TW201510623A - Method for producing substrate having liquid crystal alignment film for in-plane switching liquid crystal display elements - Google Patents

Abstract

The present invention provides a highly reliable in-plane switching liquid crystal display element which is provided with alignment control ability at high efficiency and has excellent screen burn-in characteristics. The present invention achieves the above-described objective by a method for producing a substrate having a liquid crystal alignment film, in which a liquid crystal alignment film for in-plane switching liquid crystal display elements provided with alignment control ability is obtained by performing: [I] a step for forming a coating film by applying a polymer composition to a substrate having a conductive film for in-plane switching, said polymer composition containing (A) a photosensitive side-chain polymer which exhibits liquid crystallinity within a predetermined temperature range and (B) an organic solvent; [II] a step for irradiating the coating film obtained in step [I] with polarized ultraviolet light having an extinction ratio of 10:1 or more; and [III] a step for heating the coating film obtained in step [II].

Description

Method for manufacturing substrate having liquid crystal alignment film for transverse electric field drive type liquid crystal display element

The present invention relates to a method of producing a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device. More specifically, it relates to a novel method for producing a liquid crystal display element having excellent afterimage characteristics.

A display device in which a liquid crystal display element is lightweight, thin, and low in power consumption has been known, and in recent years, it has been surprisingly developed for use in large-scale television applications. The liquid crystal display element is composed of, for example, a liquid crystal layer sandwiched between a transparent substrate and one of the electrodes. Further, the liquid crystal display element is such that the liquid crystal is in a desired alignment state between the substrates, and an organic film made of an organic material is used as the liquid crystal alignment film.

In other words, the constituent members of the liquid crystal alignment film-type liquid crystal display element are formed on the surface in contact with the liquid crystal of the substrate on which the liquid crystal is sandwiched, and serve to shape the liquid crystal in a predetermined direction between the substrates. Further, in addition to the role of the liquid crystal alignment film in a certain direction such as a direction in which the liquid crystal is aligned in a direction parallel to the substrate, a role of controlling the pretilt angle of the liquid crystal may be required. The ability to control liquid crystal alignment in such a liquid crystal alignment film (hereinafter referred to as The control energy is imparted by the alignment treatment of the organic film constituting the liquid crystal alignment film.

A method of aligning the liquid crystal alignment film which is used for the alignment control can be conventionally known as a rubbing method. The rubbing method is a method of rubbing (friction) the surface of the polyvinyl alcohol or the polyimide film or the polyimide film on the substrate with a cloth such as cotton, nylon or polyester in a certain direction to make the liquid crystal in the wiping direction (friction) Direction) The method of alignment. Since this rubbing method can easily realize the alignment state of the relatively stable liquid crystal, it is used in the manufacturing process of the conventional liquid crystal display element. In addition, as the organic film used for the liquid crystal alignment film, a polyimine-based organic film having excellent reliability such as heat resistance or electrical properties is mainly selected.

However, the rubbing method of wiping the surface of the liquid crystal alignment film formed of polyimide or the like has a problem of generating dust or generating static electricity. Further, in recent years, due to the high definition of the liquid crystal display element or the unevenness due to the switching of the active element by the electrode on the substrate or the liquid crystal driving, the liquid crystal alignment film cannot be uniformly wiped with the cloth. On the surface, it is sometimes impossible to achieve uniform liquid crystal alignment.

Therefore, the photo-alignment method is actively reviewed as an additional alignment treatment method of the liquid crystal alignment film which does not rub.

There are various methods for the photo-alignment method, but the anisotropic property 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.

A major photo-alignment method is known as a decomposing photo-alignment method. For example, the polyimine film is irradiated with polarized ultraviolet rays, and the polarization direction dependence of the ultraviolet absorption of the molecular structure is used to cause decomposition in the opposite direction. And use The polyimine which remains without being decomposed aligns the liquid crystal (see, for example, Patent Document 1).

Further, a photo-alignment type or a photo-isomerization type photo-alignment method is also known. For example, polyvinyl cinnamate is used, and a polarized ultraviolet ray is irradiated to cause a dimerization reaction (crosslinking reaction) in a double bond portion of two side chains parallel to the polarized light. Further, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). Further, when a side chain type polymer having azobenzene in a side chain is used, a polarized ultraviolet ray is irradiated, and an isomerization reaction occurs in the azobenzene portion of the side chain parallel to the polarized light to align the liquid crystal to be orthogonal to the polarization direction. Direction (see, for example, Non-Patent Document 2).

As described above, the alignment treatment method of the liquid crystal alignment film by the photo-alignment method does not require rubbing, and there is no fear of generating dust or generating static electricity. Further, even if the substrate of the liquid crystal display element having the uneven surface is subjected to the alignment treatment, it becomes an alignment treatment method of the liquid crystal alignment film suitable for the industrial production process.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

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

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

[Summary of the Invention]

As described above, the photo-alignment method is an alignment treatment method for a liquid crystal display element, and has a large advantage in that it does not require the rubbing step itself as compared with the conventional rubbing method. Further, the optical alignment method can change the irradiation amount of the polarized light to control the alignment control energy as compared with the friction method in which the alignment control energy is substantially constant by friction. However, when the optical alignment method is to achieve the same level of alignment control energy as in the case of the rubbing method, a large amount of polarized light irradiation amount is required, and a stable liquid crystal alignment may not be achieved.

For example, in the decomposition type photoalignment method described in Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp of 500 W for 60 minutes, and it is necessary to irradiate a large amount of ultraviolet rays for a long time. Further, in the case of the dimerization type or the photoisomerization type photoalignment method, it is necessary to irradiate a large amount of ultraviolet rays of several J (joules) to several tens of J. Further, in the photo-crosslinking type or the photo-isomerization type photo-alignment method, since the thermal stability or the light stability of the liquid crystal alignment is inferior, when it is a liquid crystal display element, there is a problem that alignment failure or image sticking occurs. In particular, in the case of a lateral electric field-driven liquid crystal display device, since the liquid crystal molecules are switched in the plane, the liquid crystal is likely to be misaligned after the liquid crystal is driven, so that the display is caused by the AC driving. Become a big issue.

Therefore, the photo-alignment method requires a liquid crystal alignment which is highly efficient or stable in the alignment treatment, and a liquid crystal alignment film or a liquid crystal alignment agent which can impart high alignment control energy to the liquid crystal alignment film with high efficiency.

Further, according to the findings of the present inventors, it has been found that in the liquid crystal display device of the transverse electric field driving method as described above, the obtained liquid crystal display element has a problem in black-level in color display, and thus the tone of the image is generated. Do not reconcile. This is a phenomenon caused by the confusion of the initial alignment and must be solved.

An object of the present invention is to provide a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device which is excellent in image retention characteristics and excellent in image retention characteristics, and a transverse electric field drive type liquid crystal display device having the substrate.

Further, in addition to the above object, an object of the present invention is to provide a lateral electric field drive type liquid crystal display element which can solve the above black level problem and a liquid crystal alignment film for the element.

An object of the present invention is to provide a method for producing a substrate having a liquid crystal alignment film in a margin region in which a polarized ultraviolet ray having a good liquid crystal alignment property of a liquid crystal alignment film can be enlarged.

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

<1> A method for producing a substrate having a liquid crystal alignment film, which is a system A liquid crystal alignment film for a lateral electric field drive type liquid crystal display device to which an alignment control energy is imparted is obtained by the following steps: [I] a photosensitive side chain type polymer containing (A) liquid crystallinity in a specific temperature range and (B) a step of applying a polymer composition of an organic solvent to a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] irradiating the coating film obtained in [I] with an extinction ratio of 10:1 or more a step of polarizing ultraviolet rays; and [III] a step of heating the coating film obtained in [II].

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

<3> In the above <1> or <2>, the component (A) may have any one of photosensitive side chains selected from the group consisting of the following formulas (1) to (6):

(wherein A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or a carbon number of 1~ Alkyl groups of 12, and the hydrogen atoms to which they are bonded may also be substituted with a halogen group; Y ₁ represents a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5. a ring of ~8 alicyclic hydrocarbons, or a group of the same or different 2 to 6 rings selected from the substituents bonded via a bonding group B, and the hydrogen atoms bonded thereto may be independent By -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, a halogen group, The alkyl group having 1 to 5 carbon atoms or the alkyloxy group having 1 to 5 carbon atoms is substituted; the 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~ a group of 8 alicyclic hydrocarbons, and a combination of such groups, the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH =CH-CN, halo group, alkyl group with 1 to 5 carbon atoms, or carbon number 1 to 5 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 X is 2, X may be the same or different; Cou means couma a -6-yl or coumarin-7-yl group, and the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN , a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q Each of them is independently 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 of the bond of -CH=CH- 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; 11 is 0 or 1; 12 is an integer of 0~2; when 11 and 12 are 0, when T is a single bond, A Also indicates a single bond; when 11 is 1, when T is a single bond, B also represents a single bond; H and I are independent Is selected from the divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations of those of the group).

