KR102204768B1 - Method for manufacturing substrate having liquid crystal alignment film for in-plane-switching-type liquid crystal display element - Google Patents

Abstract

The present invention provides a transverse electric field drive type liquid crystal display device having high efficiency, high efficiency, and excellent burn-in characteristics. The present invention provides a polymer composition containing [I] (A) a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) diisobutylcarbinol, and (C) an organic solvent, A step of forming a coating film by applying it on a substrate having a conductive film for driving; [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] By having;, it provides the manufacturing method of the board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements to which the orientation control ability was given.

Description

TECHNICAL FIELD The manufacturing method of a substrate having a liquid crystal alignment layer for a transverse electric field driving type liquid crystal display device TECHNICAL FIELD {METHOD FOR MANUFACTURING SUBSTRATE HAVING LIQUID CRYSTAL ALIGNMENT FILM FOR IN-PLANE-SWITCHING-TYPE LIQUID CRYSTAL DISPLAY ELEMENT}

The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display device. Specifically, it relates to a novel method for manufacturing a liquid crystal display device having a liquid crystal alignment film having excellent burn-in properties, high linearity at an end, and small swelling at an end.

A liquid crystal display element is known as a light-weight, thin, and low-power display device, and has recently made remarkable development, such as being used for large-sized television applications. The liquid crystal display element is configured by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes, for example. And in a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired alignment state between substrates.

That is, the liquid crystal aligning film is a constituent member of a liquid crystal display element, is formed on a surface of a substrate holding the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a predetermined direction between the substrates. In addition, in addition to the role of aligning the liquid crystal in a predetermined direction, such as a direction parallel to the substrate, the liquid crystal aligning film may require a role of controlling the pretilt angle of the liquid crystal. The ability to control the alignment of the liquid crystal in such a liquid crystal alignment film (hereinafter referred to as alignment control ability) is imparted by performing alignment treatment on the organic film constituting the liquid crystal alignment film.

As a method of alignment treatment of a liquid crystal alignment film for imparting alignment control ability, a rubbing method has conventionally been known. The rubbing method refers to the direction of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate in a certain direction with a cloth such as cotton, nylon, or polyester, and rubbing (rubbing direction) It is a method of aligning the liquid crystal. This rubbing method has been used in a conventional liquid crystal display device manufacturing process because it can easily achieve a relatively stable liquid crystal alignment state. And, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability and electrical properties such as heat resistance has been mainly selected.

However, in the rubbing method of rubbing the surface of a liquid crystal alignment film made of polyimide or the like, oscillation and generation of static electricity may be a problem. In addition, due to the recent high-definition of liquid crystal display elements and irregularities caused by electrodes on the corresponding substrate or switching active elements for liquid crystal drive, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment can be achieved. There were cases where there was no

Therefore, as another alignment treatment method of a liquid crystal alignment film not subjected to rubbing, a photoalignment method is actively studied.

Although there are various methods of the photo-alignment method, anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

As the main photoalignment method, a decomposition type photoalignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition occurs using the polarization direction dependence of ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned with the polyimide remaining without decomposition (see, for example, Patent Document 1).

Moreover, photo-crosslinking type and photo-isomerization type photoalignment method are also known. For example, polyvinyl cinnamate is used, polarized ultraviolet rays are irradiated, and a dimerization reaction (crosslinking reaction) is caused at the double bond portion of two side chains parallel to polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side-chain polymer having azobenzene in the side chain is used, polarized ultraviolet rays are irradiated, an isomerization reaction is generated in the azobenzene portion of the side chain parallel to the polarization, and the liquid crystal is aligned in a direction orthogonal to the polarization direction ( For example, see Non-Patent Document 2).

As in the above example, in the alignment treatment method of the liquid crystal alignment film by the photoalignment method, rubbing is not required, and there is no fear of oscillation or generation of static electricity. In addition, alignment treatment can be performed also on a substrate of a liquid crystal display element having irregularities on the surface, and it becomes an alignment treatment method of a liquid crystal alignment film suitable for an industrial production process.

