TWI628219B - 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 solves the above-mentioned problem by a polymer composition containing: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) having one in the molecule An amine compound having a primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group being bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, 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] will A step of applying the composition 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] applying [II] The obtained coating film is subjected to a heating step.

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. For example, the polyimide film is irradiated with polarized ultraviolet light, and the polarization direction dependence of ultraviolet absorption of the molecular structure is used to cause anisotropic decomposition. Moreover, Lee The liquid crystal is aligned with polyfluorene imide that remains undecomposed (see, for example, Patent Document 1).

Moreover, a photo-alignment method of a photo-crosslinking type or a photo-isomerization type is also known. For example, a polyvinyl cinnamate is irradiated with polarized ultraviolet rays, and a dimerization reaction (crosslinking reaction) occurs at the double bond portion of the two side chains parallel to the polarized light. In addition, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). When using a side chain polymer with azobenzene on the side chain, the polarized light is irradiated with ultraviolet rays, and an isomerization reaction occurs in the azobenzene portion of the side chain parallel to the polarized light, so that the liquid crystal is aligned 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.

[Previous 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)

[Summary of Invention]

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 irradiation amount of polarized light 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, poor alignment or display afterimage may occur. In particular, in a liquid crystal display element driven by a lateral electric field, since liquid crystal molecules are switched in-plane, alignment of the liquid crystal is likely to be shifted after the liquid crystal is driven, which causes a large problem of display sticking caused by AC driving.

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, the object of the present invention is to provide, in addition to the above objects, a lateral electric field drive type liquid crystal element having a liquid crystal alignment film interface that adsorbs ionic impurities in the liquid crystal and has an improved voltage holding ratio, and a liquid crystal alignment for the element. membrane.

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 characterized by (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a primary amine group and a nitrogen-containing aromatic group in the molecule Heterocyclic, and the aforementioned primary amine group is bonded to an amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group and (C) an organic solvent.

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

<3> In the item <1> or <2>, the component (B) is represented by the following formula A- [1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. , Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocyclic ring),

<4> The polymer composition according to any one of the items <1> to <3>, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (1) to (6) :

(Wherein 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 carbon number 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 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can be independent of each other 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, halo, C1-C5 alkyl group or C1-C5 alkyloxy group is substituted; Y ₂ is selected from bivalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon number 5 ~ The alicyclic hydrocarbons of 8 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, 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 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 items <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 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 when n = 0, B is a single bond);

<6> In any one of the items <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 items <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 items <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 items <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 items <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 items <1> to <10>, the component (A) has a 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] the above-mentioned <1> ~ <11> The step of applying the composition of any one of the items on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] A step of irradiating the obtained coating film with [I] with polarized ultraviolet light; And [III] a step of heating the coating film obtained in [II].

<13> A substrate characterized by having the above-mentioned method of <12> A liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by the method.

<14> A lateral electric field drive type liquid crystal display element, characterized in that it has a substrate according to the item <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: the step of preparing the substrate (the first substrate) of the above item <13>; and obtaining the liquid crystal alignment film The step of the second substrate is to obtain a liquid crystal alignment film that imparts alignment control ability by having the following steps [I '] to [III']: [I '] coating the second substrate with the following component (A) ~ (C) Polymer coating to form a coating film: (A) Photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) 1 or more molecules having two or more hydroxyl groups, Alkyl, alkoxy, alkoxyalkyl, ethylene oxide, epoxy, isocyanate, oxetanyl, cyclocarbonate, trialkoxysilyl, and polymerizable unsaturated bonds A crosslinkable compound selected from at least one substituent and (C) an organic solvent; [II '] a step of irradiating polarized ultraviolet rays to the coating film obtained by [I']; [III '] applying [II' ] The step of heating the obtained coating film; and [IV] obtaining the liquid crystal display element Step, which makes the system via the liquid crystal of the first and second substrate of the liquid crystal alignment film opposite way, so that the first and second substrates arranged opposite to each.

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

In addition, the following inventions were found.

<P1> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises obtaining a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that imparts alignment control energy by having the following steps:

[I] The step of applying a polymer composition containing (A), (B), and (C) to a substrate having a conductive film for lateral electric field driving to form a coating film: (A) within a specific temperature range A photosensitive side chain polymer exhibiting liquid crystallinity, (B) a molecule having a primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group Amine compounds and (C) organic solvents.

[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 component (B) may be a divalent organic compound having the following formula A- [1] (wherein Y ₁₁ is an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group) Group, Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocyclic ring).

<P4> 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 (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 An alkylene group of 12 and the hydrogen atom bonded thereto may be substituted with a halogen group; 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 ~ 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 (A) component 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-mentioned <P1> to <P3>, the (A) component 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, l, m1 and m2 have the same definitions as above.

<P8> In any one of <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 (A) component 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, and R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH -CN, halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons.

