of the side chains 8 of the coating film 7, the liquid crystal components and the photosensitive groups of the side chains 8 are also randomly aligned, and the coating film 7 is isotropic.

In the first embodiment of the present embodiment, when the amount of ultraviolet irradiation in step [II] is within a range of 1% to 15% of the maximum amount of ultraviolet irradiation, ΔA is irradiated with polarized light to the isotropic coating film 1. UV. That is, as shown in FIG. 1 (b), the photosensitive group of the side chain 2a having a photosensitive group in the side chain 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays causes a photoreaction such as a dimerization reaction preferentially. . As a result, the density of the side chains 2a subjected to the photoreaction becomes slightly higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, the coating film 1 is imparted with very little anisotropy.

In the first embodiment of the present embodiment, when the amount of ultraviolet radiation in step [II] is within a range of 15% to 70% of the maximum amount of ultraviolet radiation, △ A is irradiated with polarized light to the isotropic coating film 3. UV. As a result, as shown in FIG. 2 (b), the photosensitive group of the side chain 4a having a photosensitive group in the side chain 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially caused a photoreaction such as a dimerization reaction. As a result, the density of the side chains 4a undergoing photoreaction becomes slightly higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, a small anisotropy is imparted to the coating film 3.

In the second aspect of this embodiment, a liquid crystal alignment film using a side chain polymer having a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) is used, [II] When the ultraviolet irradiation amount in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. The results are shown in FIG. 3 (b), which are arranged on the side parallel to the direction of polarization of the ultraviolet rays. The photosensitive group of the side chain 6a having a photosensitive group in the chain 6 preferentially causes a photoreaction such as light Fries rearrangement. As a result, the density of the side chain 6a subjected to the photoreaction becomes slightly higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, a very small anisotropy is imparted to the coating film 5.

In the second aspect of this embodiment, a coating film using a side chain polymer having a structure having a light Fryes rearrangement base represented by the above formula (19) is used, and the ultraviolet irradiation amount in step [II] is ΔA When it is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. As a result, as shown in FIG. 4 (b), the photosensitive groups of the side chains 8a having the photosensitive groups in the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially cause light reactions such as light Fries rearrangement. . As a result, the density of the side chains 8a subjected to the photoreaction becomes higher in the polarization direction of the ultraviolet rays, and as a result, a small anisotropy is imparted to the coating film 7.

Next, in the first aspect of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 15% of the maximum ultraviolet irradiation amount, the coating film 1 after the polarized light irradiation is heated, It becomes a liquid crystal state. As a result, as shown in FIG. 1 (c), the coating film 1 differed in the amount of cross-linking reaction between the direction parallel to and perpendicular to the direction of polarized light irradiated with ultraviolet rays. In this case, since the amount of cross-linking reaction generated in a direction parallel to the direction of polarized light irradiated with ultraviolet rays is very small, the cross-linking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the direction of polarized light irradiated with ultraviolet rays is higher than the liquid crystallinity in the parallel direction, and self-organized in a direction parallel to the direction of polarized light irradiated with ultraviolet rays to reorient the side chain 2 containing the liquid crystal component. As a result, very little anisotropy of the coating film 1 caused by the photo-crosslinking reaction It is increased by heat, and gives greater anisotropy to the coating film 1.

Similarly, in the first embodiment of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 after the polarized light irradiation is heated. , Into a liquid crystal state. As a result, as shown in FIG. 2 (c), the amount of cross-linking reaction between the side chain polymer film 3 and the direction parallel to the direction of polarized light irradiated with ultraviolet rays is different. Therefore, self-organization is performed in a direction parallel to the direction of polarized light irradiated with ultraviolet rays to realign the side chain 4 containing the liquid crystal component. As a result, the small anisotropy of the coating film 3 caused by the photo-crosslinking reaction is increased by heat, and a larger anisotropy is imparted to the coating film 3.