In addition, when a liquid crystal aligning agent (also referred to as "coating solution") used to form a liquid crystal aligning film is applied to a substrate, industrially, it is generally carried out by a flexographic printing method or an inkjet coating method. At that time, in the solvent of the coating solution, in addition to N-methyl-2-pyrrolidone or γ-butyrolactone, which are solvents (also referred to as ``good solvents'') having excellent resin solubility, a liquid crystal aligning film is applied. In order to improve film uniformity, butyl cellosolve or the like, which is a solvent with low resin solubility (also referred to as a "poor solvent"), is mixed and used (see, for example, Patent Document 2).

Japanese Patent Publication No. 3893659 Japanese Laid-Open Patent Publication No. Hei 2-37324

M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992). K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As described above, the photo-alignment method has a great advantage because it does not require the rubbing process itself as compared to the rubbing method that has been industrially used as an alignment treatment method for a liquid crystal display element. And, compared with the rubbing method in which the orientation control ability becomes almost constant by rubbing, in the photoalignment method, it is possible to control the orientation control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, when it is desired to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of irradiation of polarized light may be required, and stable alignment of the liquid crystal may not be achieved in some cases.

For example, in the decomposition type photoalignment method described in Patent Literature 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp having an output of 500 W for 60 minutes. It becomes necessary. In addition, even in the case of a dimerization type or a photoisomerization type photoalignment method, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J is sometimes required. Further, in the case of a photo-crosslinking type or a photo-isomerizing type of photo-alignment method, the thermal stability and photo-stability of liquid crystal alignment are inferior, and thus there is a problem that alignment failure and display burn-in occur when a liquid crystal display device is used. In particular, in a transverse electric field drive type liquid crystal display device, since liquid crystal molecules are switched in-plane, misalignment of the liquid crystal after liquid crystal drive is liable to occur, and display burn-in caused by AC drive is a major problem.

Therefore, in the photoalignment method, high efficiency of alignment treatment and realization of stable liquid crystal alignment are required, and a liquid crystal alignment film or a liquid crystal aligning agent capable of efficiently imparting high alignment control ability to a liquid crystal alignment film is required.

In addition, in recent years, liquid crystal display elements have been used for mobile applications such as smart phones and mobile phones. In these applications, in order to secure as many display surfaces as possible, a sealing agent used to bond between substrates of a liquid crystal display element is present at a position close to the end of the liquid crystal alignment film. For this reason, when the coating film properties at the ends of the liquid crystal alignment film are deteriorated, that is, when the ends of the liquid crystal alignment film are not straight, or when the ends of the liquid crystal alignment film are swelling, the adhesion effect between the substrates of the sealing agent is lowered, and the liquid crystal Display characteristics and reliability of the display element may be deteriorated.

In the present invention, a substrate having a liquid crystal alignment film for a liquid crystal display device of a horizontal electric field driving type liquid crystal display device with high efficiency, an alignment control ability is imparted, excellent burn-in characteristics, high linearity at the end, and small swelling at the end, and a transverse electric field having the substrate An object of the present invention is to provide a driving type liquid crystal display device.

The inventors of the present invention found out the following invention as a result of intensive examination in order to achieve the above-described subject.

<1> (A) photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range,

(B) diisobutylcarbinol, and

(C) organic solvent

A polymer composition containing, particularly, a composition for producing a liquid crystal aligning film for a transverse electric field drive type liquid crystal display device.

In <2> said <1>, it is good for (A) component to have a photosensitive side chain which causes photocrosslinking, photoisomerization, or photofleece transition.

In <3> said <1> or <2>, it is good for (A) component to have any 1 type of photosensitive side chain chosen from the group which consists of following formula (1)-(6).

[Formula 1]

In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- It represents O- or -O-CO-CH=CH-;

S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be substituted with a halogen group;

T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;

Y ₂ is 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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be substituted with -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ ;

X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen Group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;

For q1 and q2, one side 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 combinations thereof; provided , When X is -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 the number of P is 2 or more. In this case, P may be the same or different, and 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 both 0, when T is a single bond, A also represents a single bond;

When l1 is 1, when T is a single bond, B also represents a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

In any one of <4> said <1>-<3>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;

l represents the integer of 1-12;

m represents the integer of 0-2, m1 and m2 represent the integer of 1-3;

n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

[Formula 2]

In any one of <5> said <1>-<3>, it is good for (A) component to have any 1 type of photosensitive side chain selected from the group which consists of following formula (11)-(13).