<P10> In any of the above <P1> to <P3>, the component (A) may have There is 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 to obtain a lateral electric field drive type liquid crystal display element by having the following steps: a step of preparing the substrate (first substrate) of the above <P12>; obtaining a first substrate having a liquid crystal alignment film 2 substrate step, which obtains a liquid crystal that imparts alignment control ability by having the following steps [I '] to [III'] Alignment film:

[I '] A step of applying a polymer composition containing the following components (A), (B), and (C) to the second substrate to form a coating film: (A) exhibiting liquid crystallinity in a specific temperature range (B) an amine compound having a primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) Organic solvents.

[II '] a step of irradiating the coating film obtained in [I'] with polarized ultraviolet light;

[III '] a step of heating the coating film obtained in [II']; and

[IV] The step of obtaining a liquid crystal display element 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) The molecule has one primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Amine compounds and (C) organic solvents.

<P17> In the above-mentioned <P16>, the component (B) may be the above-mentioned formula A- [1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is An amine compound represented by a nitrogen-containing aromatic heterocyclic ring).

According to the present invention, it is possible 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.

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

In addition, according to the present invention, in addition to the above-mentioned effects, a liquid crystal alignment film having a lateral electric field driving type in which an ionic impurity in the liquid crystal is adsorbed at the interface of the liquid crystal alignment film and which has an improved voltage retention can be provided.

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 crosslinked organic group is used for a photosensitive side chain, and the introduced anisotropy is small. Of the situation.

[Fig. 2] 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 large. Of the situation.

[Fig. 3] A diagram schematically illustrating an example of anisotropic introduction processing in a method for producing 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.

[Form of Implementing 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, the slight anisotropy exhibited by polarized light irradiation becomes a driving force. The liquid crystal side chain polymer itself reorganizes effectively due to self-organization. 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: [I] A photosensitive side chain polymer containing (A) a liquid crystal exhibiting property in a specific temperature range, and (B) having one in the molecule A polymerizable composition in which a primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and (C) an organic solvent are coated with a lateral electric field drive A step of forming a coating film on the substrate of the conductive film used; [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].

A liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted is obtained by the above steps, and a substrate having the liquid crystal alignment film can be obtained.

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.

In addition to using a substrate without a conductive film for lateral electric field drive instead of a substrate with a conductive film for lateral electric field drive, the second substrate uses the above steps [I] to [III] (due to the use of a driver without lateral electric field drive) The substrate of the conductive film is sometimes referred to as steps [I '] to [III'] in this application for the sake of convenience, and a second substrate having a liquid crystal alignment film to which alignment control ability is given can be obtained.

A method for manufacturing a lateral electric field-driven liquid crystal display device has the following steps [IV]:

[IV] A step of obtaining the liquid crystal display element by arranging the first and second substrates obtained by facing the liquid crystal alignment films of the first and second substrates through the liquid crystal. 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 to contain a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, has a primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the aforementioned primary amine group is bonded to a fat The polymerizable composition of an amine compound of an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group and an organic solvent is coated on a substrate having a conductive film for driving a lateral electric field to form a coating film.

<Substrate>

There is no particular limitation on the substrate, but the manufactured liquid crystal display element is In the transmissive type, it is preferable to use a substrate having 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 type polymer exhibiting liquid crystallinity in a specific temperature range; (B) having one primary amine group and nitrogen in the molecule An amine compound having an aromatic heterocyclic ring and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; 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. A liquid crystal component and a photosensitive group that is crosslinked or isomerized by light sensing and bonded to the front end Structure, or has a main chain and a side chain bonded to the side chain, and the side chain has a structure of a phenylbenzoate group that becomes a liquid crystal component and 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. Free radically polymerizable groups such as maleic acid esters, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and at least 1 The structure of the main chain composed of species and the side chain composed of 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, 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, l, m, m1, and R have the same definitions as above. Righteousness.

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 crystal side chain monomer that do not exhibit liquid crystallinity, or to copolymerize a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity. Combined. 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, methoxytrimethacrylate Glycol ester, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, methyl formate 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like. Also available are glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxelan) (meth) acrylate (Meth) acrylate compounds having a cyclic ether group such as butyl) 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 hydrogen peroxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-third Peroxides, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkylperesters (peroxy Tert-butyl neodecanoate, tert-butyl peroxypivalate, tert-peroxy 2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, Ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 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)- Methyl ethyl ketone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3 , 4,4'-tris (third butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxy Styryl) -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'-methoxy Phenylstyryl) -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 (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) 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'-Di (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-dimethylaminopropylfluorenyl) carbazole, 3,6-bis (2-methyl-2-morpholinylpropylfluorenyl) -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) diphenyl Ketone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4'-bis (methoxycarbonyl) -4,3'- Bis (third butylperoxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (third butylperoxycarbonyl) benzophenone, 2 -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalene-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H ) -Subunit) -1- (2-benzylidene) ethanone and the like. These compounds may 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 monoacetic acid Ester 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, Amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl Ether, cyclohexanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propanoic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy- N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N- Methylpropan-acyl amine.

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 carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight. 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% by mass, better 5 Amount% ~ 30% by 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. During the polymerization, various monomer components, solvents, and initiators may be added.

[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 is considered in consideration of the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film, The weight-average molecular weight determined by GPC (gel permeation chromatography) method is preferably 2000 to 1,000,000, and more preferably 5000 to 100,000.

