TWI626266B - Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element - Google Patents

Abstract

The present invention provides a lateral electric field drive type liquid crystal display device capable of imparting alignment control ability with high efficiency and excellent afterimage characteristics. The present invention solves the above-mentioned problems by a polymer composition containing: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) 1 in a molecule having 2 More than one by hydroxyl, hydroxyalkyl, alkoxy, alkoxyalkyl, Oxirane Group, epoxy, isocyanate, oxetane group, cyclocarbonate , A crosslinkable compound of at least one substituent selected from trialkoxysilyl and a polymerizable unsaturated binding group, and (C) an organic solvent. In particular, the above-mentioned problems are solved by a manufacturing method of a substrate having a liquid crystal alignment film. The aforementioned manufacturing method obtains a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that is provided with alignment control energy by having the following steps: [I] 将A step of applying the composition on a substrate having a conductive film for driving a lateral electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] applying [II] A step of heating the obtained coating film.

Description

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

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

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

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

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

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

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

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

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

In addition, the photo-alignment method of a photo-crosslinking type or a photo-isomerization type is also A known. For example, a polyvinyl cinnamate is irradiated with polarized ultraviolet rays, and a dimerization reaction (crosslinking reaction) occurs at the double bond portion of the two side chains parallel to the polarized light. The liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). When using a side chain polymer with azobenzene on the side chain, the polarized light is irradiated with ultraviolet rays, and an isomerization reaction occurs in the azobenzene portion of the side chain parallel to the polarized light, so that the liquid crystal is aligned orthogonal to the polarization direction. (See, for example, Non-Patent Document 2).

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

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

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

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

[Invention Summary]

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

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

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

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

In addition, the object of the present invention is to provide a lateral electric field driving type having an improved voltage holding ratio, in addition to the above-mentioned object, to increase the film density of the liquid crystal alignment film, and the impurities existing in the liquid crystal alignment film will not move to the liquid crystal side A liquid crystal element and a liquid crystal alignment film for the element.

In addition, the object of the present invention is to provide, in addition to, or in addition to, the above-mentioned object, a lateral electric field drive type liquid crystal element having improved adhesion by improving the interaction between a liquid crystal alignment film and a sealant, and a device for the same. Liquid crystal alignment film.

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

<1> A polymer composition characterized by (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) 1 or more molecules having a hydroxyl group or a hydroxyalkyl group , Alkoxy, alkoxyalkyl, ethylene oxide, epoxy, isocyanate, Crosslinkable compound of at least one kind of substituent selected from oxetanyl group, cyclocarbonate group, trialkoxysilyl group and polymerizable unsaturated bonding group, and (C) organic solvent.

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

<3> As described in <1> or <2>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (1) to (6):

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

<4> As in the above <1> or <2>, the component (A) may have a photosensitive side chain selected from the group consisting of the following formulae (7) to (10):

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

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

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

<6> As 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 , 1, m1 and m2 have the same definitions as above.

<7> As 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> As described in said <1> or <2>, (A) component may have a photosensitive side chain chosen from the following formula (18) or (19).

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

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

<9> As described in said <1> or <2>, (A) component may have a photosensitive side chain represented by following formula (20).

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

<10> As described in any one of <1> to <9>, the component (A) may have a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31).

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

Y ₃ is a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to each other may also be independently substituted with -NO ₂ , -CN, halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, carbon number 5 Alicyclic hydrocarbons of ~ 8, alkyl groups of 1 to 12 carbons, or alkoxy groups of 1 to 12 carbons; l represents an integer of 1 to 12, m represents an integer of 0 to 2, but formula (23) ~ In (24), the total of all m is 2 or more, and in formulas (25) to (26), the total of all m is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom , -NO ₂ , -CN, halo, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon and alkyl or alkyloxy group having 5 to 8 carbon atoms Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<11> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is given: [I] the above-mentioned <1> ~ <10> the step of applying the composition of any one to a substrate having a conductive film for lateral electric field driving to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the coating film obtained in [II].

<12> A substrate having a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by the method of <11> above.

<13> A lateral electric field drive type liquid crystal display element, characterized in that The substrate having the item <12> above.

<14> A method for manufacturing a liquid crystal display element, which is characterized by obtaining a lateral electric field drive type liquid crystal display element by the following steps: a step of preparing the substrate (first substrate) of the above item <12>; and obtaining a liquid crystal alignment film The step of the second substrate is to obtain a liquid crystal alignment film imparting alignment control ability by having the following steps [I '] to [III']: [I '] coating a polymer containing the following components on the second substrate Steps of forming a coating film with a composition: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) 1 or more molecules having a hydroxyl group, a hydroxyalkyl group, and an alkoxy group , Alkoxyalkyl, ethylene oxide, epoxy, isocyanate, oxetanyl, cyclocarbonate, trialkoxysilyl, and polymerizable unsaturated bonding group selected at least 1 A crosslinkable compound of a substituent group and (C) an organic solvent; [II '] a step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; and [III '] applying the coating obtained in [II'] A step of heating the film; and [IV] a step of obtaining a liquid crystal display element, which is performed by liquid crystal Said first and second liquid crystal substrate film of the opposing alignment manner, so that the first and second substrates arranged opposite to each.