Similarly, in the second aspect of this embodiment, a coating film of a side chain polymer using a structure having a photo-isomerizable group or a light Fryes rearrangement group represented by the above formula (18) is used. II] When the ultraviolet irradiation amount in the step is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 5 after polarized light irradiation is heated to become a liquid crystal state. As a result, as shown in FIG. 3 (c), the coating film 5 has different amounts of Fryce rearrangement reactions between the parallel and vertical directions of the polarized light direction irradiated with ultraviolet rays. In this case, the liquid crystal alignment force of the Frye rearrangement which is generated in a direction perpendicular to the polarized light direction irradiated with ultraviolet rays is stronger than the liquid crystal alignment force of the side chain before the reaction. Self-organizing causes the side chain 6 containing the liquid crystal component to re-align. As a result, the very small anisotropy of the coating film 5 caused by the Fries rearrangement reaction is increased due to heat, and a greater anisotropy is imparted to the coating film 5.

Similarly, in the second aspect of the present embodiment, a utilization tool is used. The coating film of a side chain polymer having a light Fries rearrangement structure represented by the above formula (19), the ultraviolet irradiation amount in the step [II] is 1% of the maximum ultraviolet irradiation amount of △ A In the range of ~ 70%, the coating film 7 after the polarized light irradiation is heated to become a liquid crystal state. As a result, as shown in FIG. 4 (c), the side chain type polymer film 7 has different amounts of light Fryce rearrangement reaction between the direction parallel to and perpendicular to the direction of polarized light irradiated with ultraviolet rays. Because the light Fryce rearrangement body 8 (a) has stronger anchoring force than the side chain 8 before rearrangement, when a certain amount of light Frye rearrangement body is generated, it is parallel to the polarization direction of the ultraviolet light The orientation is self-organized to reorient the side chain 8 containing the liquid crystal component. As a result, the small anisotropy of the coating film 7 caused by the Fries rearrangement reaction is increased by heat, and a greater anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can be a liquid crystal alignment film with excellent alignment control performance by sequentially radiating the coating film with polarized ultraviolet rays and heat treatment to efficiently introduce anisotropy.

In addition, the coating film used in the method of the present invention optimizes the amount of polarized ultraviolet radiation to the coating film and the heating temperature of the heat treatment. This makes it possible to efficiently introduce anisotropy into the coating film.

The optimum amount of polarized ultraviolet radiation for introducing a highly effective anisotropy into the coating film used in the present invention corresponds to the photocrosslinking reaction or photoisomerization reaction, or photo-Fryes in the photosensitive film of the coating film. The amount of rearrangement reaction is the optimal amount of polarized ultraviolet radiation. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, when there are few photosensitive groups in the side chain undergoing photocrosslinking reaction, photoisomerization reaction, or photofrye rearrangement reaction, the coating film cannot be formed. For sufficient light response. At this time, sufficient self-organization cannot be performed even after heating. In addition, the coating film used in the present invention has a structure having a photocrosslinkable group. As a result of irradiating polarized ultraviolet light, when the photosensitive group of the side chain of the crosslink reaction is excessive, the crosslink reaction between the side chains proceeds excessively. At this time, the obtained coating film becomes rigid, which may prevent subsequent self-organization by heating. In addition, as for the coating film used in the present invention, and the structure having a light Fryce rearrangement base is irradiated with polarized ultraviolet light, when the photosensitive group of the side chain of the light Fryce rearrangement reaction becomes excessive, the Liquid crystallinity is excessively reduced. At this time, the liquid crystallinity of the obtained film is also lowered, which may prevent subsequent self-organization by heating. In addition, when a structure with a light Fryce rearrangement is irradiated with polarized ultraviolet light, when the amount of ultraviolet radiation is too large, the side chain polymer will photoly decompose, which may prevent subsequent self-organization by heating. Happening.

Therefore, in the coating film used in the present invention, the optimum amount of the photo-crosslinking reaction or the photo-isomerization reaction or the photo-Frys rearrangement reaction of the photosensitive group of the side chain by irradiation of polarized ultraviolet rays is such that The photosensitive group of the side chain polymer film is preferably 0.1 mol% to 40 mol%, and more preferably 0.1 mol% to 20 mol%. When the amount of the photosensitive group of the side chain that undergoes the photoreaction is in this range, the self-organization of the subsequent heat treatment can be effectively performed, and anisotropy in the film can be formed with high efficiency.