[Preparation 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 preferably prepared in the form of a solution in which a resin component for forming a resin film is dissolved in an organic solvent. 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, polyimide, and the like, which are not photosensitive side-chain polymers that exhibit liquid crystallinity.

<Amine compound>

The polymer composition used in the present invention contains a specific amine compound, specifically, it has a primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic ring. Hydrocarbyl amine Compound.

When the specific amine compound is a polymer composition used in the present invention to form a liquid crystal alignment film, it is not particularly limited as long as it has the following effects i) and / or ii). i) At the interface of the liquid crystal alignment film, ionic impurities in the liquid crystal are adsorbed, and / or ii) the voltage retention is improved.

The amount of the specific amine compound is not particularly limited as long as it produces the above-mentioned effects. Among 100 parts by mass of the polymer composition used in the present invention, it may be 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring. , Cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, ring Nonadecane ring, cycloeicosane ring, tricyclic eicosane ring, tricyclic eicosane ring, bicycloheptane ring, decalin ring, norbornene ring and adamantane ring. It is preferably a ring formed from 3 to 20 carbon atoms, more preferably a ring formed from 3 to 15 carbon atoms, and even more preferably a non-aromatic cyclic hydrocarbon group formed from a ring formed from 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the amine compound contains at least one, preferably one to four aromatics selected from the group consisting of the following formulas [20a], [20b], and [20c] Cyclic hydrocarbons.

(In the formula, Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms.)

Specifically, there are a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, Thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoline ring , Phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like. The carbon atom of these nitrogen-containing aromatic heterocyclic rings may have a hetero atom-containing substituent.

A more preferable amine compound is an amine represented by the following formula A- [1] (wherein Y ₁₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring) Compound. In Formula A- [1], Y ₁₂ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferred Y ₁₁ in the formula A- [1] may be a divalent organic group having one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. The non-aromatic cyclic hydrocarbon group has the above-mentioned structure, for example. Y _{11 is more} preferably, for example, an aliphatic hydrocarbon group having 1 to 15 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, Cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y _{11 is} particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, -CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group contained in Y _{11 which} is not adjacent to the amine group may be -O-, -NH-, -CO-O-, -O- CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S (O) _2- , -CF _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, divalent Cyclic hydrocarbon or heterocyclic ring. In addition, a hydrogen atom bonded to an arbitrary carbon atom may be a straight or branched chain alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, Substituted by a hydroxyl group.

Specific examples of the divalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, and cyclobutane Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, Cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, three Cycdocosane ring, bicycloheptane ring, decalin ring, norbornene ring, adamantane ring, etc.

Specific examples of the divalent heterocyclic ring include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, and a purine. Ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole (benzimidazole) ring, benzoimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. .

Y ₁₂ is a nitrogen-containing aromatic heterocyclic ring in formula A- [1], which is the same as the above, and is an aromatic group containing at least one structure selected from the group consisting of formula [20a], formula [20b], and formula [20c]. Group of cyclic hydrocarbons. The specific example has the above-mentioned structure. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole (benzoimidazole) ring, quinoxaline ring, azepine ring, diazepine ring, naphthyl ring, phenazine ring, phthalazine ring.

In addition, from the viewpoint of the ease of electrostatic interaction between a nitrogen-containing aromatic heterocyclic ring and a carboxyl group in a specific polyimide, such as a salt or a hydrogen bond, Y ₁₁ and Y ₁₂ contain the formula [20a], formula [ 20b] or formula [20c] is preferably bonded with non-adjacent substituents.

In addition, the carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y _{12 in} Formula A- [1] may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. .

A preferred combination of Y ₁₁ and Y ₁₂ in Formula A- [1] is that Y ₁₁ is a group having an aliphatic hydrocarbon group selected from carbon atoms of 1 to 20 and a non-aromatic cyclic hydrocarbon group selected from carbon atoms of 3 to 20 One type of divalent organic group, Y ₁₂ is selected from the group consisting of pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ( benzimidazole ring, benzoimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthalene ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₂ may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A more preferable amine compound is an amine compound represented by the following formula A- [2].

(Wherein Y ₁₃ is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, and Y ₁₄ is a single bond, -O-, -NH-, -S-, -SO ₂ -or carbon A divalent organic group of 1 to 19. The total number of carbon atoms in Y ₁₃ and Y ₁₄ is 1 to 20. Y ₁₅ is a nitrogen-containing aromatic heterocyclic ring.)

Y ₁₃ in Formula A- [2] is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. Specific examples include straight or branched chain alkylenes having 1 to 10 carbon atoms, unsaturated alkylenes having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, Cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, tricyclic behenane ring, bicycloheptane ring, Decahydronaphthalene ring, norbornene ring, adamantane ring, etc. Preferred are straight or branched chain alkylenes having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane Ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring. Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

-CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group which is not adjacent to the amine group contained in Y ₁₃ can be -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -S (O) _2- , -CF _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, divalent ring Substituted hydrocarbyl and heterocyclic. In addition, a hydrogen atom system bonded to an arbitrary carbon atom may be a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, or Substituted by a hydroxyl group. The so-called cyclic hydrocarbon group and heterocyclic system have the same meanings as those defined for Y ₁₁ in Formula A- [1].