<4> In the above <1> or <2>, the component (A) may have any one of photosensitive group selected from the group consisting of the following formulas (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, and m1 and m2 represent 1 to 3; Integer; n represents an integer from 0 to 12 (but when n=0, B is a single bond).

<5> In the above <1> or <2>, the component (A) may have any photosensitive side chain selected from the group consisting of the following formulas (11) to (13):

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

<6> In the above <1> or <2>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15):

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

<7> In the above <1> or <2>, 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.

<8> In the above <1> or <2>, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19):

Wherein 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 alkyloxy group having 1 to 5 carbon atoms).

<9> In the above <1> or <2>, 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 described above.

<10> In any one of <1> to <9>, the component (A) may have any one of liquid crystal side chains selected from the group consisting of the following formulas (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 a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring and a fat having a carbon number of 5-8. a cyclic hydrocarbon, and a group of such a combination, the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or carbon. Substituted with an alkyloxy group of 1 to 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, naphthalene a ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; and 1 represents 1 to 12 In the integer, m represents an integer from 0 to 2, but in the formulas (23) to (24), the total of all m is 2 or more, and in the formulas (25) to (26), the total of all m is 1 or more, and 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 hetero ring, and An alicyclic hydrocarbon having 5 to 8 carbon atoms and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<11> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which is produced by any one of the above <1> to <10>.

<12> A transverse electric field drive type liquid crystal display device characterized by having the substrate of the above <11>.

<13> A method of producing a liquid crystal display device, comprising the steps of: obtaining a lateral electric field drive type liquid crystal display device: preparing the substrate (first substrate) of the above <11>; and obtaining the liquid crystal alignment film The second substrate step of obtaining a liquid crystal alignment film imparted with alignment control energy by having the following steps [I'] to [III']: [I'] a step of forming a coating film by coating a polymer composition containing the following components (A) and (B) on a second substrate: (A) a photosensitive side chain type exhibiting liquid crystallinity in a specific temperature range a polymer and (B) an organic solvent; [II'] a step of irradiating the polarized ultraviolet light to the coating film obtained in [I']; [III'] a step of heating the coating film obtained in [II']; [IV] A step of obtaining a liquid crystal display device in which the first and second substrates are opposed to each other such that the liquid crystal alignment films of the first and second substrates face each other via a liquid crystal.

<14> A transverse electric field drive type liquid crystal display element characterized by being produced by the method of the above <13>.

<15> A composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which comprises (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent.

Further, on the other hand, the following invention was found.

<P1> A method for producing a substrate having a liquid crystal alignment film which is obtained by the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device to which an alignment control energy is imparted: [I] will contain (A) a step of forming a coating film by applying a polymerizable side chain type polymer exhibiting liquid crystallinity and a polymer composition of (B) an organic solvent in a specific temperature range to a substrate having a conductive film for driving a transverse electric field; [II] a step of irradiating the coating film obtained in [I] with a polarized ultraviolet light having an extinction ratio of 10:1 or more; and [III] A step of heating the coating film obtained in [II].

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

<P3> In the above <P1> or <P2>, the component (A) may have any photosensitive side chain selected from the group consisting of the following formulas (1) to (6):

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may also be substituted with a halogen group; T is a single bond or a carbon number of 1~ An alkyl group of 12, and a hydrogen atom bonded thereto may be substituted with a halogen group; Y ₁ represents a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5. a ring of ~8 alicyclic hydrocarbons, or a group of 2 to 6 ring systems selected from the same or different substituents bonded through the bonding group B, and the hydrogen atoms bonded thereto may also be bonded thereto. Each independent -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, halogen a group, an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms; Y ₂ is selected from a bivalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number a group of 5 to 8 alicyclic hydrocarbons and a combination of the above, wherein the hydrogen atoms bonded thereto may also independently pass through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halo group, alkyl group having 1 to 5 carbon atoms, 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 means coumarin-6-yl or coumarin-7 a group, and the hydrogen atom bonded thereto may also be independently passed through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a carbon number of 1 to 5 a group, or an alkyloxy group having a carbon number of 1 to 5; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; and P and Q are each independently selected from a single bond, 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 the above, 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, a naphthalene ring, and a combination. a benzene ring, a furan ring, a pyrrole ring, and a combination of these.

<P4> In the above <P1> or <P2>, the component (A) may have any photosensitive side chain selected from the group consisting of the following formulas (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, and 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).

<P5> In the above <P1> or <P2>, the component (A) may have any one selected from the group consisting of the following formulas (11) to (13). Side chain.

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

<P6> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

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

<P7> In the above <P1> or <P2>, 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.

<P8> In the above <P1> or <P2>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formula (18) or (19).

Wherein 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms.

<P9> In the above <P1> or <P2>, 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 described above.

<P10> In any one of the above <P1> to <P9>, the component (A) may have any one of liquid crystal side chains selected from the group consisting of the following formulas (21) to (31).

In the formula, A, B, q1 and q2 have the same definitions as above; Y ₃ is a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring and a fat having a carbon number of 5-8. a group of a cyclic hydrocarbon, and a combination of the above, wherein the hydrogen atoms bonded thereto may also independently pass through -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or carbon. Substituted with an alkyloxy group of 1 to 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, naphthalene a ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; and 1 represents 1 to 12 In the integer, m represents an integer from 0 to 2, but in the formulas (25) to (26), the total of all m is 2 or more, and in the formulas (27) to (28), the total of all m is 1 or more, and 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 hetero ring, and An alicyclic hydrocarbon having 5 to 8 carbon atoms; and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<P11> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which is produced by any one of the above <P1> to <P10>.

<P12> A transverse electric field drive type liquid crystal display element having the substrate of the above <P11>.

<P13> A method of producing a liquid crystal display device, comprising: obtaining a lateral electric field drive type liquid crystal display element by the following steps: preparing a substrate (first substrate) of the above <P11>; A step of obtaining a second substrate having a liquid crystal alignment film obtained by the following steps [I'] to [III'] to obtain a liquid crystal alignment film imparting alignment control energy:

[I'] a step of forming a coating film by coating a polymer composition containing the following components (A) and (B) on a second substrate: (A) a photosensitive side exhibiting liquid crystallinity in a specific temperature range Chain polymer and (B) organic solvent.

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

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

[IV] A step of obtaining a liquid crystal display device in which the first and second substrates are opposed to each other such that the liquid crystal alignment films of the first and second substrates face each other via the liquid crystal.

<P14> A transverse electric field drive type liquid crystal display element manufactured by the method of <P13> above.

<P15> A composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which comprises (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent.

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 device which is excellent in image retention characteristics and excellent in image retention characteristics, and a lateral electric field drive type liquid crystal display device having the substrate.

Transverse electric field driven liquid crystal manufactured by the manufacturing method of the present invention Since the display element can impart the alignment control energy with high efficiency, the display characteristics are not impaired even if it is continuously driven for a long time.

Moreover, according to the present invention, in addition to the above-described effects, it is possible to provide a lateral electric field drive type liquid crystal display device having high reliability without deteriorating the characteristics such as voltage holding ratio even under severe conditions such as high temperature and humidity. Liquid crystal alignment film for components.

1‧‧‧Side chain polymer film

2, 2a‧‧‧ side chain

3‧‧‧Side chain polymer film

4, 4a‧‧‧ side chain

5‧‧‧Side chain polymer film

6, 6a‧‧‧ side chain

7‧‧‧Side chain polymer film

8, 8a‧‧‧ side chain

[Fig. 1] is a view schematically showing an example of an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used for a photosensitive side chain, and the introduced anisotropy is small. Diagram of the situation.

FIG. 2 is a view schematically showing an example of an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used for a photosensitive side chain, and the introduced anisotropy is large. Diagram of the situation.

[Fig. 3] is a view schematically showing an example of an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, and an organic layer causing light Fres rearrangement or isomerization is used in a photosensitive side chain. Base, a diagram of a situation in which the introduced anisotropy is small.