<15> A lateral electric field drive type liquid crystal display element, characterized in that it is manufactured by the method of <14>.

In addition, the following inventions were found.

<P1> A method for manufacturing a substrate having a liquid crystal alignment film, which comprises the following steps to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that imparts alignment control energy: [I] will contain (A), ( Steps of coating the polymer composition of B) and (C) on a substrate having a conductive film for lateral electric field driving to form a coating film: (A) Photosensitive side chain type exhibiting liquid crystallinity in a specific temperature range Molecules, (B) 1 or more molecules containing 2 or more of hydroxyl, hydroxyalkyl, alkoxy, alkoxyalkyl, ethylene oxide, epoxy, isocyanate, oxetanyl, and cyclocarbonic acid A crosslinkable compound having at least one substituent selected from an ester group, a trialkoxysilyl group, and a polymerizable unsaturated bonding group, and (C) an organic solvent.

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

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

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

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

<P4> In said <P1> or <P2>, (A) component may have any kind of photosensitive side chain chosen from the group which consists of following formula (7)-(10).

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

<P5> In said <P1> or <P2>, (A) component may have any kind of photosensitive side chain chosen from the group which consists of following formula (11)-(13).

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

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

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

<P7> In said <P1> or <P2>, (A) component may have a photosensitive side chain represented by following formula (16) or (17).

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

<P8> In said <P1> or <P2>, (A) component may have a photosensitive side chain represented by following formula (18) or (19).

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

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

<P9> In said <P1> or <P2>, (A) component may have a photosensitive side chain represented by following formula (20).

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

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

In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and lipid having 5 to 8 carbon atoms. Cyclic hydrocarbons, and groups of groups of these, the hydrogen atoms bonded to them may each independently pass -NO ₂ , -CN, halo, 1 to 5 carbon alkyl groups, or carbon 1 to 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l represents 1 to 12 Integer, m represents an integer from 0 to 2, but in formulas (25) to (26), the total of all m is 2 or more, and in formulas (27) to (28), the total of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and Alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF _2- . <P11> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which is manufactured by any one of the above-mentioned <P1> to <P10>.

<P12> A lateral electric field drive type liquid crystal display device having the substrate of <P11>.

<P13> A method for manufacturing a liquid crystal display element, which is to obtain a lateral electric field drive type liquid crystal display element by having the following steps: a step of preparing the substrate (first substrate) of the above <P11>; obtaining a first substrate having a liquid crystal alignment film 2 substrate steps, by There are the following steps [I '] to [III'] to obtain a liquid crystal alignment film that imparts alignment control ability: [I '] A second substrate is coated with the following components (A), (B), and (C) Polymer composition to form a coating film: (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, (B) 1 or more molecules having a hydroxyl group, a hydroxyalkyl group, an alkane Oxy, alkoxyalkyl, ethylene oxide, epoxy, isocyanate, oxetanyl, cyclocarbonate, trialkoxysilyl, and polymerizable unsaturated bond A crosslinkable compound having at least one substituent and (C) an organic solvent.

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

<P14> A lateral electric field drive type liquid crystal display device manufactured by the aforementioned <P13>.

<P15> A composition for manufacturing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which contains the following components: (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, (B) There are two or more hydroxyl groups, hydroxyalkyl groups, alkoxy groups, alkoxyalkyl groups, ethylene oxide groups, epoxy groups, isocyanate groups, Crosslinkable compound of at least one kind of substituent selected from oxetanyl group, cyclocarbonate group, trialkoxysilyl group and polymerizable unsaturated bonding group, and (C) 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 element capable of imparting alignment control ability with high efficiency and excellent afterimage characteristics, and a lateral electric field drive type liquid crystal display element having the substrate.

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

In addition, according to the present invention, in addition to the above-mentioned effects, it is possible to increase the film density of the liquid crystal alignment film, and the impurities existing in the liquid crystal alignment film do not move to the liquid crystal side, and have a lateral electric field drive type liquid crystal element with improved voltage retention. And a liquid crystal alignment film for the device.

In addition, according to the present invention, in addition to or in addition to the above-mentioned effects, a lateral electric field-driven liquid crystal element having improved adhesion by improving the interaction between a liquid crystal alignment film and a sealant, and a liquid crystal for the element are provided. Alignment film.

1‧‧‧ side chain polymer film

2, 2a‧‧‧ side chain

3‧‧‧ side chain polymer film

4, 4a‧‧‧ side chain

5‧‧‧ side chain polymer film

6, 6a‧‧‧ side chain

7‧‧‧ side chain polymer film

8, 8a‧‧‧ side chain

[Fig. 1] Schematic illustration of the production of a liquid crystal alignment film used in the present invention An example of the anisotropic introduction process in the method. A crosslinked organic group is used for the photosensitive side chain, and the introduced anisotropy is small.

[Fig. 2] A diagram schematically illustrating an example of anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. A crosslinkable organic group is used for a photosensitive side chain, and the introduced anisotropy is large. Of the situation.

