TWI668491B - Manufacturing method of substrate with liquid crystal alignment film for lateral electric field driving type liquid crystal display element - Google Patents

Abstract

The present invention provides a lateral electric field-driven liquid crystal display device having a liquid crystal alignment film that is provided with alignment controllability with high efficiency, excellent afterimage characteristics, high linearity at the end portion, and small bulge at the end portion. The present invention solves the above-mentioned problems by a method for manufacturing 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] A step of applying a polymer composition containing the following (A) and (B) to a substrate having a conductive film for driving a lateral electric field to form a coating film; (A) a photosensitive material exhibiting liquid crystallinity in a specific temperature range (B) Organic solvents having both good solvents and poor solvents of the above-mentioned side-chain polymers, and organic solvents having 10% by mass or more of a good solvent having a boiling point of 180 ° C or higher, the good solvent contains Organic solvents selected from those with a boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm, and / or the aforementioned poor solvents are those containing propylene glycol monobutyl ether Solvent.

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

Description

Manufacturing method of substrate with liquid crystal alignment film for lateral electric field driving 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 device having a liquid crystal alignment film having excellent afterimage characteristics, high linearity at the end portion, and small bulge at the end portion.

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. In addition, 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 control ability) is imparted by performing an alignment treatment on an organic film constituting the 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 molecular structure of violet is used. The dependence of the polarized light direction absorbed by the outer line causes the dissociation to be generated. Then, the liquid crystal is aligned by using polyimide remaining without being decomposed (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.

When a liquid crystal alignment agent (also referred to as a “coating solution”) for forming a liquid crystal alignment film is applied to a substrate, a letterpress method or an inkjet coating method is generally used in industry. In this case, the solvent of the coating solution is generally N-methyl-2-pyrrolidone or γ-butyrolactone, etc., in addition to N-methyl-2-pyrrolidone or γ-butyrolactone, which is a solvent that is excellent in the solubility of the resin. The coating film is uniform, and a butyl cellosolve or the like having a resin with a low solubility solvent (also referred to as "poor solvent or weak solvent") is mixed and used (see, for example, Patent Document 2).

[Leading technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-37324

[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, the decomposed light described in Patent Document 1 described above For the alignment method, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes, etc., and it is necessary to irradiate a large amount of ultraviolet rays 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.

In recent years, liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones. In these applications, in order to ensure as much of the display surface as possible, a sealant for indirect application of the substrate of the liquid crystal display element exists near the end of the liquid crystal alignment film. Therefore, when the coating property of the end portion of the liquid crystal alignment film is reduced, that is, when the end portion of the liquid crystal alignment film is non-linear or the end portion is swollen, the adhesion effect between the substrates of the sealant may be reduced, and sometimes Reduce the display characteristics or reliability of the liquid crystal display element.

An object of the present invention is to provide a substrate for a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which is capable of imparting alignment control ability with high efficiency, excellent afterimage characteristics, high linearity at the end portion, and small bulge at the end portion. And a lateral electric field drive type liquid crystal display element having the substrate.

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 in that: [I] (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range and (B) a good solvent having the aforementioned side chain polymer And poor solvents, and an organic solvent having a good solvent having a boiling point of 180 ° C. or higher per 100 parts by mass of a good solvent, the good solvent is selected from a group having a boiling point of 100 to 230 ° C. and a surface tension One or more specific good solvents with a solvent of less than 41.0 dyn / cm, and / or an organic solvent in which the aforementioned poor solvent contains propylene glycol monobutyl ether.

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

<3> In the above <1> or <2>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-imidazolidinone (DMI), propylene glycol monomethyl ether (PGME) The above.

<4> In the above <1> or <2>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP).

<5> In any one of the above <1> to <4>, 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 hydrogen atoms bonded to them may be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkylene, and the hydrogen atom bonded to it may be substituted with halo; 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 Rings of alicyclic hydrocarbons, or the same or different 2 to 6 rings selected from their substituents, are bonded through a bonding group B, and hydrogen atoms bonded to them can 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 group, and carbon number 1 ~ 5 alkyl group, or alkyloxy group with 1 to 5 carbon atoms; Y ₂ is selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and 5 to 8 carbon lipids The cyclic hydrocarbons, and the groups of these groups, and the hydrogen atoms bonded to them may also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH- CN, halo, alkyl with 1 to 5 carbons, or alkane with 1 to 5 carbons Substituent group; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in the Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, - CH = CH -, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; Cou means coumarin- 6-yl or coumarin-7-yl, and the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen Group, 1 to 5 carbon atoms, 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 independent 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 When = CH-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 each other. It can be 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, and T is a single bond, A also indicates Single bond; when l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from 2 The benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations of those of the group).

<6> As in any one of the above <1> to <4>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (7) to (10):

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

<7> As in any one of the above <1> to <3>, the component (A) may have any photosensitive side chain selected from the group consisting of the following formulae (11) to (13):

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

<8> As in any one of the above <1> to <4>, the component (A) may have 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.

<9> As in any one of the above <1> to <4>, 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.

<10> As described in any one of said <1> to <4>, (A) component may have a photosensitive side chain selected from 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.

<11> As in any one of said <1> to <4>, (A) component may have a photosensitive side chain represented by following formula (20).

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

<12> In any one of said <1> to <10>, (A) component may have a liquid crystal side chain chosen from the group which consists of any one of following formula (21)-(31).

In the formula, A, B, q1, and q2 have the same definitions as described above.