Y ₁₄ in Formula A- [2] is a single bond, -O-, -NH-, -S-, -SO ₂ -or a divalent organic group having 1 to 19 carbon atoms. This divalent organic group having 1 to 19 carbon atoms has a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and the like. Specific examples of such Y _{14 are} as follows.

For example, there are single bonds, -O-, -NH-, -S-, -SO _2- , hydrocarbon groups having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-, -NH -CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O- Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring , Cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicocosane ring, tricycloicocosane ring, tricyclocosane ring, bicycloheptane ring , Decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole Ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, three Azine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazol e) ring, benzoimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, An azole ring, a piperazine ring, a piperidine ring, a dioxane ring, a morpholine ring, and the like. Y ₁₄ may contain two or more of these.

Specific examples containing two or more of these are -NH-CH _2- , -NH-C ₂ H _4- , -NH-C ₃ H _6- , -NH-C ₄ H _8- , -S-CH _2- , -SC ₂ H _4- , -SC ₃ H _6- , -SC ₄ H _8- , -O-CH _2- , -OC ₂ H _4- , -OC ₃ H _6- , -OC ₄ H _8- , -NH-CO-CH _2- , -NH-CO-C ₂ H _4- , -NH-CO-C ₃ H _6- , -NH-CO-C ₄ H _8- , -CO-CH ₂ -,- CO-C ₂ H _4- , -CO-C ₃ H _6- , -CO-C ₄ H _8- , -CO-NH-CH _2- , -CO-NH-C ₂ H _4- , -CO-NH -C ₃ H _6- , -CO-NH-C ₄ H _8- , -NH-CH ₂ -CH (CH ₃ )-, -NH-C ₂ H ₄ -CH (CH ₃ )-, -NH-C ₃ H ₆ -CH (CH ₃ )-, -NH-C ₄ H ₈ -CH (CH ₃ )-, -S-CH ₂ -CH (CH ₃ )-, -SC ₂ H ₄ -CH (CH ₃ ) -, -SC ₃ H ₆ -CH (CH ₃ )-, -SC ₄ H ₈ -CH (CH ₃ )-, -O-CH ₃ -CH (CH ₃ )-, -OC ₂ H ₄ -CH (CH ₃ )-, -OC ₃ H ₆ -CH (CH ₃ )-, -OC ₄ H ₈ -CH (CH ₃ )-, -NH-CO-CH ₂ -CH (CH ₃ )-, -NH-CO- C ₂ H ₄ -CH (CH ₃ )-, -NH-CO-C ₃ H ₆ -CH (CH ₃ )-, -NH-CO-C ₄ H ₈ -CH (CH ₃ )-, -CH (OH ) -CH _2- , -CH (OH) -C ₂ H _4- , -CH (OH) -C ₃ H _6- , -CH (OH) -C ₄ H _8- , -CH (CH ₂ OH)- CH _2- , -CH (CH ₂ OH) -C ₂ H _4- , -CH (CH ₂ OH) -C ₃ H _6- , -CH (CH ₂ OH) -C ₄ H _8- , -NH-CH (CH ₂ OH) -CH _2- , -CO-NH-CH (CH ₂ OH) -CH _2- , -NH-CO-CH (CH ₂ OH) -CH _2- , -CO-CH (CH ₂ OH)- CH _2- , -S-CH (CH ₂ OH) -CH _2- , -O-CH (CH ₂ OH) -CH _2- , -CH (N (CH ₃ ) ₂ )-, -C ₆ H _4- O-, -C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH _2- , -C ₆ H ₄ -S- and so on.

Y ₁₅ in formula A- [2] is a nitrogen-containing aromatic heterocyclic ring, and has the same definition as Y ₁₂ in formula A- [1]. A specific example thereof has the same structure as the Y ₁₂ described above. Among these, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ( benzoimidazole) ring, quinoxaline ring, azepine ring, diazepine ring, naphthyl ring, phenazine ring or phthalazine ring.

In addition, from the viewpoint of the ease of electrostatic interactions between the nitrogen-containing aromatic heterocyclic ring and a salt of a carboxyl group in a specific polyimide, such as hydrogen bonding, Y ₁₄ is the formula [20a] and [20b] contained in Y ₁₅ ] Or formula [20c] is preferably a bond of non-adjacent carbon atoms.