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

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

[Mode for Carrying Out the Invention]

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

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

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

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

The method for manufacturing a substrate with a liquid crystal alignment film of the present invention has the following steps: It obtains a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control energy is given by having the following steps: [I] will contain ( A) Photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, (B) 1 or more molecules having a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group, or ethylene oxide Crosslinkable compounds of at least one substituent selected from the group consisting of amino, epoxy, isocyanate, oxetanyl, cyclocarbonate, trialkoxysilyl, and polymerizable unsaturated bonding groups, and (C ) A step of applying a polymerizable composition of an organic solvent on a substrate having a conductive film for lateral electric field drive to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] Step of heating the coating film obtained in [II].

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

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

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

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

<Step [I]>

Step [I] is to contain a photosensitive side-chain polymer exhibiting liquid crystallinity in a specific temperature range, and one or more molecules having a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an alkoxyalkyl group, and a ring Crosslinkable compound of at least one selected from oxyethane, epoxy, isocyanate, oxetanyl, cyclocarbonate, trialkoxysilyl, and polymerizable unsaturated bonding group A polymerizable composition containing an organic solvent and an organic solvent is applied to a substrate having a conductive film for driving a lateral electric field to form a coating film.

<Substrate>

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

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

<Conductive film for lateral electric field drive>

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

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

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

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

<Polymer composition>

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

The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity within a specific temperature range; (B) 2 or more of a molecule consisting of a hydroxyl group and a hydroxyl group Alkyl, alkoxy Group, alkoxyalkyl group, ethylene oxide group, epoxy group, isocyanate group, oxetanyl group, cyclocarbonate group, trialkoxysilyl group, and polymerizable unsaturated bonding group. A crosslinkable compound of one substituent; and (C) an organic solvent.

<< (A) side chain polymer >>

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

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

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

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

(A) Photosensitive bond on the side chain polymer main chain Side chains, which are sensitive to light and cause cross-linking reactions, isomerization reactions, or light Fries rearrangements. The structure of the photosensitive side chain is not particularly limited, and it is preferably a structure that induces a cross-linking reaction or photo-Fries rearrangement by light induction, and more preferably a cross-linking reaction. At this time, even if exposed to external stress such as heat, the achieved alignment control performance can be stably maintained for a long time. The structure of the photosensitive side chain polymer film exhibiting liquid crystallinity is not particularly limited as long as it satisfies this characteristic, but it is preferred that it has a rigid liquid crystal component on the side chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, Stable liquid crystal alignment.

The structure of the polymer may be, for example, having a main chain and a bond therewith. A side chain having a liquid crystal component such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, and the like, and the light sensing with the front end Structure of a photosensitive group that undergoes a cross-linking reaction or an isomerization reaction, or has a main chain and a side chain bonded to the side chain, and the side chain has a phenyl benzyl which becomes a liquid crystal component and undergoes a light Fries rearrangement Structure of an acid ester group.

Photosensitive side chain polymer film that exhibits liquid crystallinity A more specific example of the structure is preferably a compound selected from the group consisting of a hydrocarbon, an acrylate, a (meth) acrylate, an itaconate, a fumarate, a maleate, and α-methylene-γ- A main chain composed of at least one of radical polymerization groups such as butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and a group consisting of The structure of the side chain formed by at least one of (1) to (6).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<< Method for manufacturing photosensitive side chain polymer >>

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

[Photoreactive side chain monomer]

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

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

A more specific example of the photoreactive side chain monomer, for example, has Selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, ethylene, maleimide, A polymerizable group composed of at least one of a radical polymerizable group such as pinene and a group of siloxanes, and a photosensitive side chain formed from at least one of the above formulae (1) to (6), For example, a photosensitive side chain formed from at least one of the above formulae (7) to (10), a photosensitive side chain formed from at least one of the above formulas (11) to (13), and the above formula are preferable. The photosensitive side chain represented by (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the photosensitive side chain represented by the above formula (18) or (19), the above The structure of the photosensitive side chain represented by Formula (20) is preferable.

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

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

[Liquid crystal side chain monomer]

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

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

More specific examples of the liquid crystalline side chain monomer are preferably those having Selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, ethylene, maleimide, The polymerizable group composed of at least one group of radical polymerizable groups such as pinene and the side chain structure formed of at least one of the above formulae (21) to (31) are preferred.

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

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

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

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

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

Examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and anthryl methacrylate Methyl ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methacrylic acid 2- Methoxyethyl, methoxytrimethacrylate Glycol ester, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, methyl formate 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like. Also available are glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxelan) (meth) acrylate (Meth) acrylate compounds having a cyclic ether group such as butyl) methyl ester.