[Fig. 4] is a view schematically showing an example of an anisotropic introduction process in a method for producing a liquid crystal alignment film used in the present invention, and an organic layer causing light Fres rearrangement or isomerization is used in a photosensitive side chain. Base, a diagram of a situation in which the introduced anisotropy is large.

[Formation of the Invention]

As a result of active research by the present inventors, the following findings have been obtained to complete the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side chain type polymer (hereinafter also referred to as a side chain type polymer) which exhibits liquid crystallinity, and the coating film obtained by using the polymer composition has A film of a photosensitive side chain type 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. In addition, after the polarized light irradiation, the step of heating the side chain type polymer film is a coating film (hereinafter also referred to as a liquid crystal alignment film) to which alignment control energy is imparted. At this time, a slight anisotropy exhibited by the polarized light irradiation becomes a driving force, and the liquid crystalline side chain type polymer itself is effectively realigned by self-organization. As a result, high-efficiency alignment treatment as a liquid crystal alignment film can be realized, and a liquid crystal alignment film imparted with high alignment control energy can be obtained.

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

<Method for Producing Substrate Having Liquid Crystal Alignment Film> and <Method for Manufacturing Liquid Crystal Display Element>

The method for producing a substrate having a liquid crystal alignment film of the present invention has the following steps: [I] a polymer containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent. Composition coating a step of forming a coating film on a substrate having a conductive film for driving a transverse electric field; [II] a step of irradiating the coating film obtained in [I] with an ultraviolet ray having an extinction ratio of 10:1 or more; and [III] II] a step of heating the obtained coating film.

By the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device to which an alignment control energy is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, in addition to the substrate (first substrate) obtained above, a lateral electric field drive type liquid crystal display element can be obtained by preparing the second substrate.

The second substrate is used in addition to the substrate having the conductive film for driving the transverse electric field instead of the substrate having the conductive film for driving the transverse electric field, by using the above steps [I] to [III] (because the use does not have the lateral electric field drive) Since the substrate of the conductive film is referred to as a step [I'] to [III']) in the present application for convenience, a second substrate having a liquid crystal alignment film to which alignment control energy is imparted can be obtained.

The method for producing a lateral electric field drive type liquid crystal display device has the following step [IV]: [IV] the first and second substrate pairs obtained as described above are obtained by facing the liquid crystal alignment films of the first and second substrates via liquid crystal The step of obtaining a liquid crystal display element in a configuration. Thereby, a lateral electric field drive type liquid crystal display element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] which are provided in the production method of the present invention will be described.

<Step [I]>

In the step [I], a polymer composition containing a photosensitive side chain type polymer and an organic solvent exhibiting liquid crystallinity in a specific temperature range is applied onto a substrate having a conductive film for driving a transverse electric field to form a coating film. .

<Substrate>

The substrate is not particularly limited. However, when the liquid crystal display device to be produced is of a transmissive type, it is preferred to use a substrate having high transparency. In this case, a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.

Further, in consideration of the application to the reflective liquid crystal display element, an opaque substrate such as a germanium wafer may be used.

<Conductive film for driving a transverse electric field>

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

In the case where the liquid crystal display device is of a transmissive type, the conductive film may be, for example, ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide), but is not limited thereto.

Further, in the case of a reflective liquid crystal display device, the conductive film may be, for example, a material that reflects light such as aluminum, but is not limited thereto.

A conventionally known method can be used for the method of forming a conductive film on a substrate.

<Polymer composition>

The polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, particularly a conductive film.

The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent.

<<(A) Side chain type polymer>>

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

The (A) side chain type polymer may be reacted with light having a wavelength in the range of 250 nm to 400 nm, and liquid crystallinity may be exhibited in a temperature range of 100 ° C to 250 ° C.

The (A) side chain type polymer is preferably a photosensitive side chain having a reaction in the wavelength range of 250 nm to 400 nm.

The (A) side chain type polymer exhibits liquid crystallinity in a temperature range of from 100 ° C to 250 ° C, and therefore preferably has a mesogenic group.

(A) The side chain type polymer chain has a photosensitive side chain bonded to the main chain, and causes a crosslinking reaction, an isomerization reaction, or a light-Fles rearrangement in response to light. The structure of the photosensitive side chain is not particularly limited, and is preferably a structure which causes a crosslinking reaction or a light-floating rearrangement for light induction, and more preferably causes a crosslinking reaction. At this time, even if it is exposed to external stress such as heat, the achieved alignment control energy can be stably maintained for a long period of time. The structure of the side chain type polymer film which exhibits liquid crystal sensitivity is not particularly limited as long as it satisfies the characteristics, but it is preferably a liquid crystal having a straight chain structure on the side chain structure. (Mesogen) ingredients. In this case, when the side chain type polymer is used as the liquid crystal alignment film, 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 may have a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenyl benzoate group, an azobenzene group, or the like. a liquid crystal component having a structure in which a photosensitive group which is bonded to a front end portion to cause light crosslinking or a isomerization reaction, or a main chain and a side chain bonded thereto, and the side chain has a liquid crystal composition And the structure of the phenyl benzoate group of the light Fres rearrangement reaction.

More specifically, the structure of the side chain type polymer film which exhibits liquid crystal sensitivity is preferably selected from the group consisting of hydrocarbons, acrylates, methacrylates, maleimides, norbornenes, and decanes. The structure of at least one of the main chain and the side chain formed by at least one of the following formulas (1) to (6).

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or a carbon number of 1 to 12 An alkyl group, and the hydrogen atom to which they are bonded may be substituted with a halogen group; Y ₁ represents a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5-8 The ring of the alicyclic hydrocarbon or the group of the same or different 2 to 6 rings selected from the substituents bonded via the bonding group B, and the hydrogen atoms bonded thereto may also be independently -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, a halogen group, carbon The alkyl group having 1 to 5 atoms or the alkyloxy group having 1 to 5 carbon atoms is substituted; the 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 groups of the alicyclic hydrocarbons and combinations thereof, the hydrogen atoms to which they are bonded may also independently pass through -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 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 X is 2, X may be the same or different; Cou means coumarin-6 - or coumarin-7-yl, and the hydrogen atoms to which they are bonded may also be independently via -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halo , an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; and P and Q are each independently A group consisting of a bivalent 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 -CO-O-, -O-CO-CH=CH-, P or Q on the side of the -CH=CH- bond is an aromatic ring, and when the number of P is 2 or more, P may be the same or different When the number of Q is 2 or more, Q may be the same or different from each other; 11 is 0 or 1; 12 is an integer of 0 to 2; when both 11 and 12 are 0, A is a single bond when T is a single bond; When 11 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from a divalent benzene ring, 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 formulas (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, and 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).

The side chain may be selected from the group consisting of the following formulas (11) to (13) Any one of the photosensitive side chains selected by the group.

In the formula, A, X, l, 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 , l, m1 and m2 have the same definitions as described 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.

Further, 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 described 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 described above.

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

In the formula, A, B, q1 and q2 have the same definitions as above; Y ₃ is a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring and a fat having a carbon number of 5-8. a group of a cyclic hydrocarbon, and a combination of the above, wherein the hydrogen atoms bonded thereto may also independently pass through -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or carbon. Substituted with an alkyloxy group of 1 to 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, naphthalene a ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; and 1 represents 1 to 12 In the integer, m represents an integer from 0 to 2, but in the formulas (23) to (24), the total of all m is 2 or more, and in the formulas (25) to (26), the total of all m is 1 or more, and 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 hetero ring, and An alicyclic hydrocarbon having 5 to 8 carbon atoms; and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

The present invention provides novel compounds (1) to (11) represented by the following formulas (1) to (11) as photoreactive and/or liquid crystal side chain monomers; and the following formulas (12) to (17) Compounds (12) to (17).

Wherein 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; and u represents 0 or 1; and Py Represents 2-pyridyl, 3-pyridyl or 4-pyridyl; further, v represents 1 or 2.

<<Manufacturing method of photosensitive side chain type polymer>>

The photosensitive side chain type polymer which exhibits liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having a photosensitive side chain and a liquid crystal side chain monomer.

[Liquid Crystal Side Chain Monomer]

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

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

More specific examples of the liquid crystal side chain monomer preferably have at least one selected from the group consisting of a hydrocarbon, a (meth) acrylate, a maleimide, a decene, and a decane. Main chain, and by the above formula (21) The structure of at least one of the formed side chains of ~(31) is preferable.