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, and The hydrogen atoms to which they are bonded may each be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; 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, carbon number 5 Alicyclic hydrocarbons of ~ 8, alkyl groups of 1 to 12 carbons, or alkoxy groups of 1 to 12 carbons; l represents an integer of 1 to 12, m represents an integer of 0 to 2, but formula (23) ~ In (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, halo, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon and alkyl or alkyloxy group having 5 to 8 carbon atoms Group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- ).

<13> 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 to a substrate having a conductive film for lateral electric field drive to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the coating film obtained in [II].

<14> A substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by the method of <13> above.

<15> A lateral electric field drive type liquid crystal display element, characterized in that it has a substrate according to the item <14>.

<16> A method for manufacturing a liquid crystal display element, which is characterized by obtaining a lateral electric field drive type liquid crystal display element by the following steps: a step of preparing the substrate (the first substrate) of the above item <14>; and obtaining a liquid crystal alignment film The step of the second substrate is to obtain a liquid crystal alignment film to which alignment control ability is given by having the following steps [I '] to [III']: [I '] coating the second substrate with the following components (A ) And (B) polymer coatings to form a coating film: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a good polymer having the aforementioned side chain polymer An organic solvent having both a solvent and a poor solvent, and having a boiling point of 180 ° C. or higher per 10 mass% or more of a good solvent, the good solvent is selected from a group having a boiling point of 100 to 230 ° C. Those with a tension of less than 41.0 dyn / cm, one or more specific good solvents, and / or organic solvents in which the aforementioned poor solvent contains propylene glycol monobutyl ether; [II '] irradiates the coating film obtained in [I'] Step of polarized ultraviolet light; [III ' The coating film [II '] obtained by the step of heating; to And [IV] a step of obtaining a liquid crystal display element, in which the liquid crystal alignment films of the first and second substrates are opposed to each other through a liquid crystal, and the first and second substrates are arranged to face each other.

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

In addition, the following inventions were found.

<P1> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that imparts alignment control energy: [I] will contain (A) and ( B) The step of coating the polymer composition on a substrate having a conductive film for lateral electric field driving to form a coating film: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B ) An organic solvent having both the good solvent and the poor solvent of the side-chain polymer, and having 100% by mass or more of a good solvent having a boiling point of 180 ° C. or more per 100 parts by mass of the good solvent, the good solvent is One or more specific good solvents of a solvent having a free boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm, and / or an organic solvent of the aforementioned poor solvent containing propylene glycol monobutyl ether.

[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 <P1> or <P2>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF) , N, N-dimethylacetamide (DMAc), 1,3-dimethyl-imidazolinone (DMI), propylene glycol monomethyl ether (PGME) selected from the group of one or more.

<P4> In the above-mentioned <P1> or <P2>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP).

<P5> In any one of the above <P1> to <P4>, 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 hydrogen atoms bonded to them can also be replaced with halogen groups; T is a single bond or 1 to carbon number 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.

<P6> In any one of <P1> to <P4>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (7) to (10).

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

<P7> In any one of <P1> to <P3>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

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

<P8> In any one of <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

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

<P9> In any one of <P1> to <P4>, 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.

<P10> In any one of <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).

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

<P11> In any one of <P1> to <P4>, the component (A) may have a photosensitive side chain represented by the following formula (20).

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

<P12> In any one of <P1> to <P10>, the component (A) may have 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 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- .

<P13> A substrate having a liquid crystal alignment film for a liquid crystal display element of a lateral electric field drive type, which is manufactured by any one of the above-mentioned <P1> to <P12>.

<P14> A lateral electric field drive type liquid crystal display device having the substrate of <P13>.

<P15> A method for manufacturing a liquid crystal display element, which obtains a lateral electric field drive type liquid crystal display element by having the following steps: The step of preparing the substrate (first substrate) of the above-mentioned <P13>; the step of obtaining the second substrate having a liquid crystal alignment film, which is obtained by having the following steps [I '] to [III'] Liquid crystal alignment film: [I '] Applying a polymer composition containing the following components (A) and (B) on a second substrate to form a coating film: (A) Displaying liquid crystallinity in a specific temperature range (B) has both a good solvent and a poor solvent for the above-mentioned side chain polymer, and has a good boiling point of 180% or more per 100 parts by mass of the good solvent. An organic solvent of a solvent, the good solvent is one containing more than one specific good solvent selected from a solvent having a boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm, and / or the poor solvent is propylene glycol monobutylene 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] A step of obtaining a liquid crystal display element It is a method in which the liquid crystal alignment films of the first and second substrates are opposed to each other through the liquid crystal, and the first and second substrates are arranged to face each other.

<P16> A lateral electric field drive type liquid crystal display device manufactured by the above <P15>.

<P17> 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 that exhibits liquid crystallinity in a specific temperature range, (B) An organic solvent having both the good solvent and the poor solvent of the above-mentioned side chain polymer and having a good solvent having a boiling point of 180 ° C. or more per 100 parts by mass of the good solvent, the good solvent is selected from the group consisting of Those having a boiling point of 100 to 230 ° C. and a surface tension of less than 41.0 dyn / cm are one or more specific good solvents, and / or the aforementioned poor solvents are organic solvents containing propylene glycol monobutyl ether.

<P18> In the above <P17>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N -One or more selected from the group consisting of dimethylacetamide (DMAc), 1,3-dimethyl-imidazolinone (DMI), and propylene glycol monomethyl ether (PGME).