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

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

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

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

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

Free radical thermal polymerization initiator is heated to decomposition temperature Compounds that generate free radicals as described above. Examples of such a radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), and difluorenyl peroxides (ethyl fluorenyl peroxide) , Benzamyl peroxide, etc.), peroxides (hydrogen peroxide, third butyl peroxide, cumene peroxide, etc.), dialkyl peroxides (di-third butadiene Peroxides, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkylperesters (peroxy Tert-butyl neodecanoate, tert-butyl peroxypivalate, tert-peroxy 2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, Ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2,2'-bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

Free radical photopolymerization initiators The compound polymerized by the group is not particularly limited. Examples of such a radical photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl Propyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4 ' -Cumyl acetone, 1-hydroxycyclohexylphenyl ketone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethyl Oxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1- Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid Isoamyl ester, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4,4'-tri (third butylperoxy Carbonyl) benzophenone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4 '-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloro (Methyl) -s-triazine, 2- (4'-pentoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (Ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s -Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxan Azole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o- (Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -(4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ' , 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinylpropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( 1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 3,3', 4,4'- Tetra (third hexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (third butylperoxycarbonyl) benzophenone, 3, 4'-bis (methoxycarbonyl) -4,3'-bis (third butylperoxycarbonyl) benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis ( Third butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazole-2-ylidene) -1-naphthalene-2-yl-ethanone, Or 2- (3-methyl-1,3-benzothiazole-2 (3H) -subunit) -1- (2-benzylidene) ethanone and the like. These compounds may be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and emulsification polymerization can be used. Law, suspension polymerization, dispersion polymerization, precipitation polymerization, block polymerization, solution polymerization, etc.

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

N, N-dimethylformamide, N, N-dimethylacetamide, N-formamidine Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene , Γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl Isopropyl ketone, methyl lysin, ethyl lysin, methyl lysin acetate, ethyl lysin acetate, butyl carbitol, ethyl carbitol, ethylene glycol , Ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol mono Methyl 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, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propylene carbonate , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methyl Butyl oxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropylamine, 3-butoxy-N, N-dimethylpropylamine and the like.

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

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

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

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

[Recycling of polymers]

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

Considering the molecular weight of the (A) side chain polymer of the present invention When the strength of the coating film, the workability when the coating film is formed, and the uniformity of the coating film, the weight-average molecular weight determined by GPC (gel permeation chromatography) method is preferably 2000 to 1,000,000, and more preferably 5000 to 100,000.

[Modulation of polymer composition]

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

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

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

<Crosslinkable compound having two or more specific groups in one molecule>

The polymer composition used in the present invention is a crosslinkable compound having two or more specific groups in one molecule.

When the compound is a polymer composition used in the present invention to form a liquid crystal alignment film, any one, two, three, or all of the following effects i) to iv) is not particularly limited. i) increase the film density of the liquid crystal alignment film, or ii) the impurities existing in the liquid crystal alignment film will not move to the liquid crystal side, or iii) have an improved voltage retention rate, and / or iv) increase the liquid crystal alignment film Interaction with sealants to improve adhesion.

The amount of a compound having two or more specific groups in one molecule, as long as It is not particularly limited when it has the effects described above, and it is 0.1 to 150 parts by mass, preferably 0.1 to 100 parts by mass, and more preferably 1 to 100 parts by mass of the polymer component of the polymer composition used in the present invention. 50 parts by mass.

The "specific group" of a compound having two or more specific groups in one molecule may be selected from the group consisting of hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, ethylene oxide, epoxy, and isocyanate. Group, oxetanyl group, cyclocarbonate group, trialkoxysilyl group and polymerizable unsaturated bonding group, for example, vinyl, (meth) acrylfluorenyl, and (meth) acrylfluorene Hordes.

Two or more radicals are selected from the above groups and may be the same or different.

Hereinafter, a cross-linkable compound having two or more specific groups in one molecule will be described by way of example, but it is not limited thereto. The compound is contained in the composition and may contain one kind or a combination of two or more kinds.

Crosslinkable compound having an epoxy group or an isocyanate group, and examples thereof include bisphenol acetone diglycidyl ether, phenol novolak (Phenol Novolac) an epoxy resin, cresol novolac epoxy resins, triglycidyl isocyanurate Acid ester, tetraglycidylaminodiphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl Glyceryl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetamidine diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1- Trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol , Tetraglycidyl-m-xylylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3 -Epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1 -(4- (1- (4- (2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

The cross-linkable compound having an oxetanyl group is a cross-linkable compound having at least two oxetanyl groups represented by the following formula [4].

Specifically, for example, a crosslinkable compound represented by the following formula [4a] to [4k].

A crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, such as an amino group having a hydroxyl group or an alkoxy group Examples of the lipid include melamine resin, urea resin, melamine diamine resin, glycoluril-formaldehyde resin, succinimidylamine-formaldehyde resin, and ethylene urea-formaldehyde resin.

This crosslinkable compound can be prepared by using, for example, a hydrogen atom of an amine group. Methylol or alkoxymethyl or a substituted melamine derivative, benzomelamine derivative or glycoluril. This melamine derivative or benzomelamine derivative may exist in the form of a dimer or a trimer. Each of these triazine rings preferably has 3 to 6 hydroxymethyl or alkoxymethyl groups.