In the formula, A, X, 1, m, m2, and R have the same definition as above.

[Formula 3]

In any one of <6> said <1>-<3>, it is good for (A) component to 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.

[Formula 4]

In any one of <7> said <1>-<3>, it is good for (A) component to have a photosensitive side chain represented by following formula (16) or (17).

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

[Formula 5]

In any one of <8> said <1>-<3>, it is good for (A) component to 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 definition as above.

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

[Formula 6]

In any one of <9> said <1>-<3>, it is good for (A) component to have a photosensitive side chain represented by following formula (20).

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

[Formula 7]

In any one of <10> said <1>-<9>, it is good for (A) component to have any 1 type of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31) .

In the formula, A, B, q1 and q2 have the same definition as 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing heterogeneous A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) In WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1-3;

R ₂ is 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group, Or an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

[Formula 8]

<11> [I] The polymer composition of any one of the above <1> to <10>, particularly the composition for producing a liquid crystal alignment film for a transverse electric field driving type liquid crystal display element, is applied by coating on a substrate having a conductive film for transverse electric field driving Process of forming a film;

[II] The step of irradiating the polarized ultraviolet rays to the coating film obtained in [I]; And

[III] Step of heating the coating film obtained in [II];

A method for producing a substrate having the liquid crystal alignment film, wherein the liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which the alignment control ability is provided is obtained.

<12> The board|substrate which has the liquid crystal aligning film for transverse electric field drive type liquid crystal display elements manufactured by the method of said <11>.

The transverse electric field drive type liquid crystal display element which has the board|substrate of <13> said <12>.

Step of preparing the <14> substrate (first substrate) of the <12>;

[I'] Step of forming a coating film by applying the polymer composition of any one of the above <1> to <10>, particularly the composition for producing a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, on a second substrate;

[II'] A step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; And

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

The process of obtaining the liquid crystal aligning film to which the alignment control ability was given by having, and obtaining the 2nd board|substrate which has the liquid crystal aligning film; And

[IV] Step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the liquid crystal alignment films of the first and second substrates face each other through the liquid crystal;

By having a transverse electric field drive type liquid crystal display element, the manufacturing method of the liquid crystal display element.

<15> The transverse electric field drive type liquid crystal display element manufactured by the method of said <14>.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element, and a transverse electric field drive type liquid crystal display element having the substrate, which is highly efficient and provides an alignment control ability and has excellent burn-in characteristics.

Since the transverse electric field drive type liquid crystal display device manufactured by the method of the present invention is highly efficient and has an orientation control ability, display characteristics are not impaired even if it is continuously driven for a long time.

Moreover, the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which the linearity of the edge part of a liquid crystal aligning film is high, and the swelling of the edge part of a liquid crystal aligning film is small.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically illustrating an anisotropy introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, when a crosslinkable organic group is used in the photosensitive side chain, and the introduced anisotropy is small It is a drawing of.
Fig. 2 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, in which a crosslinkable organic group is used in the photosensitive side chain, and the introduced anisotropy is large It is a drawing of.
3 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, and an organic group causing a fleece transition or isomerization is used in the photosensitive side chain, and introduced It is a drawing in the case of small anisotropy.
4 is a diagram of an example schematically illustrating an anisotropic introduction treatment in a method for producing a liquid crystal alignment film used in the present invention, and an organic group causing a fleece transition or isomerization in a photosensitive side chain is used, and introduced It is a figure in the case of large anisotropy.
5 is a diagram illustrating an example of a coated film image of an optical microscope used to evaluate the linearity of an end portion of a liquid crystal aligning film.
It is a figure which shows an example of the coating film image of an optical microscope used to evaluate the swelling of the edge part of a liquid crystal aligning film.

As a result of conducting intensive research, the present inventors have obtained the following knowledge and have come to complete the present invention.

The polymer composition used in the production method of the present invention has a photosensitive side chain polymer (hereinafter, also referred to simply as a side chain polymer) capable of expressing liquid crystal properties, and the coating film obtained by using the polymer composition is , A film having a photosensitive side-chain type polymer capable of expressing liquid crystallinity. The rubbing treatment is not applied to this coating film, and alignment treatment is performed by polarization irradiation. And after polarized light irradiation, it becomes the coating film (hereinafter also referred to as a liquid crystal alignment film) to which the orientation control ability was given through the process of heating the side chain polymer film. At this time, the small anisotropy expressed by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently rearranged by self-organization. As a result, high-efficiency alignment treatment is realized as a liquid crystal alignment film, and a liquid crystal alignment film to which high alignment control ability is provided can be obtained.