The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y _{15 in} Formula A- [2] may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in Formula A- [2] is that Y ₁₃ is a straight or branched chain alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a cyclopentane. Alkanes, cyclohexanes, cycloheptanes, cyclooctanes, cyclononanes, cyclodecanes, cycloundecanes, cyclododecanes, cyclotridecanes, cyclotetradecanes Ring, norbornene ring or adamantane ring, Y ₁₄ is a single bond, linear or branched alkylene group with 1 to 10 carbon atoms, -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -S-, -SO _2- , -CF _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) ₂ -,- -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, -CH (OH)-, -NH-CH ₂ -,- NH-C ₂ H _4- , -NH-C ₃ H _6- , -NH-C ₄ H _8- , -S-CH _2- , -SC ₂ H _4- , -SC ₃ H _6- , -SC ₄ H _8- , -O-CH _2- , -OC ₂ H _4- , -OC ₃ H _6- , -OC ₄ H _8- , -NH-CO-CH _2- , -NH-CO-C ₂ H ₄ -, -NH-CO-C ₃ H _6- , -NH-CO-C ₄ H _8- , -CO-CH _2- , -CO-C ₂ H _4- , -CO-C ₃ H ₆ -,- CO-C ₄ H _8- , -CO-NH-CH _2- , -CO-NH-C ₂ H _4- , -CO-NH-C ₃ H _6- , -CO-NH-C ₄ H _8- , -NH-CH ₂ -CH (CH ₃ )-, -NH-C ₂ H ₄ -CH (CH ₃ )-, -NH-C ₃ H ₆ -CH (CH ₃ )-, -NH-C ₄ H ₈ -CH (CH ₃ )-, -S-CH ₂ -CH (CH ₃ )-, -SC ₂ H ₄ -CH (CH ₃ ) -, -SC ₃ H ₆ -CH (CH ₃ )-, -SC ₄ H ₈ -CH (CH ₃ )-, -O-CH ₃ -CH (CH ₃ )-, -OC ₂ H ₄ -CH (CH ₃ )-, -OC ₃ H ₆ -CH (CH ₃ )-, -OC ₄ H ₈ -CH (CH ₃ )-, -NH-CO-CH ₂ -CH (CH ₃ )-, -NH-CO- C ₂ H ₄ -CH (CH ₃ )-, -NH-CO-C ₃ H ₆ -CH (CH ₃ )-, -NH-CO-C ₄ H ₈ -CH (CH ₃ )-, -CH (OH ) -CH _2- , -CH (OH) -C ₂ H _4- , -CH (OH) -C ₃ H _6- , -CH (OH) -C ₄ H _8- , -CH (CH ₂ OH)- CH _2- , -CH (CH ₂ OH) -C ₂ H _4- , -CH (CH ₂ OH) -C ₃ H _6- , -CH (CH ₂ OH) -C ₄ H _8- , -NH-CH (CH ₂ OH) -CH _2- , -CO-NH-CH (CH ₂ OH) -CH _2- , -NH-CO-CH (CH ₂ OH) -CH _2- , -CO-CH (CH ₂ OH ) -CH _2- , -S-CH (CH ₂ OH) -CH _2- , -O-CH (CH ₂ OH) -CH _2- , -CH (N (CH ₃ ) ₂ )-, -C ₆ H _{4 -O -, - C 6 H} 4 -NH -, - C 6 H 4 -CO-NH-, -C 6 H 4 -NH-CO -, - C 6 H 4 -CO -, - C 6 H 4 -CH _2- , -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane Alkane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane , A benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, phenalene ring or, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine Ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, azepine ring, diazepine ring, Naphthalene ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group may also contain a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom.

A more preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in Formula A- [2] is that Y ₁₃ is a straight or branched chain alkylene having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, and a cyclopentane. Alkane ring, cyclohexane ring, cycloheptane ring, norbornene ring, or adamantane ring, Y ₁₄ is a single bond, straight or branched chain alkylene with 1 to 5 carbon atoms, -O-, -NH -, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -S (O) _2- , -CH (OH)-,- NH-CH _2- , -S-CH _2- , -O-CH _2- , -OC ₂ H _4- , -NH-CO-CH _2- , -CO-CH _2- , -CO-NH-CH ₂ -, -NH-CH ₂ -CH (CH ₃ )-, -S-CH ₂ -CH (CH ₃ )-, -O-CH ₃ -CH (CH ₃ )-, -NH-CO-CH ₂ -CH (CH ₃ )-, -CH (OH) -CH _2- , -CH (OH) -C ₂ H _4- , -CH (CH ₂ OH) -CH _2- , -NH-CH (CH ₂ OH)- CH _2- , -CO-NH-CH (CH ₂ OH) -CH _2- , -NH-CO-CH (CH ₂ OH) -CH _2- , -CO-CH (CH ₂ OH) -CH _2- , -S-CH (CH ₂ OH) -CH _2- , -O-CH (CH ₂ OH) -CH _2- , -CH (N (CH ₃ ) ₂ )-, -C ₆ H ₄ -O-,- C ₆ H ₄ -NH-, -C ₆ H ₄ -CO-NH-, -C ₆ H ₄ -NH-CO-, -C ₆ H ₄ -CO-, -C ₆ H ₄ -CH ₂ -,- C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane , A benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, phenalene ring or, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine Ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, azepine ring, diazepine ring, Naphthalene ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Formula A- Y [2] of _13, Y ₁₄ and Y ₁₅ and more preferably of a combination of lines Y ₁₃ is a C 1-5 straight-chain or branched alkylene of, cyclopropane ring, cyclobutane ring , Cyclopentane ring or cyclohexane ring, Y ₁₄ is a single bond, straight or branched chain alkylene with 1 to 5 carbon atoms, -O-, -NH-, -CO-O-, -O-CO -, -CO-NH-, -NH-CO-, -CO-, -CH (OH)-, -NH-CH _2- , -S-CH _2- , -O-CH _2- , -NH-CO -CH _2- , -CO-CH _2- , -CO-NH-CH _2- , -NH-CH ₂ -CH (CH ₃ )-, -S-CH ₂ -CH (CH ₃ )-, -O- CH ₃ -CH (CH ₃ )-, -NH-CO-CH ₂ -CH (CH ₃ )-, -CH (OH) -CH _2- , -CH (OH) -C ₂ H _4- , -CH ( CH ₂ OH) -CH _2- , -NH-CH (CH ₂ OH) -CH _2- , -CO-NH-CH (CH ₂ OH) -CH _2- , -NH-CO-CH (CH ₂ OH) -CH _2- , -CO-CH (CH ₂ OH) -CH _2- , -S-CH (CH ₂ OH) -CH _2- , -O-CH (CH ₂ OH) -CH _2- , -CH ( _{N (CH 3) 2) -} , - C 6 H 4 -O -, - C 6 H 4 -NH -, - C 6 H 4 -CO-NH-, -C 6 H 4 -NH-CO -, - C ₆ H ₄ -CO-, -C ₆ H ₄ -CH _2- , -C ₆ H ₄ -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring , Norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, or anthracene ring, Y ₁₅ is a pyrrole ring , An imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzoimidazole ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A particularly preferred combination of Y ₁₃ , Y ₁₄ and Y ₁₅ in Formula A- [2] is that Y ₁₃ is a linear or branched alkylene, cyclobutane ring, or cyclohexane ring having 1 to 5 carbon atoms, Y ₁₄ is a single bond, -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH)-, benzene ring, naphthalene ring, fluorene ring, Anthracene ring, Y ₁₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₁₅ may have a halogen atom and / or a substituent of an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Specific examples of the specific amine compound of the component (B) of the present invention include compounds M1 to M156.