This melamine derivative or benzomelamine derivative Examples of the product include MX-750 for each triazine ring on the market, which is substituted with an average of 3.7 methoxymethyl melamine ring, an average of 3.7 methoxymethyl melamine substituted derivativ, One triazine ring is substituted by methoxymethyl groups with an average of 5.8 MW-30 (above manufactured by Sanwa Chemical Co., Ltd.) or CYMEL300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated melamine, CYMEL 235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, CYMEL 506, 508 and other butoxymethylated melamine, such as CYMEL1141 Methoxymethylated isobutoxymethylated melamine containing carboxyl groups, such as methoxymethylated ethoxymethylated benzomelamines such as CYMEL1123, methoxylated groups such as CYMEL1123-10 Methylated butoxymethylated benzomelamine, such as butoxymethylated benzomelamine, such as CYMEL1128, carboxyl-containing methoxy groups such as CYMEL1125-80 Methylated ethoxymethylated benzomelamine (the above was made by Mitsui Cyyanamid). Examples of glycoluril include butoxymethylated glycoluril such as CYMEL1170, methylolated glycoluril such as CYMEL1172, and methoxymethylolated glycolurol such as Powder link 1174.

A benzene or phenolic compound having a hydroxyl or alkoxy group, such as Examples include 1,3,5-gins (methoxymethyl) benzene, 1,2,4-gins (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) Benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

As the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, tetraalkoxysilane and the like can be used.

Specific examples of the compound having two or more trialkoxysilyl groups include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 4,4'- Bis (trimethoxysilyl) biphenyl, 4,4'-bis (triethoxysilyl) biphenyl, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane , Bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethylene, bis (triethoxysilyl) ethylene, 1,3-bis (trimethyl Oxysilylethyl) tetramethyldisilaxane, 1,3-bis (triethoxysilylethyl) tetramethyldisilaxane, bis (triethoxysilylmethyl) amine , Bis (trimethoxysilylmethyl) amine, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) Carbonate, bis (3-triethoxysilylpropyl) carbonate, bis [(3-trimethoxysilyl) propyl] disulfide, bis [(3-triethoxysilyl) propyl Yl] disulfide, bis [(3-trimethoxysilyl) propyl] thiourea, bis [(3-triethoxysilyl) propyl] thiourea, bis [(3-trimethyl Silicon-based Alkyl) propyl] urea, bis [(3-triethoxysilyl) propyl] urea, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (triethoxy Silylmethyl) benzene, tris (trimethoxysilylpropyl) amine, tris (triethoxysilylpropyl) amine, 1,1,2-tris (trimethoxysilyl) ethane, 1,1,2-tris (triethoxysilyl) ethane, tris (3-trimethoxysilylpropyl) tricyanate, tris (3-triethoxysilylpropyl) tris Polycyanate and other compounds.

Crosslinkable compounds with polymerizable unsaturated bonds, such as Examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) propenyloxyethoxytrihydroxy Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as methylpropane, glycerol polyglycidyl ether poly (meth) acrylate, etc. In addition, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) Base) acrylate, butanediol di (meth) acrylate, neopentyl alcohol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type two (Meth) acrylate, 1,6-n-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether bis (methyl) Base) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxyl Cross-linking compounds having two polymerizable unsaturated groups in the molecule such as valeric acid neopentyl alcohol di (meth) acrylate, and for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (methyl Acrylate), glycerol mono (meth) acrylate, 2- (meth) acryloxyethyl phosphate, N-hydroxymethyl (meth) acrylamide, etc. Saturated crosslinkable compound.

Alternatively, a compound represented by the following formula [5] may be used.

(In formula [5], A ₁ represents a group selected from the group consisting of cyclohexyl ring, bicyclohexyl ring, benzene ring, biphenyl ring, third phenyl ring, naphthalene ring, fluorene ring, anthracene ring or phenanthrene ring. n-valent group, A ₂ represents a group selected from the following formula [5a] or [5b], and n represents an integer of 1 to 4).

<Organic solvent>

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

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- Pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfene, tetramethylurea, pyridine, dimethylfluorene, hexamethylfluorene , Γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N -Dimethylpropanamine, 1,3-dimethyl-imidazolinone, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketones, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol Third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol mono Methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, and the like. These can be used alone or in combination.

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

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

For example, isopropanol, methoxymethylpentanol, methyl lysin, ethyl lysin, butyl lysin, methyl lysin acetate, ethyl lysin acetate, butyl card Ethanol, ethyl carbitol, ethyl carbitol acetate, ethylenedi Alcohol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol Tributyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl Methyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl Ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate Ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl ester , Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methyl Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl Acid ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol , Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other organic solvents with low surface tension.

These weak solvents can be used alone or in combination. use. When using a solvent as described above, avoid significantly reducing the solubility of the entire solvent contained in the polymer composition, and it is preferably 5 mass% of the entire solvent ~ 80 mass%, more preferably 20 mass% to 60 mass%.

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

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

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

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropane Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7- Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-acetoxy Triethoxysilyl-3,6-diazanonyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethyl) -3-aminopropyl Trimethoxysilane, N-bis (oxyethyl) -3-aminopropyltriethoxysilane, and the like.