<P19> In the above-mentioned <P17> or <P18>, the specific good solvent in the component (B) may be N-ethyl-2-pyrrolidone (NEP).

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, which is provided with 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, the liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment film having a high linearity at the end portion of the liquid crystal alignment film and a small bulge at the end portion of the liquid crystal alignment film.

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

9‧‧‧LCD alignment film

10‧‧‧ITO (Indium Tin Oxide) evaporation substrate

11‧‧‧LCD alignment film

12‧‧‧ITO (Indium Tin Oxide) evaporation substrate

[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.

[Fig. 5] Fig. 5 is a view showing an example of a coating film image of an optical microscope for evaluating the linearity of an end portion of a liquid crystal alignment film.

[Fig. 6] Fig. 6 is a view showing an example of a coating film image of an optical microscope for evaluating expansion of the end portion of a liquid crystal alignment film.

[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, a slight anisotropy exhibited by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is effectively realigned 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 is as follows Steps: It is to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided by having the following steps: [I] A photosensitive side containing (A) exhibiting liquid crystallinity in a specific temperature range Chain polymer and (B) organic solvents having both the good solvent and the poor solvent of the above-mentioned side chain polymer, and organic solvents having 10% by mass or more of a good solvent having a boiling point of 180 ° C. or more per 100 parts by mass of the good solvent The good solvent is one containing more than one specific good solvent selected from solvents having a boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm, and / or the poor solvent is one containing propylene glycol monobutyl ether. A step of applying a polymerizable composition of an organic solvent on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the obtained coating film of [II].

In addition, through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is provided can be obtained, 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.

The second substrate uses a substrate without a conductive film for lateral electric field drive instead of a substrate with a conductive film for lateral electric field drive. By using the above steps [I] to [III] Conductive film substrate, so for convenience, sometimes in the application These steps are referred to as steps [I '] to [III']), and a second substrate having a liquid crystal alignment film to which alignment control ability is provided can be obtained.

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

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

<Step [I]>

Step [I] is to form a coating film by coating a polymerizable composition containing a photosensitive side chain polymer and an organic solvent exhibiting liquid crystallinity in a specific temperature range on a substrate having a conductive film for lateral electric field driving. .

<Substrate>

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

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

<Conductive film for lateral electric field drive>

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

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

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

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

<Polymer composition>

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

The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range and (B) 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 may react with light in a wavelength range of 250 nm to 400 nm, and it may be a liquid crystal in a temperature range of 100 ° C to 300 ° C.

(A) The side chain polymer is preferably a photosensitive side chain having a reaction 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 to have a rigid mesogen component on the side-chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

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

A more specific example of the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is preferably one selected from the group consisting of hydrocarbons, (meth) acrylates, itaconates, fumarates, and horses. Free radically polymerizable groups such as maleic acid esters, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and at least 1 Seeds The structure of the main chain and the side chain formed by at least one of the following formulae (1) to (6).

In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkylene group with 1 to 12 carbon atoms, and hydrogen atoms bonded to them can be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl groups, and hydrogen atoms bonded to them 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 bonded to them 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 The alicyclic hydrocarbons, and the groups of their combinations, and the hydrogen atoms bonded to them 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 -Or coumarin-7-yl, 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 alkyl groups, or 1 to 5 alkyloxy groups; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q are each independently A group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, but X is -CH = CH When -CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of P is 2 or more, P may be the same as or different from each other. When the number of Q is 2 or more, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer of 0 ~ 2; when l1 and l2 are 0, and A is a single bond when T is a single bond; When l1 is 1, B is also a single bond when T is a single bond; H and I are each independently selected from a divalent benzene ring and naphthalene , Biphenyl ring, a furan ring, a pyrrole ring, and a group of their portfolio.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<< Method for manufacturing photosensitive side chain polymer >>

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

[Photoreactive side chain monomer]

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

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

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 (mesogenic group) 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 radical polymerizable groups such as butyrolactone, styrene, ethylene, maleimide, norbornene, etc. and at least 1 in the group The structure of the polymerizable group constituted by the species and the side chain formed by at least one of the above formulae (21) to (31) is preferable.

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

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

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl 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 Wait.

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and anthryl methacrylate Methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methacrylic acid 2- Methoxyethyl, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, methyl 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl methacrylate- 8-tricyclodecyl ester and the like. 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.

There is no method for manufacturing a side chain polymer in this embodiment It is particularly limited, and a method widely used in industry can be used. Specifically, it can manufacture by cationic polymerization, radical polymerization, and anionic polymerization of the vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, a radical polymerization is particularly preferable from the viewpoint of easy reaction control.

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

A radical thermal polymerization initiator is a compound that generates a radical by heating above a decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), and difluorenyl peroxides (ethyl fluorenyl peroxide) , Benzamyl peroxide, etc.), peroxides (hydrogen peroxide, third butyl peroxide, cumene peroxide, etc.), dialkyl peroxides (di-third butadiene 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 the compound that initiates radical polymerization is irradiated with light. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethyl Amine) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2 -Methylphenylacetone, 2-hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, cumene benzoin ether, isobutyl benzoin ether, 2 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- ( (Methylthio) phenyl] -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1,4- Ethyl 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'-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyl (Oxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2,6-bis (tri (Chloromethyl) -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) benzene Benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-methyl (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2-methyl-2-morpholinylpropanyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadiene-1- ) -Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) Benzophenone, 3,3 ', 4,4'-tetrakis (third hexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-di (section Tributylperoxycarbonyl) 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-benzothiazole-2-ylidene) -1 -Naphthyl-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, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl lysone, ethyl lysone, methyl Fibrinolysin acetate, ethyl plasmin acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl acetate 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 Ethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl Ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 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 Ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methyl Oxypropionic 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-dimethylpropanamide and the like.