Better compounds are, for example, M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125 , M128 ~ M137, M139 ~ M143, M149 ~ M156. M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116 , M118 ~ M121, M125, M134 ~ M136, M139, M140, M143, M150, M152 ~ M156.

<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 in under.

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, three Glycol methyl ether. 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.

Such as isopropanol, methoxymethylpentanol, methyl fibrinolysin, ethyl solvent Cellulose, butylcellosolvin, methylcellosolvate acetate, ethylcellosolvin acetate, butylcarbitol, ethylcarbitol, ethylcarbitol 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 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 ethyl Acid ester, 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, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methyl Ethoxy propionate, 3-ethoxy propionic acid, 3-methoxy propionic acid, propyl 3-methoxy propionate, butyl 3-methoxy propionate, 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 organic solvents with low surface tension.

These weak solvents can be used alone or in combination. use. 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. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the resin component contained in the polymer composition.

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-aminopropyl Triethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 , 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethyl Oxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethyl) -3-amine Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and the 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, glycerin Diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N' -Tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) 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 2-hydroxy ketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxydi Benzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2 -(4-bisphenolylmethylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylene) -3-methyl-β-naphthylthiazoline, 2- ( 4-Biphenoyl methylene) -3-methyl-β-naphthylthiazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthylthiazole Oxazoline), oxazoline (2-benzylidene methylene-3-methyl-β-naphthyloxazoline, 2- (β-naphthylidene) Methylene) -3-methylbenzoxazoline, 2- (α-naphthylmethylidene) -3-methylbenzooxazoline, 2- (4-biphenolylmethylene ) -3-methylbenzoxazoline, 2- (β-naphthylmethylidene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoxymethylene ) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitro Aniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitropinene (5-nitropinene), (2-[(m-hydroxy-p-methoxy ) Styryl] 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 to irradiate 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 substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain 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 amount of exposure is the amount of polarized ultraviolet light that achieves the difference between the absorbance of ultraviolet light in the direction parallel to the polarized ultraviolet light in the coating film and the absorbance of ultraviolet light in the vertical direction. It is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

<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 set to a lower limit of a temperature lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain polymer used by the lower limit, and lower than the upper limit of the liquid crystal temperature range by 10 ° C It is preferable that the temperature is in the range of 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 temperature above the glass transition temperature (Tg) when the side chain polymer or coating film surface is transferred from the solid phase to the liquid crystal phase, and the liquid crystal phase transition occurs from the liquid crystal phase phase to the isotropic phase (such as Xiang Xiang) Temperature below the isotropic transition temperature (Tiso).

The thickness of the coating film formed after heating is preferably 5 nm to 300 nm, and more preferably 50 nm to 150 nm, for the same reason described in step [I].

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 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 the same as those in step [I] except that the substrate without the conductive film for lateral electric field driving is used instead of the substrate with the conductive film for lateral electric field driving in step [I]. ] ~ [III] The same goes. The difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the aforementioned 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 substrate, a method of injecting liquid crystal under reduced pressure and sealing, or dropping the liquid crystal A method for attaching a substrate and sealing the liquid crystal alignment film surface on which a spacer is dispersed, and the like. 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.