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

Specific epoxy-containing compounds, such as ethylene glycol Diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6- Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamine Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

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

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

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, and carbonyl Dicoumarin, aromatic 2-hydroxy ketone, and aromatic 2-hydroxy ketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxydi Benzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2 -(4-bisphenolylmethylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylene) -3-methyl-β-naphthylthiazoline, 2- ( 4-Biphenoyl methylene) -3-methyl-β-naphthylthiazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthylthiazole Phthaloline), oxazoline (2-benzylidenemethylene-3-methyl-β-naphthyloxazoline), 2- (β-naphthylidenemethylene) -3-methylbenzo Oxazoline, 2- (α-naphthylidenemethylene) -3-methylbenzooxazoline, 2- (4-biphenoxymethylene) -3-methylbenzene Oxazoline, 2- (β-naphthyridinemethylene) -3-methyl-β-naphthoxazoline, 2- (4-bisphenolylmethylene) -3-methyl- β-naphthoxazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p- Nitroaniline, 2,4,6-trinitroaniline) or nitropinene (5-nitropinene), (2-[(m-hydroxy-p-methoxy) styryl) benzo Thiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2 -Naphthalenecarboxylic acid, 9-anthracene methanol and 9-anthracenecarboxylic acid), benzopyran, azoindole, furancoumarin, and the like.

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

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

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

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

After the polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, a hot plate, a heat cycle type oven, or A heating means such as an IR (infrared) type oven evaporates the solvent at 50 to 200 ° C, preferably 50 to 150 ° C to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase development temperature of the side chain polymer.

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

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

<Step (II)>

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

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

<Step [III]>

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

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

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

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

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

By having the above steps, the manufacturing method of the present invention can be implemented Anisotropy is now introduced into the coating film with high efficiency. Moreover, a substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<Step [IV]>

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

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

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

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

In the following description, an embodiment using a side chain polymer having a structure having a photo-crosslinkable group as a photoreactive group is referred to as a first form, and using a light Fries rearrangement group as a photoreactive group may cause a difference. An embodiment of the structured side chain polymer is called a second embodiment.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Therefore, the coating film used in the method of the present invention The coating film is sequentially irradiated with polarized ultraviolet rays and heat treatment, and anisotropy is efficiently introduced, which can be a liquid crystal alignment film with excellent alignment control.

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

Introduction of high-efficiency anisotropy to the coating film used in the present invention The optimum irradiation amount of polarized ultraviolet rays corresponds to the optimum irradiation amount of polarized ultraviolet rays in the coating film in which the photosensitive group undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photo-Frys rearrangement reaction. . As a result of irradiating the coating film used in the present invention with polarized ultraviolet light, the photocrosslinking reaction, photoisomerization reaction, or photo-Fries rearrangement reaction has a small number of photosensitive groups on the side chain, and the sufficient photoreaction amount cannot be obtained . At this time, sufficient self-organization cannot be performed even after heating. In addition, the coating film used in the present invention has a structure having a photocrosslinkable group. As a result of irradiating polarized ultraviolet light, when the photosensitive group of the side chain of the crosslink reaction is excessive, the crosslink reaction between the side chains proceeds excessively. At this time, the obtained coating film becomes rigid, which may prevent subsequent self-organization by heating. In addition, as for the coating film used in the present invention, and the structure having a light Fryce rearrangement base is irradiated with polarized ultraviolet light, when the photosensitive group of the side chain of the light Fryce rearrangement reaction becomes excessive, the Liquid crystallinity is excessively reduced. At this time, the liquid crystallinity of the obtained film is also lowered, which may prevent subsequent self-organization by heating. In addition, when a structure with a light Fryce rearrangement is irradiated with polarized ultraviolet light, when the amount of ultraviolet radiation is too large, the side chain polymer will photoly decompose, which may prevent subsequent self-organization by heating. Happening.

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

The coating film used in the method of the present invention uses polarized ultraviolet light The amount of light irradiation is optimized to optimize the amount of the photocrosslinking reaction or photoisomerization reaction or the photo-Fries rearrangement reaction of the photosensitive groups in the side chain of the side chain polymer film. Therefore, together with the subsequent heat treatment, it is possible to efficiently introduce anisotropy into the coating film used in the present invention. At this time, the preferable amount of polarized ultraviolet rays can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

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

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

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

As such, the liquid crystal display element provided by the present invention displays light External stress such as heat or heat shows high reliability.

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

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

[Example]

Examples of methacrylic monomers MA1 and MA2 As shown below.

In addition, MA1 and M2 were respectively synthesized as follows. That is, MA1 is synthesized by the synthesis method described in the patent document (WO2011-084546). MA2 is synthesized by a synthesis method described in a patent document (Japanese Patent Application Laid-Open No. 9-118717).

The cross-linking agents T1 to T14 used in the examples are shown below.

T1 to T14 are synthesized by the methods shown below.

T1: diethoxy (3-glycidyloxypropyl) methylsilane (manufactured by Tokyo Chemical Industry).

T2: Tetraethoxysilane (manufactured by Tokyo Chemical Industry).

T3: N, N, N ', N'-TETRAGLYCIDYL-4,4'-DIAMINO DIPHENYLMETHANE (made by Aldrich).

T4: Butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone.

T5: Triglycidyl cyanurate (manufactured by Tokyo Chemical Industry).

T6: well-known compound.

T7: 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylic acid ester (manufactured by Aldrich).

T8: well-known compound.

T9: Dipentaerythritol hexaacrylate (DAICEL-CYTEC AG).

T10: 2,4,6-tri [bis (methoxymethyl) amino] -1,3,5-triazine (manufactured by Tokyo Chemical Industry).