The (A) side chain type polymer can be obtained by the polymerization reaction of the above-mentioned photoreactive side chain monomer exhibiting liquid crystallinity. Further, copolymerization of a photoreactive side chain monomer which does not exhibit liquid crystallinity and a liquid crystal side chain monomer, or copolymerization of a photoreactive side chain monomer which exhibits liquid crystallinity and a liquid crystal side chain monomer And got it. Further, it is copolymerizable with other monomers within a range that does not impair the liquid crystal display ability.

Other monomers are listed, for example, as monomers which are commercially available for free radical polymerization.

Specific examples of the other monomer include an unsaturated carboxylic acid, an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

Specific examples of the unsaturated carboxylic acid are exemplified by acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.

The acrylate compound is exemplified by, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, phenyl acrylate, 2,2,2-trifluoroacrylate. Ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydro acrylate Oxime ester, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate and acrylic acid 8-ethyl-8-tricyclodecyl ester and the like.

Methacrylate compounds are exemplified by, for example, methacrylic acid Methyl ester, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, decyl methyl methacrylate, phenyl methacrylate, methyl 2,2,2-trifluoroethyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxy methacrylate Triethylene glycol ester, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (meth)acrylic acid (3-ethyl-3-oxocyclo) can also be used. A (meth) acrylate compound having a cyclic ether group such as butyl)methyl ester.

The vinyl compound is exemplified by, for example, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

The styrene compound is exemplified by, for example, styrene, methylstyrene, chlorostyrene, bromostyrene or the like

The maleidinide compound is exemplified by, for example, maleic imine, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method for producing the side chain type polymer of the present embodiment is not particularly limited, and a method widely used industrially can be used. Specifically, a liquid crystal side chain monomer or a photoreactive side chain monomer can be used. The base is produced by cationic polymerization or radical polymerization or anionic polymerization. Among these, from the viewpoint of easy reaction control and the like, a radical polymerization is particularly preferred.

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

The radical thermal polymerization initiator is a compound which generates a radical by heating to a temperature higher than a decomposition temperature. Such radical thermal polymerization initiators are exemplified by, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), and dithiol peroxides (ethyl hydrazine peroxide). , benzamidine peroxide, etc.), peroxides (hydrogen peroxide, tert-butyl peroxide, cumene peroxide, etc.), dialkyl peroxides (di-tertiary) Peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxy Tert-butyl decanoate, tert-butyl peroxypivalate, triamyl peroxy 2-ethylcyclohexanoate, etc.), persulfate (potassium persulfate, sodium persulfate, An azo compound (azobisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). These radical thermal polymerization initiators may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound which initiates radical polymerization by irradiation with light. Such radical photopolymerization initiators can be exemplified by benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and iso Propyl xanthones, 2,4-diethylthioxanthone, 2-ethylhydrazine, acetophenone, 2-hydroxy-2-methyl Phenylacetone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoine ether, isobutyl benzoin ether, 2,2- Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzathrone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 4-dimethylamine Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri (third Butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-double (trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N , N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethane) -5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2- (p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonyl bis (7- Diethylamine coumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-indole (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'- Bisimidazole, 3-(2- Methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinylpropanyl)-9-n-dodecylcarbazole, 1-hydroxyl Cyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(trihexylperoxycarbonyl)benzophenone , 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3' - bis(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2 ( 3H)-Subunit)-1-(2-benzylidene)ethanone. These compounds may be used singly 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 bulk polymerization method, a solution polymerization method, or the like can be used.

The organic solvent used for the polymerization reaction of the photosensitive side chain type polymer which exhibits liquid crystallinity is not particularly limited as long as it can dissolve the polymer formed. Specific examples thereof are as follows.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl caprolactone Amine, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Cellulose acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, B Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, two 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, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, 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 Acetate Glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3 - ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl -2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N- Dimethylpropionamide and the like.

These organic solvents may be used singly or in combination. Further, even a solvent which does not dissolve the produced polymer may be used in the above organic solvent insofar as the produced polymer does not precipitate.

Further, in the radical polymerization, oxygen in the organic solvent serves as a cause of hindering the polymerization reaction, and therefore it is preferred that the organic solvent be degassed as much as possible.

The polymerization temperature in the radical polymerization may be any temperature from 30 ° C to 150 ° C, but preferably in the range of from 50 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high and it is difficult to uniformly stir, so the monomer concentration is preferably 1% by mass. 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the above 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 small, and when the ratio is small, the molecular weight of the obtained polymer becomes large, so the radical initiator The ratio is preferably from 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators, and the like may be added during the polymerization.

[Recovery of Polymers]

When the polymer produced by recovering the reaction solution of the side chain type polymer which exhibits liquid crystallinity obtained by the above reaction is recovered, the reaction solution is placed in a poor solvent to precipitate the polymer. can. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, and A. Ethyl ethyl ether, water, and the like. The polymer which has been precipitated in a poor solvent is recovered by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. The bad solvent at this time is listed as an example. When three or more kinds of poor solvents selected from the above are used, such as alcohols, ketones, hydrocarbons, etc., it is preferable because the purification efficiency can be further improved.

The molecular weight of the (A) side chain type polymer of the present invention is a weight average molecular weight measured by a GPC (gel permeation chromatography) method in consideration of the strength of the obtained coating film, workability at the time of formation of a coating film, and uniformity of a coating film. It is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.

[Modulation of polymer composition]

The polymer composition used in the present invention is preferably a coating liquid suitable for forming a liquid crystal alignment film. In other words, the polymer composition used in the present invention is preferably prepared by forming a solution in which a resin component for a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain type polymer which exhibits liquid crystallinity as described above. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, even more preferably from 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the resin components may be the side chain type polymer which exhibits liquid crystallinity, but may be mixed in a range which does not impair the liquid crystal display performance and photosensitivity. Other polymers than others. In this case, the content of the other polymer in the resin component is from 0.5% by mass to 80% by mass, preferably from 1% by mass to 50% by mass.

These other polymers are exemplified by, for example, a polymer composed of poly(meth)acrylate, polyglycolic acid or polyimine, and not a photosensitive side chain type polymer which exhibits liquid crystallinity.

<<Organic solvent>>

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

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 3-methoxy-N,N-dimethylpropyl Indoleamine, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, B Kefenyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, propyl carbonate, diglyme Ether, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-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 may be used alone or in combination.

The polymer composition used in the present invention may contain components other than the above components (A) and (B). Examples thereof include a solvent or a compound which improves uniformity of film thickness or surface smoothness when a polymer composition is applied, a compound which improves adhesion between a liquid crystal alignment film and a substrate, but not Limited to this.

Specific examples of the solvent (poor solvent) for improving film thickness uniformity or surface smoothness are as follows.

For example, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl card Alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octyl Alkane, diethyl ether, lactic acid Ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxy Methyl ethyl propyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropane Butyl acrylate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Acetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene A solvent having a low surface tension such as an alcohol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These poor solvents may be used alone or in combination of plural kinds. When the solvent is used as described above, the solubility of the solvent contained in the polymer composition is remarkably lowered, and it is preferably from 5% by mass to 80% by mass, more preferably from 20% by mass to 60% by mass based on the total amount of the solvent.

Examples of the compound which improves film thickness uniformity or surface smoothness include a fluorine-based surfactant, a rhodium-based surfactant, and a nonionic surfactant.

More specifically, for example, EF TOP (registered trademark) EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS), MEGAFAC (registered trademark) F171, F173, R-30 (made by DIC), Fluorad FC430, FC431 (Sumitomo 3M) 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 Co., Ltd.). The ratio of use of the surfactants is preferably from 0.01 part by mass to 2 parts by mass, more preferably from 0.01 part by mass to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include, for example, a compound containing a functional decane as shown below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxylate Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3 -ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-amine Propyltriethoxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl- 1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Base ester, 9-triethoxydecyl-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethyl)- 3-aminopropyltrimethoxydecane, N-bis(oxyethylidene)-3-aminopropyltriethoxydecane, and the like.

Further, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, in order to prevent deterioration of electrical characteristics due to the backlight when the liquid crystal display element is formed, a phenoplast such as the following may be contained in the polymer composition. Or an additive containing an epoxy group-containing compound. Specific phenolic plastic additives are shown below, but are not limited to this configuration.

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetrahydration Glyceryl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Base) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

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

A light sensitizer can also be used as the additive. Preferred are colorless sensitizers and triplet sensitizers.