In the following description, an embodiment using a side chain polymer having a structure having a photo-crosslinkable group as a photoreactive group is referred to as a first form, and using a light Fries rearrangement group as a photoreactive group may cause a difference. An embodiment of the structured side chain polymer 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 chain polymer having a structure having a photo-crosslinkable group as a photoreactive group in the first aspect of the present invention. One case Illustration. 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 the 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 side-chain structure schematically illustrating a structure using a photo-isomerizable group or a light Fries rearrangement group represented by the above formula (18) as a photo-reactive group in the second aspect of the present invention. An example of an anisotropic introduction process in a method for manufacturing a polymer liquid crystal alignment film. 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 schematic showing the high side chain type after heating Diagram of the state of the molecular film, especially when the anisotropy is small, that is, in the second aspect of the present invention, the ultraviolet irradiation amount in the step [II] is ΔA is 1% to 70% of the maximum ultraviolet irradiation amount Schematic diagram in the range of%.

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 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 process of the coating film, when the ultraviolet irradiation amount in 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 chains 2 of the coating film 1, the liquid crystal components and the photosensitive groups of the side chains 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 amount of ultraviolet irradiation in step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount of △ A, first 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 side Chain 4 randomly arranged structure. 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 a liquid crystal alignment film of the polymer type, when the ultraviolet irradiation amount in the step [II] is in 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 When the amount of ultraviolet radiation in the step [II] is within a range of 1% to 70% of the maximum amount of ultraviolet radiation of 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 aspect 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. UV. That is, as shown in FIG. 1 (b), they are arranged in a direction parallel to the polarization direction of ultraviolet rays. Among the side chains 2 having a photosensitive group, the photosensitive group of the side chain 2a preferably causes a photoreaction such as a dimerization reaction. 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 aspect of the present embodiment, when the amount of ultraviolet radiation in the step [II] is within a range of 15% to 70% of the maximum 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 15% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. As a result, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having a photosensitive group in the side chain 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially causes light reactions 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 the present embodiment, a side chain polymer using a structure having a light Fries rearrangement group represented by the above formula (19) is used. In the coating film, when the amount of ultraviolet irradiation in step [II] is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, ΔA is irradiated with polarized ultraviolet rays on the isotropic coating film 7. 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 amount of ultraviolet irradiation in step [II] is in the range of 1% to 15% of the maximum ultraviolet irradiation amount, ΔA, 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, the extremely small anisotropy of the coating film 1 caused by the photo-crosslinking reaction is increased by heat, and a greater anisotropy is imparted to the coating film 1.

Similarly, in the first aspect of the present embodiment, when the amount of ultraviolet irradiation in 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 side-chain type polymer film 3 intersects between the direction parallel to the direction perpendicular to the polarization direction of the ultraviolet light and the direction perpendicular to the polarization direction. The amount of side reaction 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 the present embodiment, a coating film of a side chain polymer using a structure having a photo-isomeric 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 coating film 5 after the 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 coating film using a side chain polymer having a structure having a light Fries rearrangement group represented by the above formula (19) is used, and the amount of ultraviolet radiation in step [II] When ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, 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 amount of light Fries rearrangement reaction between the side chain polymer film 7 and the direction parallel to and perpendicular to the direction of polarized light irradiated with ultraviolet rays does not change. with. 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 on the side chain that undergoes photocrosslinking reaction, photoisomerization or reaction, or photofrye rearrangement reaction, a sufficient photoreaction amount cannot be obtained. . 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. The coating film used in the present invention has light Structure of Fryce Rearrangement Base As a result of irradiating polarized ultraviolet light, when the photosensitive group of the side chain of the Frye Rearrangement reaction becomes excessive, the liquid crystallinity of the coating film 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, it is possible to efficiently introduce anisotropy 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 results of the ultraviolet absorption, the polarization direction of the coating film with that of the polarized ultraviolet rays was evaluated. The difference between the ultraviolet absorbance in the row direction and the ultraviolet absorbance in the vertical direction is 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 the polarized ultraviolet radiation is preferably set to 90 ° C to 190 ° C. 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 device manufactured by the method of the present invention or a lateral electric field drive having the substrate The liquid crystal display element has excellent reliability, and is suitable for large-screen and high-definition liquid crystal televisions.

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the examples.

[Example]

The methacrylic monomers MA1 and MA2 and the additives T1 and T2 used in the examples are shown below.

In addition, MA1 and MA2 were respectively synthesized as follows. That is, MA1 is synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 is synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 9-118717).

The additives T1 (3-aminomethylpyridine) and T2 (1- (3-aminopropyl) imidazole) are commercially available.

In addition, the abbreviations of the reagents used in this example are shown below.

(Organic solvents)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellolysin

(Polymerization initiator)

AIBN: 2,2’-azobisisobutyronitrile

<Synthesis example 1>

MA1 (4.99 g, 15.0 mmol) and MA2 (4.60 g, 15.0 mmol) were dissolved in THF (88.5 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed again. Then, it reacted at 50 degreeC for 30 hours, and the polymer solution of the methacrylate was obtained. liquid. 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 methacrylate polymer powder (6.0 g), and it was stirred at room temperature for 5 hours to dissolve. BC (40.0 g) was added to this solution, and a methacrylic acid polymer solution B1 was obtained by stirring.