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, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high to uniformly stir, so the monomer concentration is preferably 1% by mass ~ 50 mass%, more preferably 5 mass% to 30 mass%. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is larger than that of the monomer, the molecular weight of the obtained polymer becomes smaller, and when the ratio is smaller, the molecular weight of the obtained polymer becomes larger. The ratio is preferably 0.1 mol% to 10 mol% relative to the monomer to be polymerized. 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 poor solvent to precipitate the polymers. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butylcellolysin, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, and methyl alcohol. Ethyl ether, water, etc. The polymer precipitated after being put into a poor solvent can be recovered by filtration, and then dried at normal temperature or heating under normal pressure or reduced pressure. The polymer recovered by precipitation was redissolved in organic When the operation of reprecipitation and recovery in the solvent is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more poor solvents selected from these are used, it is preferable to improve the purification efficiency.

The molecular weight of the (A) side chain polymer of the present invention is determined by GPC (Gel Permeation Chromatography) method 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 is preferably 2,000 to 1,000,000, and more preferably 5,000 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.

These other polymers are exemplified by poly (meth) acrylates or Polymers made of polyamic acid, polyimide, or the like, and not a photosensitive side chain polymer that exhibits liquid crystallinity.

<< (B) Organic solvents >>

The organic solvent used in the polymer composition of the present invention (that is, the organic solvent of the (B) component) has an organic solvent (also referred to herein as a "good solvent") that dissolves the side chain polymer of the (A) component ) And a solvent (also referred to herein as a "poor solvent" for the side chain polymer of the component (A)) that improves the uniformity of the film thickness or the surface smoothness, and has 10 per 100 parts by mass of a good solvent An organic solvent having a mass point of 180% or more and a good solvent having a boiling point of 180% or more. The good solvent in the organic solvent of the component (B) is one or more specific good solvents (also referred to herein as "specific") selected from solvents having a boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm. "Good solvent") and / or poor solvent in the organic solvent of component (B) contains a specific poor solvent (also referred to herein as "specific poor solvent") propylene glycol monobutyl ether.

In other words, the organic solvent of the component (B) contains both a good solvent and a poor solvent of the side chain polymer of the (A) component, and each 100 mass parts of the good solvent contains 10% by mass or more of a boiling point of 180 ° C or more. An organic solvent of a good solvent. In this case, the good solvent is one containing a specific good solvent, or the poor solvent is one containing a specific poor solvent, or the good solvent is one containing a specific good solvent, and the poor solvent is one containing a specific poor solvent. That is, in the present invention, the organic solvent of the component (B) is a good solvent having a boiling point of 180 ° C. or higher per 100 mass parts of the good solvent. Agent containing at least one of a specific good solvent and a specific poor solvent.

In the present invention, in the heating and drying step, in order to keep the good solvent to the end, it is preferred that the good solvent contains 10 to 100% by mass of a good solvent having a boiling point of 180 ° C. or higher per 100 parts by mass of the good solvent. Among these, 20 to 100% by mass is preferable, and 30 to 100% by mass is more preferable.

The "good solvent having a boiling point of 180 ° C or higher" can be appropriately selected by referring to, for example, a well-known document in the aforementioned "Solvent Handbook" (Kodansha).

In the present invention, in order to improve the solubility of the polymer, the good solvent is preferably 5 to 90% by mass of the entire organic solvent contained in the liquid crystal alignment agent. Among these, 10 to 80% by mass is preferable. More preferably, it is 30 to 70% by mass.

<<< (a) Specific good solvents >>>

In the present invention, the specific good solvent that the organic solvent of the component (B) may contain is a good solvent having good solubility of polyamidic acid or soluble polyimide, compared with the commonly used N-methyl-2- Pyrrolidone (NMP) or γ-butyrolactone (γBL) has a low surface tension as a solvent and a boiling point within a predetermined range. More specifically, as described above, the boiling point is 100 to 230 ° C. and the surface tension is less than 41.0 dyn / cm.

The liquid crystal alignment agent uses a specific good solvent. Compared with a liquid crystal alignment agent that does not use a specific good solvent, the wetting and diffusivity of the coating solution for the substrate becomes higher. Even if a poor solvent with a low solubility of the resin is not used in a large amount, A liquid crystal alignment film having excellent coating film uniformity can be obtained. In addition, since the wetting and diffusivity of the coating solution (liquid crystal alignment agent) becomes high, the linearity of the end portion becomes high when used as a liquid crystal alignment film.

As mentioned above, the boiling point of the specific good solvent in the present invention is preferably 100 to 230 ° C, more preferably 110 to 230 ° C, and still more preferably 180 to 220 ° C. The surface tension of the specific good solvent in the present invention is less than 41.0 dyn / cm, more preferably less than 39.0 dyn / cm, and even more preferably 36.0 dyn / cm or less. According to a preferred aspect of the present invention, the specific good solvent is preferably one having a boiling point of 100 to 230 ° C and a surface tension of less than 41.0 dyn / cm, more preferably a boiling point of 110 to 230 ° C and a surface tension of less than 39.0 dyn. / cm, and more preferably a boiling point of 180 to 220 ° C and a surface tension of 36.0 dyn / cm or less. The specific good solvent in the present invention is one or more selected from organic solvents that satisfy such conditions of boiling point and surface tension.