Photo sensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), keto coumarin, carbonyl double Coumarin, aromatic 2-hydroxyketone, and amine-substituted aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono or di-p-(dimethylamino)-2-hydroxydiphenyl Ketone), acetophenone, anthracene, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylidene-3-methyl-β-naphthylthiazoline, 2 -(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylidenemethylene)-3-methylbenzothiazoline, 2- (4-biphenolnomethylene)-3-methylbenzothiazoline, 2-(β-naphthylmethylhydrazine Methylene)-3-methyl-β-naphthylthiazoline, 2-(4-phenphenidylmethylene)-3-methyl-β-naphthylthiazoline, 2-(p- Fluorobenzhydrylmethylene)-3-methyl-β-naphthylthiazoline), oxazoline (2-benzylidenemethylidene-3-methyl-β-naphthyloxazoline, 2-(β-naphthylmethylidene methylene)-3-methylbenzoxazoline, 2-(α-naphthylmethylidene methylene)-3-methylbenzoxazoline, 2- (4-biphenolylmethylene)-3-methylbenzoxazoline, 2-(β-naphthylmethylidenemethyl)-3-methyl-β-naphthyloxazoline, 2- (4-biphenolnomethylene)-3-methyl-β-naphthyloxazoline, 2-(p-fluorobenzhydrylmethylene)-3-methyl-β-naphthoxazole Porphyrin), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitrodecene (5-nitrodecene), (2-[( m-Hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkyl phthalone, acetophenone ketal (2,2-dimethoxy Phenylethyl ketone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-fluorene methanol, and 9-fluorene carboxylic acid), benzopyran, azo acridine, furocoumarin, and the like.

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

In addition to the above, the polymer composition may be added with a dielectric or a conductive material to change the dielectric properties or electrical conductivity of the liquid crystal alignment film, in addition to the above, in addition to the above, and may be added. The compound is used to increase the film hardness or density when the liquid crystal alignment film is formed.

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

The coating method is generally carried out by a method such as screen printing, lithography, soft printing, or ink jet method. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method), a spray method, and the like, and these may be used depending on the purpose.

After the polymer composition is applied onto a substrate having a conductive film for driving a transverse electric field, it can be heated at 50 to 200 ° C, preferably 50 by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven. The solvent was evaporated to obtain a coating film at ~150 °C. The drying temperature at this time is preferably lower than the liquid crystal phase exhibiting temperature of the side chain type polymer.

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

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

<Step (II)>

The step [II] is an ultraviolet ray having an extinction ratio of 10:1 or more, preferably an extinction ratio of 15:1 or more, and more preferably an extinction ratio of 20:1 or more, to the coating film obtained in the step [I]. The extinction ratio refers to the transmittance ratio of the P wave to the S wave of the polarizing plate at a specific wavelength used for photoreaction. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through the polarizing plate in a certain direction. The ultraviolet rays used can use ultraviolet rays having a wavelength in the range of 100 nm to 400 nm. It is preferred to select the most appropriate wavelength depending on the type of coating film to be used, through the filter, and the like. Moreover, in order to selectively induce photocrosslinking reaction, For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected. Ultraviolet light can use, for example, light emitted from a high pressure mercury lamp.

The amount of ultraviolet light irradiated by the polarized light depends on the coating film to be used. The amount of irradiation is 1% of the amount of polarized ultraviolet light which is the maximum value of ΔA (hereinafter also referred to as ΔAmax) which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction. It is preferably in the range of ~70%, more preferably in the range of 1% to 50%.

<Step [III]>

The step [III] is to heat the coating film irradiated with ultraviolet rays in the step [II]. By heating, an alignment control energy can be imparted to the coating film.

Heating means a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. 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 in which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal display temperature). For example, when the film surface of the film is coated, the liquid crystal display temperature of the surface of the coating film is estimated to be lower than the liquid crystal display temperature when the photosensitive side chain type polymer which exhibits liquid crystallinity is observed as a whole. Therefore, the heating temperature is more preferably in the temperature range in which the liquid crystal on the surface of the coating film exhibits temperature. That is, the temperature range of the heating temperature after the polarized ultraviolet ray irradiation is set to a lower limit of 10 ° C lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer used, and is 10 ° C lower than the upper limit of the liquid crystal temperature range. The temperature at which the temperature is set to the upper limit is preferably. When the heating temperature is lower than the above temperature range, there is an anisotropic increase in the coating film by heat. When the effect is insufficient, and the heating temperature is too high above the above temperature range, the state of the coating film tends to be close to the isotropic liquid state (isotropic phase). In this case, it is difficult to utilize self-organization to realign with one. direction.

Further, the liquid crystal display temperature means a glass transition temperature (Tg) or more when the surface of the side chain type polymer or the coating film is transferred from the solid phase to the liquid crystal phase, and is generated from the phase transition of the liquid crystal phase to the isotropic phase (etc. The phase of the phase is shifted to a temperature below the temperature (Tiso).

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

By the above steps, the manufacturing method of the present invention can achieve high efficiency of the anisotropic introduction of the coating film. The liquid crystal alignment film substrate can be manufactured with high efficiency.

<Step [IV]>

[IV] The substrate (the first substrate) having the liquid crystal alignment film on the conductive film for driving the transverse electric field obtained in [III] is obtained in the same manner as the above [I'] to [III']. A substrate (second substrate) having a liquid crystal alignment film which does not have a conductive film is disposed opposite to each other via a liquid crystal alignment film via a liquid crystal, and a liquid crystal cell is produced by a conventional method to produce a lateral electric field drive type liquid crystal display. The steps of the component. Further, the steps [I'] to [III'] may be performed in addition to the substrate having the conductive film for driving the transverse electric field, in addition to the substrate having the conductive film for driving the transverse electric field, and the step [I] ~[III] is also carried out. Difference between steps [I]~[III] and steps [I']~[III'] Since the point is only the presence or absence of the above-mentioned conductive film, the description of steps [I'] to [III'] is omitted.

When the liquid crystal cell or the liquid crystal display device is produced as an example, the first and second substrates are prepared, and the spacer is spread on the liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface is inside. A method of injecting a liquid crystal into a substrate, sealing it, or applying a liquid crystal drop to a liquid crystal alignment film surface on which a separator is dispersed, and bonding the substrate and sealing it. At this time, it is preferable that the substrate on one of the sides is a substrate having an electrode having a comb structure such as a lateral electric field drive. The spacer diameter at this time is preferably from 1 μm to 30 μm, more preferably from 2 μm to 10 μm. The diameter of the spacer determines the distance between one of the liquid crystal layers and the substrate, that is, the thickness of the liquid crystal layer.

In the method for producing a coated film substrate of the present invention, a polymer composition is applied onto a substrate to form a coating film, and then the polarized ultraviolet rays are irradiated. Then, by introducing a highly efficient anisotropy into the side chain type polymer film by heating, a substrate with a liquid crystal alignment film having alignment control energy of liquid crystal is produced.

The coating film used in the present invention utilizes the principle of molecular reorientation caused by the photoreaction of the side chain and the self-organization of the liquid crystal, thereby realizing the introduction of high efficiency anisotropy to the coating film. In the production method of the present invention, when the side chain type polymer has a photocrosslinkable group as a photoreactive group, a side chain type polymer is used to form a coating film on the substrate, and then the polarized ultraviolet ray is irradiated, followed by heating. A liquid crystal display element is produced.

The following description uses photocrosslinking with photoreactive groups The embodiment of the side chain type polymer having a structure of a base is referred to as a first aspect, and a side chain type polymer having a structure of a photoreactive group, a Frestle rearrangement group or a group which causes isomerization is used. The embodiment is referred to as a second aspect.

FIG. 1 is a view schematically showing an anisotropic introduction process in a method for producing a liquid crystal alignment film having a side chain type polymer having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. An example of a picture. Fig. 1(a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 1(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 1(c) The figure schematically shows the state of the side chain type polymer film after heating, and in particular, the case where the introduction has a small anisotropy, that is, in the first aspect of the invention, the amount of ultraviolet irradiation in the step [II] is such that ΔA is a schematic diagram of the range of 1% to 15% of the maximum ultraviolet irradiation amount.

FIG. 2 is a view schematically showing an anisotropic introduction process in a method for producing a liquid crystal alignment film having a side chain type polymer having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. An example of a picture. Fig. 2(a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 2(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 2(c) The graph schematically shows the state of the side chain type polymer film after heating, and in particular, the degree of anisotropy of the introduction is large, that is, in the first aspect of the invention, the amount of ultraviolet irradiation in the step [II] is Δ. A is a schematic diagram of the range of 15% to 70% of the maximum ultraviolet irradiation amount.