The coating film used in the method of the present invention optimizes the photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the side chain of the side chain type polymer film by optimizing the irradiation amount of polarized ultraviolet light. The amount of Fries rearrangement reaction is optimized. Therefore, together with the subsequent heat treatment, high efficiency is achieved. Anisotropy is introduced into the coating film used in the present invention. At this time, the preferable amount of polarized ultraviolet rays can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the vertical direction after the polarized ultraviolet radiation were measured, respectively. From the measurement result of ultraviolet absorption, the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction in the coating film was evaluated as ΔA. In addition, the maximum value of ΔA (ΔAmax) achieved in the coating film used in the present invention and the amount of polarized ultraviolet radiation to achieve it were obtained. In the manufacturing method of the present invention, based on the amount of polarized ultraviolet radiation to achieve this ΔAmax as a reference, a preferable amount of polarized ultraviolet radiation to be irradiated in the manufacture of the liquid crystal alignment film can be determined.

In the manufacturing method of the present invention, it is preferable to set the irradiation amount of polarized ultraviolet rays to the coating film used in the present invention within a range of 1% to 70% of the amount of polarized ultraviolet rays to achieve ΔAmax, and more preferably set to 1% ~ Within 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays in the range of 1% to 50% of the amount of polarized ultraviolet rays achieving △ Amax is equivalent to 0.1 of the total photosensitive group of the side chain polymer film. Molar% ~ 20 Molar% The amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

From the above, according to the manufacturing method of the present invention, in order to introduce anisotropy into the coating film with high efficiency, the liquid crystal temperature range of the side chain polymer is used as a reference, and the preferred heating temperature may be determined as described above. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C to 200 ° C, the heating temperature after polarized ultraviolet radiation is set to 90 ° C. ~ 190 ° C is preferred. Thereby, a greater anisotropy is imparted to the coating film used in the present invention.

As described above, the liquid crystal display element provided by the present invention exhibits high reliability in displaying external stress such as light or heat.

As described above, a substrate for a lateral electric field drive type liquid crystal display element manufactured by the method of the present invention or a lateral electric field drive type liquid crystal display element having the substrate is excellent in reliability, and can be applied to large-screen and high-definition liquid crystal televisions. .

[Example]

The examples use abbreviations as follows.

<Methacrylic monomer>

MA1 is synthesized by a synthesis method described in a patent document (WO2011-084546). MA2 is synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).

<Tetracarboxylic dianhydride>

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

PMDA: pyromellitic dianhydride

BODA: Bicyclic [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

<Diamine>

DDE: 4,4'-diaminodiphenyl ether

DDM: 4,4’-diaminodiphenylmethane

DA-3MG: 1,3-bis (4-aminophenyloxy) propane

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

CH ₂ Cl ₂ : dichloromethane

<Polymerization initiator>

AIBN: 2,2’-azobisisobutyronitrile

[Synthesis Example of Polyamic Acid and Polyimide] <Synthesis Example 1: Polyamic Acid>

MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed again. Then, reacted at 50 ° C for 30 hours to obtain Polymer solution of methacrylate. This polymer solution was dropped into diethyl ether (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder.

NMP (54.0 g) was added to the obtained powder (6.0 g), and stirred at room temperature for 3 hours. A methacrylate polymer solution (M1) having a solid content concentration of 10.0 wt% was obtained. At the end of stirring, the polymer was completely dissolved.

<Synthesis Example 2: Polyamic acid>

Using the same method as in Synthesis Example 1 above, MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were prepared using AIBN (0.14 g) and THF (85.45 g). Polymer solution (M2).

<Synthesis Example 3: Polyamic acid>

The tetracarboxylic dianhydride component was CBDA (1.82g), and the diamine component was DDE (2.00g). The reaction was performed at room temperature for 18 hours in NMP (34.43g) to obtain the concentration of polyamic acid (PAA-1) 10wt% solution.

<Synthesis Examples 4 to 7: Polyamic acid>

With the composition shown in Table 1 below, the polyamidic acid solutions of Synthesis Examples 4 to 7 were synthesized using the same method as in Synthesis Example 3 of the polyamic acid.