Among them, a specific specific good solvent is one that satisfies the aforementioned boiling point and surface tension, and can be appropriately selected by referring to the well-known literature values on the boiling point of the organic solvent and the surface tension.

For example, N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-imidazole Literature values for the boiling points and surface tensions of porphyrinone (DMI), propylene glycol monomethyl ether (PGME), and N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (γBL) As follows.

According to a preferred aspect of the present invention, the specific good solvent in the present invention includes N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-dimethyl Acetylamine (DMAc), 1,3-dimethyl-imidazolinone (DMI), propylene glycol monomethyl ether (PGME), and the following formulas [D-1] to [D-3] Solvents, and those that satisfy the aforementioned conditions of boiling point and surface tension.

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

According to a better aspect of the present invention, the specific good solvent in the present invention is selected from the group consisting of N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N -One or more of the group consisting of dimethylacetamide (DMAc), 1,3-dimethyl-imidazolinone (DMI), and propylene glycol monomethyl ether (PGME),

More preferably, it is selected from the group consisting of N-ethyl-2-pyrrolidone (NEP) and 1,3-dimethyl-imidazolidinone (DMI). Particularly preferred is N-ethyl-2-pyrrolidone (NEP). .

In the present invention, when the good solvent contains a specific good solvent, when the good solvent contains a good solvent having a boiling point of 180 ° C. or higher in addition to the specific good solvent, the specific good solvent is preferably 10 to 90% by mass of the entire good solvent in the organic solvent used. . More preferably, it is 30 to 80% by mass.

In the present invention, when the good solvent contains a specific good solvent, and when the specific good solvent is a good solvent having a boiling point of 180 ° C. or higher, the specific good solvent is preferably 10 to 100% by mass of the entire good solvent in the organic solvent used. More preferably, it is 30 to 100% by mass.

In the present invention, when the good solvent contains a specific good solvent, in addition to the specific good solvent, when a good solvent having a boiling point of 180 ° C or higher is included, the specific good solvent is preferably 5 to 80% by mass of the entire organic solvent contained in the liquid crystal alignment agent. . Among these, 10 to 70% by mass is preferred. More preferably, it is 20 to 60% by mass.

In the present invention, when the good solvent contains a specific good solvent, when the specific good solvent is a good solvent having a boiling point of 180 ° C. or higher, the specific good solvent is preferably 5 to 90% by mass of the total organic solvent contained in the liquid crystal alignment agent. Among these, 10 to 80% by mass is preferable. More preferably, it is 20 to 70% by mass.

<<< (b) Specific poor solvents >>>

In the present invention, the specific poor solvent that the organic solvent (B) component may contain is propylene glycol monobutyl ether.

In the present invention, when the poor solvent contains a specific poor solvent, the specific poor solvent is preferably 30 to 100% by mass of the entire poor solvent in the organic solvent used. More preferably, it is 50 to 100% by mass.

In the present invention, when the poor solvent contains propylene glycol monobutyl ether of a specific poor solvent, in order to improve the wetting and diffusion property of the coating solution to the substrate, the propylene glycol monobutyl ether is preferably the entire organic solvent contained in the liquid crystal alignment agent. 5 to 70% by mass. Among these, 10 to 70% by mass is preferred. More preferably, it is 10 to 60% by mass.

Of the total organic solvents in the liquid crystal alignment agent, the greater the amount of the specific good solvent or the specific poor solvent of the present invention, the more the effect of the present invention can be obtained, that is, the linearity of the end of the liquid crystal alignment film is high, and the liquid crystal alignment A liquid crystal alignment film with small swelling at the end of the film.

By including both the specific good solvent and the specific poor solvent of the present invention, the effect is enhanced.

According to a preferred aspect of the present invention, among the organic solvents used, 30 to 100% of the good solvents are specific good solvents and / or poor solvents with a boiling point of 180 ° C or higher, and 30 to 100% are specific Poor solvents are preferred.

<<< (c) Other organic solvents >>>

As the organic solvent used in the polymer composition used in the present invention, in addition to the specific good solvents and specific poor solvents described above, other organic solvents may be used. Such a solvent is not particularly limited as long as it is an organic solvent that dissolves a resin component. Specific examples are listed below.

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

The other organic solvents that can be used for the liquid crystal alignment agent of the present invention can be selected from organic solvents (other good solvents) that dissolve specific polymers. Specific examples of such good solvents are listed below, but are not limited thereto.

For example, there are N, N-dimethylformamidine, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfine, γ- Butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the aforementioned formula [D- 1] ~ Solvents represented by formula [D-3].

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

Among these other good solvents, N-methyl-2-pyrrolidone and γ-butyrolactone are preferably used. When the solubility of the specific polymer in a solvent is high, it is preferable to use a solvent represented by the above formula [D-1] to [D-3].

Specific examples of the other organic solvents as solvents (other poor solvents) that improve the uniformity of the film thickness or the surface smoothness are listed below.

For example, isopropanol, methoxymethylpentanol, methyl lysin, ethyl lysin, butyl lysin, methyl lysin acetate, ethyl lysin acetate, butyl card Ethanol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether 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 monoethyl ether Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-hexane Pentane, n-octane, diethyl ether, 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-methoxypropionic acid, 3- Propyl methoxypropionate, 3-methyl Butyl 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 poor solvents are preferably 1 to 60% by mass of the entire organic solvent contained in the liquid crystal alignment agent. Among them, 1 to 50% by mass is preferable. More preferably, it is 5 to 40% by mass.