In addition, in the polymer composition in the present invention, in addition to the side chain polymer as the component (A) and the organic solvent as the component (C), diisobutylcarbinol is used as the component (B).

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

<Method of manufacturing a substrate having a liquid crystal alignment film> and <Method of manufacturing a liquid crystal display device>

The method for producing a substrate having a liquid crystal alignment film of the present invention,

[I] (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range,

(B) diisobutylcarbinol, and

(C) organic solvent

A step of forming a coating film by applying the polymer composition containing the transverse electric field onto a substrate having a conductive film for driving a transverse electric field;

[II] The step of irradiating the polarized ultraviolet rays to the coating film obtained in [I]; And

[III] Step of heating the coating film obtained in [II];

Has.

By the above process, a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which an alignment control ability is provided can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate other than the obtained substrate (first substrate), a transverse electric field drive type liquid crystal display device can be obtained.

As the second substrate, in place of a substrate having a conductive film for driving a transverse electric field, in addition to using a substrate having no conductive film for driving a transverse electric field, the above steps [I] to [III] (not having a conductive film for driving a transverse electric field) Since a non-existent substrate is used, for convenience, in the present application, it may be abbreviated as steps [I'] to [III']), whereby a second substrate having a liquid crystal alignment film to which the alignment control ability is imparted can be obtained. .

The manufacturing method of the transverse electric field driving type liquid crystal display element,

[IV] Step of obtaining a liquid crystal display element by disposing the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;

Has. Accordingly, a transverse electric field drive type liquid crystal display device can be obtained.

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

<Step [I]>

In step [I], on a substrate having a conductive film for driving a transverse electric field, a polymer composition containing a photosensitive side-chain type polymer, diisobutylcarbinol, and an organic solvent that exhibits liquid crystallinity in a predetermined temperature range Apply to form a coating film.

<Substrate>

Although it does not specifically limit about a board|substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable to use a board|substrate with high transparency. In that case, it is not particularly limited, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.

Further, in consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for transverse electric field drive>

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

As the conductive film, when the liquid crystal display device is a transmission type, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. can be mentioned, but the present invention is not limited thereto.

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

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

<Polymer composition>

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

The polymer composition used in the production method of the present invention includes (A) a photosensitive side-chain type polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) diisobutylcarbinol; and (C) an organic solvent; Contains.

<<(A) side chain polymer>>

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

(A) It is good for the side chain type polymer to react with light in a wavelength range of 250 nm to 400 nm and further exhibit liquid crystallinity in a temperature range of 100°C to 300°C.

(A) It is preferable that the side chain type polymer has a photosensitive side chain which reacts to light in a wavelength range of 250 nm to 400 nm.

(A) It is preferable that the side chain polymer has a mesogenic group in order to show liquid crystallinity in the temperature range of 100 degreeC-300 degreeC.

(A) In the side chain type polymer, a side chain having photosensitivity is bonded to the main chain, and in response to light, a crosslinking reaction, an isomerization reaction, or an optical fleece potential can be caused. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction or photo-freeze dislocation in response to light is preferable, and a crosslinking reaction is more preferable. In this case, even if exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer capable of expressing liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a mesogenic component rigid in the side chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and the side chain is a mesogenic component such as a biphenyl group, terphenyl group, phenylcyclohexyl group, phenylbenzoate group, and azobenzene group. And, a structure having a photosensitive group bonded to the tip and reacting to light to perform a crosslinking reaction or isomerization reaction, or a main chain and a side chain bonded thereto, and the side chain may be a mesogen component, and an optical fleece It can be a structure having a phenylbenzoate group undergoing a potential reaction.

More specific examples of the structure of a photosensitive side-chain type polymer capable of expressing liquid crystalline properties include hydrocarbons, (meth)acrylates, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, and styrene. , Having a main chain composed of at least one member selected from the group consisting of radical polymerizable groups such as vinyl, maleimide, norbornene, and siloxane, and a side chain composed of at least one of the following formulas (1) to (6) It is preferably a structure.