<Synthesis Example 8: Polyimide>

NMP (6.7 g) was added to 10.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 5 and diluted to prepare a polyamino acid solution having a concentration of 6 wt%. 2.2 g of acetic anhydride and 1.0 g of pyridine were added to the polyfluorenic acid solution, and reacted at 50 ° C. for 3 hours to carry out the imidization. The obtained polyfluorene imine solution was cooled to about room temperature, and then put into 70 g of methanol to recover the precipitated solid. The solid was washed twice with methanol, and then dried under reduced pressure at 100 ° C. to obtain a ochre-colored powder of polyimide. 3.0 g of the obtained powder was stirred at NMP (27.0 g) at room temperature for 3 hours. A polyimide solution (SPI-1) having a solid content concentration of 10.0 wt% was obtained. At the end of stirring, the polymer was completely dissolved.

(Example 1)

To 1.2 g of the methacrylic acid polymer (M1) obtained in the above Synthesis Example 1 was added 4.8 g of a polyamic acid solution (PAA-1), and the mixture was stirred at room temperature for 1 hour. BCS (4.0 g) was added to this solution, followed by stirring at room temperature for 1 hour to obtain a polymer solution (A1) having a solid content concentration of 6.0 wt%. This polymer solution directly becomes a liquid crystal alignment agent for forming a liquid crystal alignment film.

(Examples 2 to 8, Comparative Examples 1 to 2)

With the composition shown in Table 2 below, the polymer solutions of Examples 2 to 10 were obtained in the same manner as in Example 1. Further, Comparative Examples 1 to 2 were also modulated in the same manner.

<< The production of liquid crystal cells >>

Using the liquid crystal alignment agent (A1) obtained in Example 1, a liquid crystal cell was produced in the procedure shown below. The substrate is a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and is provided with comb-shaped pixel electrodes formed by patterning an ITO film. The pixel electrode has a comb-tooth shape formed by bending a central portion and arranging a plurality of electrode elements in a zigzag shape. The width in the short-side direction of each electrode element is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrode forming each pixel is composed of electrode elements with a curved central portion and a plurality of ㄑ -shaped electrode elements arranged. Therefore, the shape of each pixel is not a rectangular shape, but is provided with a similar ㄑ character similar to the electrode element, which is bold and curved at the center shape. In addition, each pixel has a first region on the upper side and a second region on the lower side of the curved portion divided up and down with the central curved portion as a boundary. When comparing the first region and the second region of each pixel, the formation direction of the electrode elements constituting their pixel electrodes is different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode forms an angle of + 15 ° (clockwise) in the first region of the pixel, and the pixel electrode in the second region of the pixel The electrode elements form an angle of -15 ° (clockwise). That is, the directions of the first region and the second region of each pixel in the substrate surface rotation (in-plane switching) caused by the voltage applied between the pixel electrode and the counter electrode are mutually The opposite direction.

The liquid crystal alignment agent (A1) obtained in Synthesis Example 1 was spin-coated on the prepared substrate with electrodes. Then, it was dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film with a thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet light of 313 nm at 1 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 150 ° C. for 10 minutes (single firing), and then the substrate cooled to room temperature was heated again at 150 ° C. The heating plate was heated for 10 minutes (two firings) to obtain a substrate with a liquid crystal alignment film. Likewise, the irradiation amount of ultraviolet radiation of ^{1mJ / cm 2 ~ 10mJ / cm} 2 when in 1mJ / cm ² interval, and ^{10mJ / cm 2 ~ 100mJ / cm} 2 , the at 10mJ / cm ² interval, and 100mJ / cm ² In the above case, different substrates were produced at intervals of 50 mJ / cm ² . In addition, a coating film was also formed on a glass substrate having a columnar spacer having a height of 4 μm as an opposing substrate without forming an electrode, and subjected to an alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on a liquid crystal alignment film of one substrate. Next, another substrate is bonded so that the alignment direction of the liquid crystal alignment film surface becomes 0 °, and then the sealant is thermally cured to produce an empty cell. A liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having a structure of a liquid crystal display element having an IPS (lateral switching) mode.