Fig. 3 is a view schematically showing a second aspect of the present invention, Anisotropy in a method for producing a liquid crystal alignment film of a side chain type polymer having a photoisomerization group having a photoisomerization group or a photoreactive group represented by the above formula (18) Import a diagram of an example of processing. Fig. 3(a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 3(b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 3(c) The graph schematically shows the state of the side chain type polymer film after heating, and in particular, the case where the introduction has a small anisotropy, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in the step [II] is Δ. A is a schematic diagram of the range of 1% to 70% of the maximum ultraviolet irradiation amount.

FIG. 4 is a view schematically showing the manufacture of a liquid crystal alignment film of a side chain type polymer having a structure in which a photoreactive group represented by the above formula (19) is used as a photoreactive group in the second embodiment of the present invention. A diagram of an example of anisotropic import processing in a method. Fig. 4 (a) is a view schematically showing a state of a side chain type polymer film before polarized light irradiation, and Fig. 4 (b) is a view schematically showing a state of a side chain type polymer film after polarized light irradiation, and Fig. 4 (c) The graph schematically shows the state of the side chain type polymer film after heating, and in particular, the case where the degree of anisotropy of introduction is large, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in the step [II] is Δ. A is a schematic diagram of the range of 1% to 70% of the maximum ultraviolet irradiation amount.

In the first aspect of the present invention, when the ultraviolet irradiation amount in the step [II] is such that the ΔA is within the range of 1% to 15% of the maximum ultraviolet irradiation amount in the anisotropic introduction process of the coating film, 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 the side chains 2 are randomly arranged. According to the random arrangement of the side chain 2 of the coating film 1, the side The liquid crystal component and the photosensitive group of the chain 2 are also randomly aligned, and the coating film 1 is isotropic.

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

In the second aspect of the present invention, a side chain using a structure having a photoisomerization group or a light-floating rearrangement group represented by the above formula (18) is used for the anisotropic introduction treatment of the coating film. In the liquid crystal alignment film of the type polymer, when the ultraviolet irradiation amount in the step [II] is such that ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, first, the 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 the side chains 6 are randomly arranged. The liquid crystal component and the photosensitive group of the side chain 6 are also randomly aligned according to the random arrangement of the side chains 6 of the coating film 5, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, in the case of using the liquid crystal alignment film of the side chain type polymer having the structure of the Frestle rearrangement group represented by the above formula (19), the isotropic introduction process of the coating film is used. When the ultraviolet irradiation amount in the step [II] is such that ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, first, the 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 the side chains 8 are randomly arranged. Depending on the random arrangement of the side chains 8 of the coating film 7, the liquid crystal composition and the photosensitive group of the side chain 8 are also randomly aligned, and the coating film 7 is isotropic.

In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is such that ΔA is in the range of 1% to 15% of the maximum ultraviolet irradiation amount, the isotropic coating film 1 is irradiated with polarized light. Ultraviolet light. In other words, as shown in Fig. 1(b), the photosensitive group of the side chain 2a having the photosensitive group in the side chain 2 in the direction parallel to the polarization direction of the ultraviolet light preferentially causes a photoreaction such as a dimerization reaction. . As a result, the density of the side chain 2a subjected to photoreaction slightly increases in the direction of polarization of the ultraviolet ray, and as a result, the coating film 1 is imparted with a very small anisotropy.

In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is such that the ΔA is within the range of 15% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 3 is irradiated with polarized light. Ultraviolet light. 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 in the direction parallel to the polarization direction of the ultraviolet light preferentially causes a photoreaction such as a dimerization reaction. As a result, the density of the side chain 4a in which the photoreaction is carried out is slightly increased in the direction of polarization of the ultraviolet ray, and as a result, the coating film 3 is given a small anisotropy.

In the second aspect of the present invention, a liquid crystal alignment film using a side chain type polymer having a photoisomerization group or a light-floating rearrangement group represented by the above formula (18) is used, [II] When the ultraviolet irradiation amount in the step is such that ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. The result is shown on the side parallel to the direction in which the ultraviolet light is polarized, as shown in Fig. 3(b). The photosensitive group of the side chain 6a having a photosensitive group in the chain 6 preferentially causes a photoreaction such as light Fres rearrangement. As a result, the density of the side chain 6a in which the photoreaction was carried out was slightly increased in the direction of polarization of the ultraviolet ray, and as a result, the coating film 5 was given a very small anisotropy.

In the second embodiment of the present invention, a coating film of a side chain type polymer having a structure having a light Fres rearrangement group represented by the above formula (19) is used, and the ultraviolet irradiation amount in the step [II] is ΔA. When the maximum ultraviolet irradiation amount is in the range of 1% to 70%, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. As a result, as shown in Fig. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group in the side chain 8 in the direction parallel to the direction of polarization of the ultraviolet light preferentially causes photoreaction such as rearrangement of the light fels . As a result, the density of the side chain 8a subjected to photoreaction increases in the direction of polarization of the ultraviolet ray, and as a result, the coating film 7 is given a small anisotropy.

In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is such that ΔA is within the range of 1% to 15% of the maximum ultraviolet irradiation amount, the coating film 1 after the polarized light irradiation is heated. Become a liquid crystal state. As a result, as shown in Fig. 1(c), the amount of the crosslinking reaction which occurs between the coating film 1 and the direction parallel to the direction in which the ultraviolet rays are irradiated is different. In this case, since the amount of the crosslinking reaction which occurs in the direction parallel to the direction in which the ultraviolet light is irradiated is extremely small, the crosslinking reaction site acts as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the direction in which the ultraviolet light is irradiated is higher than the liquid crystallinity in the parallel direction, and self-organization is performed in a direction parallel to the direction in which the ultraviolet light is irradiated, and the side chain 2 containing the liquid crystal component is realigned. As a result, the very small anisotropy of the coating film 1 caused by the photocrosslinking reaction The coating film 1 is imparted with greater anisotropy due to the increase in heat.

Similarly, in the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is such that ΔA is within the range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 after the polarized light irradiation is heated. It becomes a liquid crystal state. As a result, as shown in FIG. 2(c), the side chain type polymer film 3 has a different amount of crosslinking reaction between the direction parallel to the direction in which the ultraviolet light is irradiated and the direction perpendicular to the vertical direction. Therefore, self-organization is performed in a direction parallel to the direction in which the ultraviolet light is irradiated, and the side chain 4 containing the liquid crystal component is realigned. As a result, the small anisotropy of the coating film 3 caused by the photocrosslinking reaction increases due to heat, giving the coating film 3 a greater anisotropy.

Similarly, in the second embodiment of the present invention, a coating film of a side chain type polymer having a photoisomerization group or a light-floating rearrangement group represented by the above formula (18) is used. When the amount of ultraviolet irradiation in the step [II] is such that ΔA is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 5 after the polarized light irradiation is heated to be in a liquid crystal state. As a result, as shown in FIG. 3(c), the amount of the light-floating rearrangement reaction of the coating film 5 which is generated between the direction parallel to the direction in which the ultraviolet rays are irradiated and the vertical direction is different. In this case, the liquid crystal alignment force of the Fres rearrangement body generated in the direction perpendicular to the polarization direction of the ultraviolet ray is stronger than the liquid crystal alignment force of the side chain before the reaction, so that it is perpendicular to the polarization direction of the ultraviolet ray. The self-organization is used to realign the side chain 6 containing the liquid crystal component. As a result, the very small anisotropy of the coating film 5 caused by the light-recovering reaction is increased by heat, giving the coating film 5 a greater anisotropy.

Similarly, in the second aspect of the present embodiment, the use device is used. A coating film of a side chain type polymer having a structure of a light Fres rearrangement group represented by the above formula (19), wherein the ultraviolet irradiation amount in the step [II] is such that ΔA is 1% of the maximum ultraviolet irradiation amount. When it is in the range of ~70%, the coating film 7 after the polarized light is heated to be in a liquid crystal state. As a result, as shown in FIG. 4(c), the side chain type polymer film 7 has a different amount of light Fres rearrangement reaction between the direction parallel to the direction in which the ultraviolet rays are irradiated and the direction perpendicular to the direction in which the ultraviolet rays are irradiated. Since the anchoring force of the light Frye rearrangement body 8(a) is stronger than the side chain 8 of the front row, a certain amount of the light-floating rearrangement body is generated in parallel with the polarization direction of the ultraviolet light. The direction is self-organized to realign the side chain 8 containing the liquid crystal component. As a result, the small anisotropy of the coating film 7 caused by the light-recovering reaction is increased by heat, giving the coating film 7 a greater anisotropy.