[Formula 9]

In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- It represents O- or -O-CO-CH=CH-;

S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be substituted with a halogen group;

T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;

Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;

Y ₂ is 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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be substituted with -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ ;

X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen Group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;

For q1 and q2, one side 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 combinations thereof; provided , When X is -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 the number of P is 2 or more. In this case, P may be the same or different, and 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 both 0, when T is a single bond, A also represents a single bond;

When l1 is 1, when T is a single bond, B also represents a single bond;

H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

The side chain is preferably any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;

l represents the integer of 1-12;

m represents the integer of 0-2, and m1 and m2 represent the integer of 1-3;

n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

[Formula 10]

The side chain is preferably any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).

In the formula, A, X, 1, m, m2, and R have the same definition as above.

[Formula 11]

It is good that the side chain is a photosensitive side chain represented by the following formula (14) or (15).

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

[Formula 12]

It is good that the side chain is a photosensitive side chain represented by the following formula (16) or (17).

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

[Formula 13]

Moreover, it is good that a side chain is a photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definition as above.

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

[Formula 14]

The side chain is preferably a photosensitive side chain represented by the following formula (20).

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

[Formula 15]

Moreover, it is good for the (A) side chain type polymer to have any 1 type of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

In the formula, A, B, q1 and q2 have the same definition as 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing heterogeneous A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) In WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1-3;

R ₂ is 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group, Or an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

[Formula 16]

<<The manufacturing method of photosensitive side chain type polymer>>

The photosensitive side chain type polymer capable of expressing the above liquid crystal properties can be obtained by polymerizing the photoreactive side chain monomer and the liquid crystal side chain monomer having the photosensitive side chain.

[Photoreactive side chain monomer]

The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at a side chain portion of the polymer when a polymer is formed.

As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferable.

[Formula 17]

More specific examples of the photoreactive side chain monomer include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. A polymerizable group consisting of at least one selected from the group consisting of a radical polymerizable group and a siloxane of, and a photosensitive side chain comprising at least one of the formulas (1) to (6), preferably, for example, the formula A photosensitive side chain consisting of at least one of (7) to (10), a photosensitive side chain consisting of at least one of formulas (11) to (13), and a photosensitive side chain represented by formula (14) or (15) , It is preferable that it is a structure which has a photosensitive side chain represented by said formula (16) or (17), a photosensitive side chain represented by said formula (18) or (19), and a photosensitive side chain represented by said formula (20).

The present application is a photoreactive and/or liquid crystalline side chain monomer, novel compounds (1) to (11) represented by the following formulas (1) to (11); and compounds represented by the following formulas (12) to (17) (12) to (17) are provided.

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 a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group. Moreover, v represents 1 or 2.

[Formula 18]

[Formula 19]

[Formula 20]

[Liquid Crystalline Side Chain Monomer]

The liquid crystal side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity, and the polymer can form a mesogenic group at a side chain portion.

As a mesogenic group possessed by the side chain, it may contribute to a mesogen structure alone such as biphenyl or phenylbenzoate, or may contribute to a mesogenic structure by hydrogen bonding between side chains such as benzoic acid. The following structures are preferable as the mesogenic group possessed by the side chain.

[Formula 21]

More specific examples of the liquid crystal side chain monomers include hydrocarbons, (meth)acrylates, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. It is preferable that it is a structure having a polymerizable group consisting of at least one selected from the group consisting of a radical polymerizable group and a siloxane and a side chain consisting of at least one of the formulas (21) to (31).

(A) The side chain type polymer can be obtained by polymerization reaction of the photoreactive side chain monomer expressing the above-described liquid crystallinity. Moreover, it can obtain by copolymerization of a photoreactive side chain monomer which does not express liquid crystallinity and a liquid crystal side chain monomer, or a photoreactive side chain monomer which expresses liquid crystallinity, and a liquid crystal side chain monomer. Further, it can be copolymerized with other monomers within a range that does not impair the ability to express liquid crystallinity.

Other monomers include, for example, industrially available monomers capable of radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acid, acrylic acid ester compound, methacrylic acid ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, and vinyl compound.