T11: 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane (manufactured by Asahi Organic Materials Industry Co., Ltd.).

T12: tris (4- (vinyloxy) butyl) trimellitic acid ester (manufactured by Aldrich).

T13: 1,3-bis (4,5-dihydro-2-benzoxazolyl) benzene (manufactured by Tokyo Chemical Industry).

T14: Vestanat B (manufactured by evonik).

The abbreviations of the reagents used in this example are shown below.

(Organic solvents)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellolysin

(Polymerization initiator)

AIBN: 2,2’-azobisisobutyronitrile

<Synthesis example 1>

MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed again. Then, it reacted at 50 degreeC for 30 hours, and obtained the polymer solution of a methacrylate. This polymer solution was dropped into diethyl ether (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (A1).

NMP (29.3 g) was added to the obtained methacrylate polymer powder (A1) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. NMP (24.7 g) and BC (40.0 g) were added to this solution, and a methacrylic acid polymer solution M1 was obtained by stirring.

<Synthesis example 2>

MA1 (4.99 g, 15.0 mmol) and MA2 (4.60 g, 15.0 mmol) were dissolved in THF (88.5 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed. Then, it was made to react at 50 degreeC for 30 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into diethyl ether (1000 ml), and the obtained precipitate was poured into The precipitate after filtration was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (A2).

NMP (54.0 g) was added to the obtained methacrylate polymer powder (A2) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. BC (40.0 g) was added to this solution, and a methacrylic acid polymer solution M2 was obtained by stirring.

<Example 1>

0.015 g of T1 was added to 5.0 g of the methacrylic polymer solution M1 obtained in Synthesis Example 1, and stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent A1.

Using this liquid crystal alignment agent A1, a liquid crystal cell was produced in the procedure shown below. The substrate is a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and is provided with comb-shaped pixel electrodes formed by patterning an ITO film.

The pixel electrode has a curved central portion and is arranged in plural. Comb-like shape composed of letter-shaped electrode elements. The width in the short-side direction of each electrode element is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrode forming each pixel is composed of electrode elements with a curved central portion and a plurality of ㄑ -shaped electrode elements arranged. Therefore, the shape of each pixel is not a rectangular shape, but is provided with a similar ㄑ character similar to the electrode element, which is bold and curved at the center shape.

Each pixel has a first region on the upper side and a second region on the lower side of the curved portion divided up and down with the curved portion in the center as a boundary. Compare each pixel In the first region and the second region, the formation directions of the electrode elements constituting their pixel electrodes are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode forms an angle of + 15 ° (clockwise) in the first region of the pixel, and the pixel electrode in the second region of the pixel The electrode elements form an angle of -15 ° (clockwise). That is, the directions of the first region and the second region of each pixel in the substrate surface rotation (in-plane switching) caused by the voltage applied between the pixel electrode and the counter electrode are mutually The opposite direction.

<< Modulation of liquid crystal cells >>

The liquid crystal alignment agent A1 obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Next, it was dried on a hot plate at 70 ° C. for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, the coating film surface was irradiated with ultraviolet light of 313 nm at 20 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. In addition, a coating film was also formed on a glass substrate having a columnar spacer having a height of 4 μm as an opposing substrate without forming an electrode, and subjected to an alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on a liquid crystal alignment film of one substrate. Next, another substrate is bonded so that the alignment direction of the liquid crystal alignment film surface becomes 0 °, and then the sealant is thermally cured to produce an empty cell. A liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the empty cell by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having a structure of a liquid crystal display element having an IPS (lateral switching) mode.

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

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

<Adhesiveness evaluation> << Sample production >>

Samples for adhesion evaluation were prepared as follows. The liquid crystal alignment agent was coated on an ITO substrate of 30 mm × 40 mm, and dried on a hot plate at 70 ° C. for 90 seconds. Next, the coating film surface was irradiated with ultraviolet light of 313 nm at 20 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film having a thickness of 100 nm.

After coating a 6 μm bead spacer on this substrate, a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was dropped on a liquid crystal alignment film of one of the substrates. Next, another substrate was bonded so that the width of the sealant became 1 cm, and the substrate was fixed with a jig, and then thermally cured at 150 ° C. for 1 hour to prepare a sample for evaluation of adhesion.

<< Determination of adhesion >>

Next, a desktop precision universal testing machine manufactured by Shimadzu Corporation was used. AGS-X 500N, after fixing the end portions of the upper and lower substrates of the sample substrate, squeezed from the upper portion of the central portion of the substrate, and measured the pressure (N) at the time of peeling. The results of the voltage holding ratio (VHR) and the adhesion measurement results are shown in Table 1 together with the composition of the liquid crystal alignment agent of Example 1.

<Examples 2 to 18>

A liquid crystal alignment 组成 A2 to A18 of Examples 2 to 18 was obtained by the same method as in Example 1 except that the composition shown in Table 1 was used. The liquid crystal cells and samples for adhesiveness evaluation were prepared using these. The voltage holding ratio (VHR) and adhesion were measured by the same method as in Example 1. The results are also shown in Table 1.