Therefore, the coating film used in the method of the present invention can be applied to the coating film by irradiating polarized ultraviolet rays and heat treatment in order, and the anisotropic property can be introduced efficiently, and the liquid crystal alignment film excellent in the alignment control property can be obtained.

Further, the coating film used in the method of the present invention optimizes the amount of irradiation of the polarized ultraviolet rays to the coating film and the heating temperature of the heat treatment. Thereby, the introduction of the anisotropy into the coating film with high efficiency can be achieved.

The irradiation amount of the optimum polarized ultraviolet light which introduces high-efficiency anisotropy to the coating film used in the present invention corresponds to the photo-crosslinking reaction or photoisomerization reaction of the photosensitive group in the coating film, or the light-floating reaction The amount of rearrangement reaction is the optimum amount of polarized ultraviolet light. When the coating film used in the present invention is irradiated with polarized ultraviolet light, the photocrosslinking reaction or the photoisomerization reaction or the photoreceptor group of the side chain of the optical Fress rearrangement reaction is small. For sufficient light response. At this time, sufficient self-organization is not possible even after heating. Further, in the coating film used in the present invention, the structure having a photocrosslinkable group is irradiated with the polarized ultraviolet light, and when the photosensitive group of the side chain of the crosslinking reaction is excessive, the crosslinking reaction between the side chains excessively proceeds. At this time, the obtained coating film becomes rigid, which may hinder the subsequent self-organization by heating. Further, as for the coating film used in the present invention, and the structure having the light-Flese rearrangement group is irradiated with the polarized ultraviolet light, when the photosensitive group of the side chain of the light flois rearrangement reaction becomes excessive, the coating film is Liquid crystallinity will be excessively lowered. At this time, the liquid crystallinity of the obtained film is also lowered, which may hinder the subsequent self-organization by heating. In addition, when the ultraviolet ray is irradiated with too much ultraviolet ray when the ultraviolet ray irradiation amount is too large, the side chain type polymer may be photodecomposed, which may hinder the subsequent self-organization by heating. Happening.

Therefore, in the coating film used in the present invention, the photosensitive group of the side chain is subjected to a photocrosslinking reaction, a photoisomerization reaction, or an optical Fleet rearrangement reaction by irradiation with polarized ultraviolet rays. The photosensitive group of the side chain type polymer film preferably has a photosensitive group content of 0.1 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the side chain in which the photoreaction is carried out to such a range, the self-organization of the subsequent heat treatment can be efficiently performed, and high anisotropy in the film can be formed.

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

That is, the coating film used in the present invention is measured for ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and ultraviolet absorption in the vertical direction after the polarized ultraviolet light irradiation. From the measurement results of the ultraviolet absorbing, the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction in the coating film was evaluated as ΔA. Further, the maximum value (ΔAmax) of ΔA achieved in the coating film used in the present invention and the amount of irradiation of the polarized ultraviolet ray thereof were obtained. In the production method of the present invention, the amount of polarized ultraviolet light which is preferably irradiated in the production of the liquid crystal alignment film can be determined based on the amount of polarized ultraviolet light irradiation at which ΔAmax is achieved.

In the production method of the present invention, it is preferable that the amount of the polarized ultraviolet rays applied to the coating film used in the present invention is in the range of 1% to 70% of the amount of the polarized ultraviolet rays to achieve ΔAmax, and more preferably 1% to 70%. Within 50%. In the coating film used in the present invention, the amount of the polarized ultraviolet ray in the range of 1% to 50% of the amount of the polarized ultraviolet ray of ΔAmax is equivalent to 0.1% of the total photosensitive base of the side chain type polymer film. Molar %~20 mol% The amount of polarized ultraviolet light for photocrosslinking reaction.

As described above, in the production method of the present invention, in order to achieve high-efficiency anisotropy of the coating film, the preferred heating temperature may be determined as described above based on the liquid crystal temperature range of the side chain type polymer. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is from 100 ° C to 200 ° C, the heating temperature after the polarized ultraviolet ray irradiation is set to 90 ° C. ~190 ° C is preferred. Thereby, the coating film used in the present invention is imparted with greater anisotropy.

As described above, the liquid crystal display element of the present invention exhibits high reliability against external stress such as light or heat.

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

The invention is illustrated by the following examples, but the invention is not limited to the examples.

[Examples]

The examples use the abbreviation as follows.

<methacrylic monomer>

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

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

<organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve

<Polymerization initiator>

AIBN: 2,2'-azobisisobutyronitrile

[Polymethacrylic acid synthesis example 1]

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

NMP (54.0 g) was added to 6.0 g of the obtained powder, and stirred at room temperature for 3 hours. Further, BCS (40.0 g) was added to the solution, and the mixture was stirred at room temperature for 1 hour to obtain a polymer solution (A1) having a solid concentration of 6.0% by weight. This polymer solution can directly become a liquid crystal alignment agent for forming a liquid crystal alignment film.

<Polymethacrylic acid synthesis example 2>

In the same manner as in the above-mentioned Synthesis Example 1, MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were polymerized in THF (85.45 g) in the presence of AIBN (0.14 g) to obtain a synthesis example. 2 methacrylate polymer solution (M2).

<Example 1> <<Liquid cell production>>

The liquid crystal cell was produced in the order shown below using the liquid crystal alignment agent (M1) obtained in Example 1. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film was disposed. The pixel electrode has a central portion bent, and a plurality of pixels are arranged A comb-like shape formed by the electrode elements of the word shape. The width of each electrode element in the short-side direction was 10 μm, and the interval between the electrode elements was 20 μm. The pixel electrode forming each pixel is curved at the central portion, and the plurality of pixels are arranged The shape of the electrode element is formed, so the shape of each pixel is not rectangular, but has a similar shape to the curved part of the electrode as the electrode element. The shape of the word. Further, each of the pixels has a first region and a second region on the lower side of the upper side of the curved portion which is divided by the curved portion at the center. When the first region and the second region of each pixel are compared, the direction in which the electrode elements constituting the pixel electrodes are formed is different. That is, when the alignment processing direction of the liquid crystal alignment film described later is the reference, in the first region of the pixel, the electrode element of the pixel electrode forms an angle of +15° (clockwise), and in the second region of the pixel, the pixel electrode The electrode elements form an angle of -15° (clockwise). In other words, in the first region and the second region of each pixel, the direction of the liquid crystal in the plane of the substrate (in-plane switching) caused by the voltage applied between the pixel electrode and the counter electrode is mutually The opposite direction is formed. The liquid crystal alignment agent (A1) obtained in Synthesis Example 1 was spin-coated on the substrate on which the above-mentioned electrode was prepared. Subsequently, the film was dried on a hot plate at 70 ° C for 90 seconds to form a liquid crystal alignment film having a film thickness of 100 nm. Then, the coating film surface was irradiated with ultraviolet rays of 313 nm of 1 mJ/cm ² through a polarizing plate having a specific extinction ratio, and then heated by a heating plate of 150 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Likewise, the irradiation amount of ultraviolet radiation of ^{1mJ / cm 2 ~ 10mJ / cm} 2 when in 1mJ / cm ² interval, and ^{10mJ / cm 2 ~ 100mJ / cm} 2 , the at 10mJ / cm ² interval, and 100mJ / cm ² In the above case, different substrates were produced at intervals of 50 mJ/cm ² . Further, a coating film was formed in the same manner as the glass substrate having a columnar spacer having a height of 4 μm as an electrode on the opposite substrate, and an alignment treatment was applied. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on a liquid crystal alignment film of one of the substrates. Then, the other substrate is bonded so that the alignment direction of the liquid crystal alignment film surface is 0°, and then the sealing agent is thermally cured to form an empty cell. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell having a liquid crystal display element of an IPS (In-Planes Switching) mode. .

(Orientation observation)

The liquid crystal cell was produced by the above method. Then, it was subjected to a 60-minute realignment treatment in an oven at 120 °C. Next, the polarizing plates were formed in an orthogonal state and observed by a polarizing microscope. Rotating the liquid crystal cell, no black when the black display state is displayed When the point or alignment was poor, the evaluation was good. The amount of irradiation of ultraviolet rays was as described above, and the results of the alignment were observed for the respective substrates, and the irradiation allowance (Margin) with good alignment was as shown in Table 1.