Regarding the liquid crystal alignment agents (A2 to A9) obtained in Examples 2 to 9, a liquid crystal cell was also prepared by the same method as A1.

(Alignment observation)

A liquid crystal cell was produced in the above-mentioned manner. Then, re-alignment treatment was performed in an oven at 120 ° C for 60 minutes. Then, the polarizing plates were placed in an orthogonal state and observed with a polarizing microscope. When the liquid crystal cell was rotated, a black display state was obtained, and no bright spot or poor alignment state was evaluated as good. UV exposure such as As described above, as a result of observing the alignment properties of the respective substrates, Table 3 shows the margins of the irradiation amounts with good alignment properties.

<< Evaluation of Voltage Holding Rate (VHR) >>

VHR evaluation is based on the obtained liquid crystal cells, at a temperature of 70 ° C., a voltage of 5 V is applied for 60 μs, the voltage after 1667 ms is measured, and how much the voltage is maintained is calculated by the voltage retention rate (VHR).

To measure the voltage holding ratio, a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technology Co., Ltd. was used.

Using the liquid crystal alignment agent (B1) obtained in Comparative Example 1 and the liquid crystal alignment agent (B2) obtained in Comparative Example 2, a liquid crystal cell was produced in the same manner as in the case where the liquid crystal alignment agent (A1) was used, and VHR was evaluated by the same method.

The results are shown in Table 3 below.

As shown in Table 3, it is known that compared with Comparative Example 1 in which the component (A) is common and does not contain the component (B), compared with Examples 1 to 5 of the present invention, the irradiation amount region (irradiation margin) is wide, Wider irradiation area achieves the desired effect. The comparison between Examples 6 to 10 and Comparative Example 2 is the same.

Claims (16)