The polymer composition used in the present invention may contain the above (A) And (B) components other than the component. This example includes, but is not limited to, a compound that improves the adhesion between the liquid crystal alignment film and the substrate when the polymer composition is applied.

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, glycerol 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-diglycidylamine Methyl) 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 (2- Benzamidine methylene-3-methyl-β-naphthyloxazoline, 2- (β-naphthylmethylene) -3-methylbenzooxazoline, 2- (α- Naphthylmethylidene) -3-methylbenzoxazoline, 2- (4-bisphenolylmethylene) -3-methylbenzoxazoline, 2- (β-naphthylmethyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenolylmethylene) -3-methyl-β-naphthoxazoline, 2- (p- Fluorobenzylmethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitro Aniline) or nitropinene (5-nitropinene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkyl Phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2-naphthalene carboxylic acid, 9-anthracene methanol and 9-anthracene Carboxylic 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 are dipping, roll coating, slit coating, spin coating (spin coating), or spray coating. Etc. 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, in order to selectively induce a photo-crosslinking reaction, for example, ultraviolet rays having a wavelength in a range of 290 nm to 400 nm can be selected to be used. 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 irradiation is to achieve the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the vertical direction. The maximum value of ΔA (hereinafter also referred to as ΔAmax) 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.

In addition, the liquid crystal display temperature refers to a glass transition temperature (Tg) or higher when the side chain polymer or the surface of the coating film is transferred from the solid phase to the liquid crystal phase. Generated from the liquid crystal phase to a temperature below the isotropic phase (isotropic phase) isotropic phase 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. A method of bonding another substrate, injecting liquid crystal under reduced pressure, and sealing, or a method of attaching the substrate and sealing after dropping liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed. At this time, one of the substrates is preferably a substrate using an electrode having a comb-like structure for driving a lateral electric field. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The method for producing a substrate with a coating film of the present invention is to apply a polymer composition on a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, anisotropy is efficiently introduced into the side-chain polymer film 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 a side chain-type high score using a structure having a photo-crosslinkable group as a photoreactive group in the first aspect of the present invention. An example of an anisotropic introduction process in a method for manufacturing a liquid crystal alignment film. 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, and Fig. 3 (b) is a diagram schematically showing a side chain polymer film after polarized light irradiation Figure 3 (c) is a diagram schematically showing the state of a side chain polymer film after heating, especially when the anisotropy introduced is small, that is, in the second aspect of the present invention, [ II] The ultraviolet irradiation amount in the step is a schematic diagram when ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount.

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 Formed on substrate Coating film 3. As shown in FIG. 2 (a), the coating film 3 formed on the substrate has a structure in which side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the liquid crystal components and photosensitive groups of the side chains 4 are also randomly aligned, and the coating film 2 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction process for the coating film, a side chain using a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) is used. In the case of 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 As shown in FIG. 1 (b), the photosensitive group of the side chain 2a having a photosensitive group in the side chain 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays causes a photoreaction such as a dimerization reaction preferentially. As a result, the density of the side chains 2a subjected to the photoreaction becomes slightly higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, the coating film 1 is imparted with very little anisotropy.

In the first 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 chain 4a undergoing 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 3.

In the second aspect of this embodiment, a liquid crystal alignment film using a side chain polymer having a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) is used, [II] When the ultraviolet irradiation amount in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. 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 this embodiment, the use of The coating film of the side chain polymer of the light Fries rearrangement structure represented by the formula (19), the ultraviolet irradiation amount in the step (II) is 1% to 70% of the maximum ultraviolet irradiation amount. Within the range, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. As a result, as shown in FIG. 4 (b), the photosensitive groups of the side chains 8a having the photosensitive groups in the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays preferentially cause light reactions such as light Fries rearrangement. . As a result, the density of the side chains 8a subjected to the photoreaction becomes higher in the polarization direction of the ultraviolet rays, and as a result, a small anisotropy is imparted to the coating film 7.

Next, in the first aspect of the present embodiment, when the 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. The results are shown in Figure 2 (c). The amount of cross-linking reaction between the parallel direction and the vertical direction of the polarized light emitted by the ultraviolet rays is different. Therefore, self-organization is performed in a direction parallel to the direction of polarized light irradiated with ultraviolet rays to realign the side chain 4 containing the liquid crystal component. As a result, the small anisotropy of the coating film 3 caused by the photo-crosslinking reaction is increased by heat, and a larger anisotropy is imparted to the coating film 3.

Similarly, in the second embodiment of the present embodiment, a coating film of a side chain polymer using a structure having a photoisomerizable group or a light Fries rearrangement group represented by the above formula (18) 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, ΔA is heated, and the coating film 5 after polarized irradiation is heated to 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 Fryce rearrangement generated perpendicular to the polarization direction of the ultraviolet light irradiation is stronger than the liquid crystal alignment force of the side chain before the reaction. The organization realigns the side chain 6 containing the liquid crystal component. 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 side chain polymer film 7 is parallel to the polarization direction of the ultraviolet light. The amount of light Fries rearrangement reaction is different between the direction and the vertical direction. 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 the coating film used in the present invention with polarized ultraviolet light, the photocrosslinking reaction, photoisomerization reaction, or photo-Fries rearrangement reaction has a small number of photosensitive groups on the side chain, and the 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-heating by heating. Organized situations. In addition, as for the coating film used in the present invention, and the structure having a light Fryce rearrangement base is irradiated with polarized ultraviolet light, when the photosensitive group of the side chain of the light Fryce rearrangement reaction becomes excessive, the Liquid crystallinity is excessively reduced. At this time, the liquid crystallinity of the obtained film is also lowered, which may prevent subsequent self-organization by heating. In addition, when a structure with a light Fryce rearrangement is irradiated with polarized ultraviolet light, when the amount of ultraviolet radiation is too large, the side chain polymer will photoly decompose, which may prevent subsequent self-organization by heating. Happening.