<Examples 2 to 4>

A liquid crystal cell was produced in the same manner as in Example 1. The mating of the liquid crystal alignment material and the polarizing plate used is shown in Table 1.

<black-level evaluation>

The liquid crystal cells produced in the first to fourth embodiments are disposed between two polarizing plates in which the polarizing axes are arranged orthogonally, and the backlight is turned on without applying a voltage, and the arrangement angle of the liquid crystal cells is adjusted to make the brightness of the transmitted light. Be the smallest. The liquid crystal cell was observed using a digital CCD camera "C8800-21C" manufactured by Hamamatsu Photonics Co., Ltd., and the image of the captured image was numerically quantized using the analysis software "ExDcam Image capture Software" of the company. When the luminance value of the liquid crystal cell is 500 to 550, when it is evaluated as "?" or 550 to 600, when it is evaluated as "○" or the like, the evaluation is "x".

<Comparative Examples 1 to 2>

A liquid crystal cell was produced in the same manner as in Examples 1 to 4 using a polarizing plate having an extinction ratio of 6:1. Using the obtained liquid crystal cells, the black matrix was evaluated in the same manner as in Examples 1 to 4. The evaluation results are shown in Table 1.

As is clear from Table 1, in Examples 1 and 2, by using a filter having a high extinction ratio, a better black level was exhibited as compared with Comparative Example 1 using a filter having an extinction ratio of 6:1. Further, in the case of Examples 1 and 2 as compared with Comparative Example 1, the irradiation amount margin was expanded from 1 to 3 to 1 to 10. In the comparison of Examples 3 and 4 with Comparative Example 2, similarly, it was observed that the black level increase and the irradiation amount margin were expanded.

1‧‧‧Side chain polymer film

2, 2a‧‧‧ side chain

Claims (14)

A method for producing a substrate having a liquid crystal alignment film which is obtained by the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which an alignment control energy is imparted: [I] will contain (A) at a specific temperature range a step of forming a coating film by applying a polymer composition of a photosensitive side chain type polymer exhibiting liquid crystallinity and (B) an organic solvent to a substrate having a conductive film for driving a transverse electric field; [II] for [I The obtained coating film is irradiated with a polarized ultraviolet light having an extinction ratio of 10:1 or more; and [III] a step of heating the coating film obtained in [II]. The method of claim 1, wherein the component (A) has a photosensitive side chain which causes photocrosslinking, photoisomerization, or Fries rearrangement. The method of claim 1 or 2, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formulas (1) to (6): (wherein A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O - or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or a carbon number of 1~ Alkyl groups of 12, and the hydrogen atoms to which they are bonded may also be substituted with a halogen group; Y ₁ represents a benzene ring selected from a monovalent group, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5. a ring of ~8 alicyclic hydrocarbons, or a group of the same or different 2 to 6 rings selected from the substituents bonded via a bonding group B, and the hydrogen atoms bonded thereto may be independent By -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, a halogen group, The alkyl group having 1 to 5 carbon atoms or the alkyloxy group having 1 to 5 carbon atoms is substituted; the 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~ a group of 8 alicyclic hydrocarbons, and a combination of such groups, the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH =CH-CN, halo group, alkyl group with 1 to 5 carbon atoms, or carbon number 1 to 5 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 X is 2, X may be the same or different; Cou means couma a -6-yl or coumarin-7-yl group, and the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN , a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q Each of them is independently 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 of the bond of -CH=CH- 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; 11 is 0 or 1; 12 is an integer of 0~2; when 11 and 12 are 0, when T is a single bond, A Also indicates a single bond; when 11 is 1, when T is a single bond, B also represents a single bond; H and I are independent Is selected from the divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations of those of the group). The method of claim 1 or 2, wherein the component (A) has any one of the photosensitive side chains selected from the group consisting of the following formulas (7) to (10): (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-; Y ₁ represents a ring selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. Or the same or different 2~6 rings selected from the substituents are bonded via a bonding group B, and the hydrogen atoms bonded thereto may also independently pass through -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, a halogen group, an alkyl group having 1 to 5 carbon atoms, Or an alkyloxy group having 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 X is 2, X may be the same or different; l represents an integer from 1 to 12; m represents an integer from 0 to 2, and m1 and m2 represent An integer from 1 to 3; n represents an integer from 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, a group of alicyclic hydrocarbons having 5 to 8 carbon atoms and a combination of the same, and the hydrogen atoms to which they are bonded may also be independent _{-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 , alkoxy group having 1 to 6 carbon atoms, or representing the same definition as Y ₁ ). The method of claim 1 or 2, wherein the component (A) has any one of photosensitive side chains selected from the group consisting of the following formulas (11) to (13): (wherein 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 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 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 having 5 to 8 carbon atoms, or the same or different selected from the substituents. 6 rings are bonded via a bond group B, and the hydrogen atoms to which they are bonded may also independently pass through -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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms, or Represents a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms). The method of claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15): (wherein 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 a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or The two or six rings of the same or different substituents selected by the substituents are bonded via a bond group B, and the hydrogen atoms to which they are bonded may also independently pass through -COOR ₀ (wherein R ₀ represents 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 a carbon number 1 to 5 alkyloxy substituted; l represents an integer from 1 to 12, and m1 and m2 represent an integer from 1 to 3. The method of claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (16) or (17): (wherein 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-, X may be the same or different when X is 2; l represents an integer from 1 to 12, and m represents an integer from 0 to 2). The method of claim 1 or 2, wherein the component (A) has a photosensitive side chain selected from any one of the group consisting of the following formula (18) or (19): (wherein 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 the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or The two or six rings of the same or different substituents selected by the substituents are bonded via a bond group B, and the hydrogen atoms to which they are bonded may also independently pass through -COOR ₀ (wherein, R ₀ 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 The alkyl group having 1 to 5 carbon atoms is substituted; one of q1 and q2 is 1 and the other is 0; l is an integer from 1 to 12, m1 and m2 are integers from 1 to 3; and R ₁ is a hydrogen atom. , -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms). The method of claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (20): (wherein 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 a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or a substituent thereof The same or different 2~6 rings are selected via a bond group B, and the hydrogen atoms bonded thereto can also independently pass through -COOR ₀ (wherein R ₀ represents a hydrogen atom or carbon) a number of 1 to 5 alkyl groups, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number of 1 to 5 Substituted by an alkyloxy group; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or - O-CO-CH=CH-, X may be the same or different when X is 2; l represents an integer from 1 to 12, and m represents an integer from 0 to 2). The method according to any one of claims 1 to 11, wherein the component (A) has any one of liquid crystal side chains selected from the group consisting of the following formulas (21) to (31): (wherein A and B have the same definitions as above; Y ₃ is selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. And the group of these groups, the hydrogen atoms to which they are bonded may also independently pass through -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or a carbon number of 1~ Substituted with an alkyloxy group of 5; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a combination a benzene ring, a furan ring, a nitrogen-containing hetero ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; one of q1 and q2 is 1 The other is 0; l represents an integer from 1 to 12, and m represents an integer from 0 to 2, but in equations (23) to (24), the total of all m is 2 or more, and equations (25) to (26) In the middle, the total of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1 to 3; and R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, and a combination. a benzene ring, a furan ring, a nitrogen-containing hetero ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -). A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device, which is produced by the method of any one of claims 1 to 10. A transverse electric field driven liquid crystal display device characterized by having a substrate of claim 11th. A method of manufacturing a liquid crystal display element, characterized by The following steps are carried out to obtain a lateral electric field-driven liquid crystal display element: a step of preparing a substrate (first substrate) of claim 11; and a step of obtaining a second substrate having the liquid crystal alignment film by the following steps [ I']~[III'], a liquid crystal alignment film to which an alignment control energy is imparted is obtained: [I'] a polymer composition containing the following components (A) and (B) is applied onto a second substrate to form a coating film. The steps are: (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range; and (B) an organic solvent; [II'] a coating film obtained by [I'] is irradiated with an extinction ratio of 10:1 or more. a step of polarizing ultraviolet light; [III'] a step of heating the coating film obtained by [II']; and [IV] a step of obtaining a liquid crystal display element, wherein the liquid crystal of the first and second substrates is passed through the liquid crystal The first and second substrates are arranged to face each other in such a manner that the alignment films face each other. A transverse electric field-driven liquid crystal display element characterized in that it is manufactured by the method of claim 13 of the patent application.