A polymer composition characterized by: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a temperature range of 100 ° C to 300 ° C, and (B) a polyimide and its precursor At least one polymer selected from the group and (C) an organic solvent, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (1) to (6): In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted with halogen groups; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to The alicyclic hydrocarbon ring of 8 or the same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can each independently pass through -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, carbon 1 to 5 alkyl or 1 to 5 carbon oxy; Y ₂ is selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8 The alicyclic hydrocarbons, and the groups of these groups, and the hydrogen atoms to which they are bonded can also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or 1 to 5 carbons Alkyloxy substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in the Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, - CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; Cou means Coumarin 6-yl group or coumarin-7-yl group, and the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN , Halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q Each is independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, but X is When -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring, and when the number of P is 2 or more, P may be mutually The same or different, when the number of Q is 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0 ~ 2; when l1 and l2 are 0, when T is a single bond, A Also represents a single bond; when l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently Since the divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and the group of combinations of these. For example, the composition of claim 1 in the scope of patent application, wherein (A) component has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement. For example, the composition of claim 1 or 2, in which the polyimide precursor of component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component. For example, for the composition of the scope of application for the patent item 1 or 2, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (7) to (10): In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-; Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or The same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded may each independently pass -COOR ₀ (where R ₀ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or Alkyloxy substituted with 1 to 5 carbons; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO- O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1 and m2 represent 1 An integer of ~ 3; n represents an integer of 0 to 12 (but when n = 0, B is a single bond); Y ₂ is selected from a bivalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon The alicyclic hydrocarbons of 5 to 8 and their groups are composed of groups, and the hydrogen atoms to which they are bonded can also independently pass through each other. -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl having 1 to 5 carbon atoms or alkyloxy having 1 to 5 carbon atoms; R represents a hydroxyl group , carbons, alkoxy of 1 to 6, or represents the same as defined in the Y _1. For example, in the composition of the scope of application for the patent item 1 or 2, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (11) to (13): In the formula, each of A independently represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O -CO-CH = CH-; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; l represents an integer from 1 to 12, m represents an integer from 0 to 2, and m1 represents an integer from 1 to 3; R Represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbons, or 2 to 6 same or different selected from their substituents Bases in which each ring is bonded via a bonding group B, and the hydrogen atoms to which they are bonded may also each independently pass -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl group with 1 to 5 carbon atoms, or alkyloxy group with 1 to 5 carbon atoms, or represents Hydroxyl or alkoxy having 1 to 6 carbon atoms. For example, in the composition of the scope of claims 1 or 2, the component (A) has a photosensitive side chain represented by the following formula (14) or (15): In the formula, each of A independently represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O -CO-CH = CH-: Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or substituted by them The selected two or six rings of the same or different groups are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can also independently pass -COOR ₀ (where R ₀ represents a hydrogen atom Or alkyl with 1 to 5 carbons), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or 1 with carbon ~ 5 alkyloxy substitution; l represents an integer from 1 to 12, m1, m2 represents an integer from 1 to 3. For example, the composition of the scope of claims 1 to 2 of the patent application, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17): In the formula, A represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO -CH = CH-; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O -CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. For example, the composition in the scope of claims 1 or 2, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formula (18) or (19): In the formula, each of A and B independently represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon ring having 5 to 8 carbon atoms, or from The same or different 2 to 6 rings selected by the same substituents are bonded to each other through a bonding group B, and the hydrogen atoms to which they are bonded may each independently pass -COOR ₀ (wherein R ₀ represents Hydrogen atom or alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo group, alkyl group having 1 to 5 carbon atoms, or carbon an alkyl group of 1 to 5 substituents; and one of those q2 q1 is 1 and the other is 0; l represents an integer of 1 to 12, m1, m2 represents an integer of 1 to 3; R & lt ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. For example, in the composition of the scope of application for the patent item 1 or 2, the component (A) has a photosensitive side chain represented by the following formula (20): In the formula, A represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO -CH = CH-; Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or selected from these substituents The same or different 2 to 6 rings are bonded through a bonding group B, and the hydrogen atoms to which they are bonded may also independently pass through -COOR ₀ (where R ₀ represents a hydrogen atom or a carbon number 1 to 5 alkyl), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or 1 to 5 carbons Alkyloxy substitution; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O -CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. For example, in the composition of the scope of application for patents 1 or 2, the component (A) has any liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): In the formula, A and B have the same definitions as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, And the combination of these groups, the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or 1 to 5 carbon atoms Alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, biphenyl Ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; one of q1 and q2 is 1 and The other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more. In formulas (25) to (26), , The total of all m is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halo, monovalent benzene ring, naphthalene ring, biphenyl Rings, furan rings, nitrogen-containing heterocycles, and alicyclic hydrocarbons and alkyl or alkyloxy groups having 5 to 8 carbon atoms; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-,- CH = N-, -CF _2- . A method for manufacturing a substrate with a liquid crystal alignment film is to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element which is provided with alignment control energy by having the following steps: [I] will apply for patents No. 1 to 10 The step of applying the composition of any one to a substrate having a conductive film for lateral electric field drive to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the coating film obtained in [II]. A substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by a method according to item 11 of the patent application. A lateral electric field drive type liquid crystal display element is characterized in that it has a substrate with the scope of application for patent item 12. A method for manufacturing a liquid crystal display element, which is characterized by obtaining a lateral electric field drive type liquid crystal display element with the following steps: a step of preparing a substrate (first substrate) for which the scope of the patent application is No. 12; In the substrate step, a liquid crystal alignment film imparting alignment control ability is obtained by having the following steps [I '] to [III']: [I '] coating a second substrate containing the following components (A) ~ ( C) The step of forming a coating film with the polymer composition: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a group consisting of polyimide and its precursor [II '] The step of irradiating the coating film obtained by [I'] with polarized ultraviolet light; [III '] The coating film obtained by [II'] A step of heating; and [IV] a step of obtaining a liquid crystal display element, in which the liquid crystal alignment films of the first and second substrates are opposed to each other through liquid crystal, and the first and second substrates are arranged to face each other. For example, the method of claim 14 of the patent scope, wherein the polyimide precursor of the component (B) is obtained by polymerizing a tetracarboxylic acid component and a diamine component. A lateral electric field-driven liquid crystal display element, which is characterized by being manufactured by a method according to item 14 or 15 of the scope of patent application.