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

The coating film used in the method of the present invention optimizes the photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the side chain of the side chain type polymer film by optimizing the irradiation amount of polarized ultraviolet light. The amount of Fries rearrangement reaction is optimized. Therefore, together with the subsequent heat treatment, 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. Absorbed by UV As a result of the measurement, the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction in the coating film was evaluated as ΔA. In addition, the maximum value of ΔA (ΔAmax) achieved in the coating film used in the present invention and the amount of polarized ultraviolet radiation to achieve it were obtained. In the manufacturing method of the present invention, based on the amount of polarized ultraviolet radiation to achieve this ΔAmax as a reference, a preferable amount of polarized ultraviolet radiation to be irradiated in the manufacture of the liquid crystal alignment film can be determined.

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

From the above, according to the manufacturing method of the present invention, in order to introduce anisotropy into the coating film with high efficiency, the liquid crystal temperature range of the side chain polymer is used as a reference, and the preferred heating temperature as described above may be determined. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 150 ° C to 250 ° C, the heating temperature after the polarized ultraviolet radiation is preferably set to 140 ° C to 240 ° 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 mentioned above, the transverse electric field produced by the method of the present invention The substrate for a driving type liquid crystal display element or a lateral electric field driving type liquid crystal display element having the substrate is excellent in reliability and can be applied to a large-screen and high-definition liquid crystal television.

[Example]

The abbreviations used in the examples are as follows.

<Methacrylic monomer>

MA1 is synthesized by a synthesis method described in a patent document (WO2011-084546).

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

BCS: Butyl Cellosolve

PB: propylene glycol monobutyl ether

<Polymerization initiator>

AIBN: 2,2’-azobisisobutyronitrile

[Synthesis of polymers]

MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the methacrylate polymer solution was obtained. 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 (A). The number average molecular weight of this polymer was 16,000, and the weight average molecular weight was 32,000.

The liquid crystal phase transition temperature of the obtained methacrylate polymer was 145 ° C to 190 ° C.

<Example 1>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. BCS (45.0 g) was added to this solution to obtain a liquid crystal alignment agent (A1) by stirring.

<Example 2>

NMP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. PB (45.0 g) was added to this solution to obtain a liquid crystal alignment agent (A2) by stirring.

<Example 3>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. PB (45.0 g) was added to this solution to obtain a liquid crystal alignment agent (A3) by stirring.

<Control1>

NMP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. BCS (45.0 g) was added to this solution to obtain a liquid crystal alignment agent (Control 1) by stirring.

Using the liquid crystal alignment agent obtained in the example of the present invention, the inkjet coating property of the liquid crystal alignment agent was evaluated. The conditions are as follows.

The liquid crystal alignment agent (A1) obtained in Example 1 of the present invention, the liquid crystal alignment agent (A2) obtained in Example 2, the liquid crystal alignment agent (A3) obtained in Example 3, and the liquid crystal alignment agent (Control 1) ) The pressure filtration was performed using a membrane filter having a pore size of 1 μm to evaluate the inkjet coating properties.

As the inkjet coater, HIS-200 (manufactured by Hitachi Plant Technologies) was used. Coating was performed on an ITO (indium tin oxide) vapor-deposited substrate washed with pure water and IPA (isopropanol), with a coating area of 80 × 72 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, The coating speed was 40 mm / second, the time from coating to temporary drying was 30 seconds, and the temporary drying was performed on a hot plate at 70 ° C and 90 seconds. Carry on.

About the obtained liquid crystal alignment film, the "linearity of an end part" and the "swell of an end part" of the liquid crystal alignment film were evaluated.

The linearity of the end portion of the liquid crystal alignment film was evaluated by observing the liquid crystal alignment film on the right end with an optical microscope (ECLIPSE ME600 manufactured by NIKON Corporation) with respect to the printing direction. Specifically, the difference between (1) and (2) in FIG. 5 of the obtained liquid crystal alignment film image observed by an optical microscope at a magnification of 25 times, that is, the length of A in FIG. 5 was measured. At this time, the images of all the liquid crystal alignment films are obtained at the same magnification. The evaluation is that the shorter the length of A, the better the linearity of the end portion of the liquid crystal alignment film.

The evaluation of the swelling of the end portion of the liquid crystal alignment film was performed by observing the liquid crystal alignment film on the right end portion with an optical microscope with respect to the printing direction. Specifically, the length of B in FIG. 6 of the obtained liquid crystal alignment film image was observed with an optical microscope at a magnification of 25 times. At this time, the images of all the liquid crystal alignment films are obtained at the same magnification. The evaluation is that the shorter the length of B, the better the swelling of the end portion of the liquid crystal alignment film.

The results are shown in the following table. In the table, the length of A and the length of B of the liquid crystal alignment film obtained in the examples are shown.