<Example 1>

0.015 g of T1 was added to the methacrylic acid polymer solution B1 (5.0 g) obtained in Synthesis Example 1, and stirred at room temperature for 3 hours to obtain a polymer solution A1. This polymer solution A1 can be directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

Using this liquid crystal alignment agent A1, 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.

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 curved portion in the center 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.

<< Modulation of liquid crystal cells >>

The liquid crystal alignment agent A1 obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Next, it was dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet light of 313 nm at 20 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. 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.

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

Using the prepared liquid crystal cell, an AC voltage of 30 Hz and 16 Vpp frequency was applied for 168 hours in a 70 ° C constant temperature environment. Then, in a state where the pixel electrode and the counter electrode of the liquid crystal cell are short-circuited, they are left at room temperature for 1 hour. The obtained liquid crystal cell was applied with a voltage of 5 V for 60 μs at a temperature of 70 ° C., and the voltage after 16.67 ms was measured. The voltage holding rate (VHR) was used to calculate how much the voltage was held. To measure the voltage holding ratio, a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technology Co., Ltd. was used.

Table 1 shows the composition and VHR results of the liquid crystal alignment agent in Example 1.

<Example 2>

In Example 1, except that T2 was used instead of T1, the polymer solution A2 of Example 2 was obtained by the same method as in Example 1, and a liquid crystal cell was prepared in the same manner as in Example 1, and the voltage holding ratio was measured. The results are shown in Table 1.

<Control 1>

Control 1 except that the polymer solution B1 obtained in Synthesis Example 1 was used as a liquid crystal alignment agent, a liquid crystal cell was prepared in the same manner as in Example 1 and a voltage holding ratio was measured. The results are shown in Table 1.

As can be seen from Table 1, in Examples 1 and 2, the use of additives improves the voltage holding ratio (VHR) compared to the control 1 without using additives.

<Residual image evaluation>

The IPS mode liquid crystal cell prepared in Example 1 was set between two polarizing plates with orthogonal polarization axes arranged, and the backlight was turned on when no voltage was applied, and the arrangement angle of the liquid crystal cell was adjusted to make the transmitted light bright. Become the smallest. In addition, from the second region to the darkest angle of the pixel to the first region to the darkest angle, the rotation angle when the liquid crystal cell is rotated is calculated as the initial alignment azimuth. Next, in an oven at 60 ° C, an AC voltage of 16 Hz _PP with a frequency of 30 Hz was applied for 168 hours. Then, the pixel electrode and the counter electrode of the liquid crystal cell were left in a short-circuited state, and then left at room temperature for 1 hour. After being left to stand, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuths before and after the AC drive was calculated from the angle Δ (deg.). The measurement was performed similarly in other examples. As a result, in all the examples, the angle Δ was 0.1 or less. After irradiating ultraviolet rays to the side-chain polymer film exhibiting liquid crystallinity, it is heated within the liquid crystal display temperature range. By self-organizing, the entire polymer is given the liquid crystal alignment energy with high efficiency. Almost no observation after long-term AC drive Deviation from the orientation.

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 primary amine group and a nitrogen-containing molecule in the molecule An aromatic heterocyclic ring, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group-containing amine compound and (C) an organic solvent. For example, the polymer composition of the first patent application range, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement. For example, the polymer composition of claim 1 or 2, wherein the component (B) is represented by the following formula A- [1] (wherein Y ₁₁ is 2 having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group Valent organic group, Y ₁₂ is an amine compound represented by a nitrogen-containing aromatic heterocyclic ring), For example, the polymer composition of claim 1 or 2, 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 both 11 and 12 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 polymer composition of the first or second application scope of the patent application, wherein 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 the groups of their 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 group having 1 to 5 carbon atoms or alkyloxy group having 1 to 5 carbon atoms; R represents hydroxyl group, carbon An alkoxy group having a number of 1 to 6 may have the same definition as Y ₁ . For example, the polymer composition of the first or second patent application range, wherein the component (A) has any kind of 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 first or second application scope 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, and the hydrogen atoms to which they are bonded can also 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 11 A step of applying the composition of any one to a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] A step of heating the coating film obtained in [II]. A substrate is characterized by having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by a method according to item 12 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 item 13 of the patent. 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. 13; 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, (B) a primary amine group and a nitrogen-containing aromatic group in the molecule Heterocyclic, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group amine compound and (C) an organic solvent; [II '] irradiates polarized ultraviolet rays to the coating film obtained by [III '] a step of heating the coating film obtained in [II']; and [IV] a step of obtaining a liquid crystal display element, which is performed by causing the liquid crystal alignment films of the first and second substrates to face each other via liquid crystal Method to make the first and second substrates To the configuration. A lateral electric field drive type liquid crystal display element, which is characterized by being manufactured by the method of claim 15 in the scope of patent application.