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

As an acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 ,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecylacrylic Rate, and 8-ethyl-8-tricyclodecyl acrylate, etc. are mentioned.

As a methacrylic acid ester compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate Rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned. Cyclic ethers such as glycidyl (meth)acrylate, (3-methyl-3-oxetanyl)methyl (meth)acrylate, and (3-ethyl-3-oxetanyl)methyl (meth)acrylate A (meth)acrylate compound having a group can also be used.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether, etc. are mentioned, for example.

As a styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

The method for producing the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferred from the viewpoint of easy reaction control and the like.

As the polymerization initiator of radical polymerization, known compounds such as a radical polymerization initiator and a reversible addition-cleaving chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides. (Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxy ketals (dibutyl Peroxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), and Sulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile and 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) I can. Such radical thermal polymerization initiators may be used singly, or may be used in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2- Ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin Ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Isoamyl benzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( 2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s- Triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-( 2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benz Oxazole, 2-(p-dimethylaminostyryl)benzthiazole, 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'-tetrakis (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-morpholinopropionyl)-9-n-dodecyl Carbazole, 1-hydroxycyclohexylphenylketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -Phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone , 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'- Di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl -3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1 -(2-benzoyl)ethanone, etc. are mentioned. These compounds may be used alone or in combination of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side-chain type polymer capable of expressing liquid crystallinity is not particularly limited as long as the produced polymer is dissolved. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, Pyridine, dimethylsulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, Methyl Cellosolve, Ethyl Cellosolve, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Carbitol, Ethyl Carbitol, Ethylene Glycol, Ethylene Glycol Monoacetate, Ethylene Glycol Monoisopropyl Ether, Ethylene Glycol Mono Butyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene Glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl- 3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene 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, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxy butyl propionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropana Mid, etc. are mentioned.

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, you may mix and use with the above-mentioned organic solvent within the range in which the produced|generated polymer does not precipitate.

Further, in radical polymerization, since oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, it is preferable to use the organic solvent degassed to the extent possible.

The polymerization temperature during radical polymerization can be selected from 30°C to 150°C, but is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. The concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial reaction is carried out at a high concentration, and then, an organic solvent can be added.

In the above-described radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the resulting polymer decreases, and if the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer increases. Therefore, the ratio of the radical initiator is 0.1 relative to the monomer to be polymerized. It is preferable that it is mol%-10 mol%. Further, at the time of polymerization, various monomer components, solvents, initiators, and the like can also be added.

[Recovery of polymer]

In the case of recovering the produced polymer from the reaction solution of the photosensitive side-chain type polymer capable of expressing liquid crystallinity obtained by the above-described reaction, the reaction solution may be added to a poor solvent to precipitate these polymers. . Poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. Can be lifted. The polymer injected into the poor solvent and precipitated can be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, if the polymer recovered by precipitation is re-dissolved in an organic solvent and the operation of reprecipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more types of poor solvents selected from these are used, the purification efficiency is further increased, so it is preferable.

The molecular weight of the (A) side-chain polymer of the present invention is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the resulting coating film, workability at the time of forming the coating film, and the uniformity of the coating film. , 2000 to 1000000 are preferable, and more preferably 5000 to 200,000.

[Preparation of polymer composition]

It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side-chain type polymer capable of expressing the liquid crystal properties described above. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, all of the resin components described above may be photosensitive side chain polymers capable of expressing the above-described liquid crystal properties, but other than those in the range not impairing the liquid crystal expression ability and photosensitive performance. Other polymers of may be mixed. In that case, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such other polymers include, for example, poly(meth)acrylate, polyamic acid, polyimide, and the like, and non-photosensitive side-chain polymers capable of expressing liquid crystallinity.

<<(B) component>>

The polymer composition used in the present invention contains, as component (B), diisobutylcarbinol represented by the following structural formula, that is, 2,6-dimethyl-4-heptanol.