From the results, it can be seen that the liquid crystal alignment film of the liquid crystal alignment agent of the example (the present invention) has high linearity at the end portion of the liquid crystal alignment film and small expansion at the end portion of the liquid crystal alignment film.

Claims (17)

A polymer composition comprising: [I] (A) a photosensitive side chain polymer having a liquid crystal group exhibiting liquid crystal properties in a temperature range of 100 ° C to 300 ° C, and (B) having the aforementioned side chain type Both organic good solvents and poor solvents, and organic solvents having a good solvent with a boiling point of 180 ° C. or higher per 100 parts by mass of good solvents. The good solvent is selected from a boiling point of 100 to 230. ℃, and one or more specific good solvents with a surface tension of less than 41.0 dyn / cm, and / or organic solvents in which the aforementioned poor solvent contains propylene glycol monobutyl ether. 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 in the second scope of the patent application, wherein the specific good solvent in the component (B) is N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF) , N, N-dimethylacetamide (DMAc), 1,3-dimethyl-imidazolinone (DMI), propylene glycol monomethyl ether (PGME) selected from the group of one or more. For example, the polymer composition of claim 3, wherein the specific good solvent in the component (B) is N-ethyl-2-pyrrolidone (NEP). For example, the polymer composition according to any one of claims 1 to 4, 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 with 1 to 12 carbon atoms, and hydrogen atoms bonded to them can also be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms 12 alkyl groups, and hydrogen atoms bonded to them 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 Rings of alicyclic hydrocarbons 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 bonded to them 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 bonded to them 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 or coumarin-7-yl, and the hydrogen atoms bonded to them may also 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). For example, the polymer composition according to any one of claims 1 to 4, 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 rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbons 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 bonded to them 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, Or alkyloxy with 1 to 5 carbon atoms; 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 An integer of 1 to 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, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, The radicals of alicyclic hydrocarbons having 5 to 8 carbons and their combinations, and the hydrogen atoms bonded to them can also be independent of each other _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, halo, or alkyl having 1 to 5 carbon atoms of the alkyl group having 1 to 5 substituents; R & lt represents a hydroxyl group , An alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ). For example, the polymer composition according to any one of claims 1 to 4, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (11) to (13): (In the formula, A each independently represents a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or- O-CO-CH = CH-; X means 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 a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms, or 2 to 2 of the same or different ones selected from their substituents. A group in which 6 rings are bonded through a bonding group B, and hydrogen atoms bonded to them may each independently pass -COOR ₀ (wherein 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 having 1 to 5 carbon atoms, or alkyloxy having 1 to 5 carbon atoms, or Represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms). For example, the composition according to any one of claims 1 to 4 in the scope of patent application, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15): (In the formula, A each 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 from among them The same or different 2 to 6 rings selected by the substituents are the bases bonded through the bonding group B, and the hydrogen atoms bonded to them can also independently pass -COOR ₀ (where R ₀ represents hydrogen Atomic or carbon number 1 to 5 alkyl group), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo group, alkyl group of 1 to 5 carbon number, or carbon number 1 to 5 alkyloxy substitution; l represents an integer of 1 to 12, m1, m2 represents an integer of 1 to 3). For example, the composition of any one of claims 1 to 4 in the scope of 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 according to any one of claims 1 to 4, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formula (18) or (19): (In the formula, A and B 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 ring having 5 to 8 carbon atoms, or from The same or different 2 to 6 rings selected by their substituents are bonded to each other through a bonding group B, and the hydrogen atoms bonded to them 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 an alkyl group having a carbon number 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; ₁ represents a hydrogen atom R & lt , -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons). For example, the composition according to any one of claims 1 to 4, wherein 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 from these substituents The selected 2 to 6 rings of the same or different rings are bonded through a bonding group B, and the hydrogen atoms bonded to them can also independently pass through -COOR ₀ (where R ₀ represents a hydrogen atom or a carbon Alkyl groups of 1 to 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl groups of 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, the composition according to any one of claims 1 to 4, wherein the component (A) has any liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): (Wherein A and B have the same definitions as above; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms. And the groups of these groups, and the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or 1 to 5 carbon atoms. 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, Benzene 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, and formulas (25) to (26) Among them, 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 Benzene ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon and alkyl group or alkyloxy group 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 12 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 in that it has a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by a method according to item 13 of the patent application. A lateral electric field-driven liquid crystal display element is characterized in that it has a substrate with the scope of application for patent item 14. 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. 14; obtaining a second liquid crystal alignment film In the substrate step, a liquid crystal alignment film provided with alignment control ability is obtained by having the following steps [I '] to [III']: [I '] coating a second substrate containing the following components (A) and (B) the step of forming a coating film with the polymer composition: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a good solvent having the aforementioned side chain polymer and Both of the poor solvents are organic solvents having a good solvent with a boiling point of 180 ° C. or higher per 100 parts by mass of the good solvent. The good solvent is selected from the group consisting of a boiling point of 100 to 230 ° C. and a surface tension of less than 100%. 41.0 dyn / cm, one or more specific good solvents, and / or the aforementioned poor solvents are organic solvents containing propylene glycol monobutyl ether; [II '] irradiate polarized light on the coating film obtained in [I'] Steps of UV [III '] a step of heating the coating film obtained in [II']; and [IV] a step of obtaining a liquid crystal display element, in which the liquid crystal alignment films of the first and second substrates are opposed to each other via liquid crystal, The first and second substrates are arranged to face each other. A lateral electric field drive type liquid crystal display element is characterized by being manufactured by the method of the 16th patent application.