<Control 1 and 2>

The liquid crystal alignment agents of Controls 1 and 2 do not have additives, and methacrylic polymer solutions M1 and M2 are used respectively. A liquid crystal cell and a sample for adhesiveness evaluation were prepared in the same manner as in Example 1 except that the methacrylic polymer solutions M1 and M2 were used as the liquid crystal alignment agent. The voltage holding ratio (VHR) and adhesion were measured by the same method as in Example 1. The results are shown in Table 1.

[Table 1]

It is known from Table 1 that the use of additives in Examples 1 to 18 improves the voltage retention rate (VHR) compared to when the additives 1 and 2 are not used.

In addition, the use of additives in Examples 1 to 5 and Example 7 has higher adhesiveness than when the additives 1 and 2 are not used.

<Residual image evaluation>

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

Claims (9)

A polymer composition comprising: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a temperature range of 100 ° C to 300 ° C; (B) 1 or more molecules having a hydroxyl group or a hydroxyl group Alkyl, alkoxy, alkoxyalkyl, Oxirane Group, epoxy, isocyanate, oxetane group, cyclocarbonate, trialkoxymethyl A crosslinkable compound of at least one selected from the group consisting of a silane group and a polymerizable unsaturated bonding group, and (C) an organic solvent. For example, the composition of claim 1 in the scope of patent application, wherein (A) component has a photosensitive side chain that causes photocrosslinking, photoisomerization, or optical Fries rearrangement. For example, the composition of the scope of claims 1 or 2, wherein the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (1) to (6): In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom to which they are bonded may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted with halogen groups; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to The alicyclic hydrocarbon ring of 8 or the same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can each independently pass through -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, carbon 1 to 5 alkyl or 1 to 5 carbon oxy; Y ₂ is selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a carbon number of 5 to 8 The alicyclic hydrocarbons, and the groups of these groups, and the hydrogen atoms to which they are bonded can also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or 1 to 5 carbons Alkyloxy substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in the Y _1; X represents a single bond, -COO -, - OCO -, - N = N -, - CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; Cou means Coumarin 6-yl group or coumarin-7-yl group, and the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN , Halo, alkyl having 1 to 5 carbons, or alkyloxy having 1 to 5 carbons; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q Each is independently a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof, but X is When -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring, and when the number of P is 2 or more, P may be mutually The same or different, when the number of Q is 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0 ~ 2; when l1 and l2 are 0, when T is a single bond, A Also represents a single bond; when l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently Since the divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and the group of combinations of these. For example, for the composition of the scope of application for the patent item 1 or 2, the component (A) has a photosensitive side chain selected from the group consisting of the following formulae (7) to (10): In the formula, A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- , Or -O-CO-CH = CH-; Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or The same or different 2 to 6 rings selected from their substituents are bonded through a bonding group B, and the hydrogen atoms to which they are bonded may each independently pass -COOR ₀ (where R ₀ Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or Alkyloxy substituted with 1 to 5 carbons; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO- O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1 and m2 represent 1 An integer of ~ 3; n represents an integer of 0 to 12 (but when n = 0, B is a single bond); Y ₂ is selected from a bivalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon The alicyclic hydrocarbons of 5 to 8 and their groups are composed of groups, and the hydrogen atoms to which they are bonded can also independently pass through each other. -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl having 1 to 5 carbon atoms or alkyloxy having 1 to 5 carbon atoms; R represents a hydroxyl group , carbons, alkoxy of 1 to 6, or represents the same as defined in the Y _1. A method for manufacturing a substrate with a liquid crystal alignment film is to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that is provided with alignment control energy by having the following steps: [I] will apply for patents No. 1 to 4 The step of applying the composition of any one to a substrate having a conductive film for lateral electric field drive to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] A step of heating the coating film obtained in [II]. A substrate is characterized by having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by a method according to item 5 of the patent application. A lateral electric field drive type liquid crystal display element is characterized in that it has a substrate with the scope of patent application No. 6. A method for manufacturing a liquid crystal display element, which is characterized by obtaining a lateral electric field drive type liquid crystal display element with the following steps: a step of preparing a substrate (the first substrate) for which the scope of the patent application is No. 6; and obtaining a second substrate with a liquid crystal alignment film In the substrate step, a liquid crystal alignment film imparting alignment control ability is obtained by having the following steps [I '] to [III']: [I '] coating a second substrate containing the following components (A) ~ ( C) The step of forming a coating film with the polymer composition: (A) a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) 1 or more molecules having two or more hydroxyl groups and hydroxyalkanes Group, alkoxy group, alkoxyalkyl group, ethylene oxide group, epoxy group, isocyanate group, oxetanyl group, cyclocarbonate group, trialkoxysilyl group and polymerizable unsaturated bonding group [II '] The step of irradiating the coating film obtained by [I'] with polarized ultraviolet light; [III '] making [II'] A step of heating the obtained coating film; and [IV] a step of obtaining a liquid crystal display element, which is First and second liquid crystal so that the substrate 2 of the liquid crystal alignment film opposite way, so that the first and second substrates arranged opposite to each. A lateral electric field drive type liquid crystal display element is characterized by being manufactured by a method according to the eighth aspect of the patent application.