[Formula 22]

When the liquid crystal aligning agent contains diisobutylcarbinol, the wettability diffusivity is suppressed compared to the liquid crystal aligning agent which does not contain the liquid crystal aligning agent, so that the linearity of the end portion when the liquid crystal aligning film is formed is improved. In addition, it is possible to suppress the swelling of the end. This is because diisobutylcarbinol is a good solvent, N-methyl-2-pyrrolidone (NMP) or N-ethyl, compared with butyl cellosolve and propylene glycol monobutyl ether, which are poor solvents, from the relationship of boiling point/vapor pressure. It is considered that it is because it is a solvent that draws a vapor pressure curve close by 2-pyrrolidone (NEP), or that the poor solvent evaporates first, thereby suppressing swelling at the end.

The content is preferably 20 to 60 parts by mass, more preferably 25 to 45 parts by mass with respect to 100 parts by mass of the organic solvent of the component (C).

<<(C) organic solvent>>

The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrroli Don, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclo Hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used individually or may be mixed and used.

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

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of a film thickness and surface smoothness.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono n-butyl ether, propylene glycol- tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methyl Toxibutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n- Hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol , 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate , Propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, Isoamyl lactate, etc. And solvents having a low surface tension of.

One type of these poor solvents may be used, or multiple types may be mixed and used for them. In the case of using a solvent as described above, in order not to significantly lower the solubility of the entire solvent contained in the polymer composition, it is preferably from 5% by mass to 80% by mass, more preferably 20 It is mass%-60 mass %.

As a compound which improves the uniformity of the film thickness and surface smoothness, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like can be mentioned.

More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahigard (registered trademark) AG710 (manufactured by Asahi Glass Corporation), Suflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical) ), etc. The ratio of these surfactants to be used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass per 100 parts by mass of the resin component contained in the polymer composition.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, the functional silane-containing compound etc. shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, etc. are mentioned.

In addition, in addition to improving the adhesion between the substrate and the liquid crystal alignment layer, the following additives of a phenoplast type or an epoxy group-containing compound may be added in the polymer composition for the purpose of preventing deterioration of electrical properties due to the backlight when the liquid crystal display device is configured. You may contain it. Specific phenoplast additives are shown below, but are not limited to this structure.

[Formula 23]

Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylamino Methyl) cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. are illustrated.

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

As an additive, a photosensitizer can also be used. Colorless sensitizers and triplet sensitizers are preferred.

As photosensitizers, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino Substituted, aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzan Tron, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methyl Benzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene) -3-Methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxa Zoline, 2-(β-naphthoylmethylene)-3-methylbenzooxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzo Oxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-(p- Fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene) ), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), Naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindoleidine, merocoumarin and the like.

Preferably, they are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

In addition to those described above, in the polymer composition, as long as the effect of the present invention is not impaired, for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film, when the dielectric material or conductive material, furthermore, a liquid crystal alignment film In order to increase the hardness and density of the film, a crosslinkable compound may be added.

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

As for the coating method, industrially, a method performed by screen printing, offset printing, flexo printing, ink jet method, or the like is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotation coating method), or a spray method, and may be used depending on the purpose.

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

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

It is also possible to form a step of cooling the substrate on which the coating film was formed to room temperature after the [I] step and before the subsequent [II] step.

<Step [II]>

In step [II], the ultraviolet ray polarized to the coating film obtained in step [I] is irradiated. When irradiating polarized ultraviolet rays on the film surface of the coating film, ultraviolet rays polarized through a polarizing plate are irradiated from a certain direction to the substrate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, in order to selectively cause a photo-crosslinking reaction, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

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

<Step [III]>

In step [III], the coating film irradiated with ultraviolet rays polarized in step [II] is heated. By heating, orientation control ability can be imparted to the coating film.

For heating, heating means, such as a hot plate, a heat circulation type oven, or an IR (infrared ray) type oven, can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is expressed.

It is preferable that the heating temperature is within the temperature range of the temperature at which the side-chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the surface of the coating film is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer capable of expressing liquid crystal properties is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is a temperature that is 10°C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side-chain polymer to be used, and a temperature 10°C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is a temperature in the range made into an upper limit. When the heating temperature is lower than the above temperature range, the amplification effect of anisotropy due to heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the state of the coating film is in an isotropic liquid state ( Isotropic), and in this case, it may become difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is equal to or higher than the glass transition temperature (Tg) at which a phase transition occurs from a solid phase to a liquid crystal phase on the surface of a side chain polymer or coating film, and an isotropic phase transition causing a phase transition from a liquid crystal phase to an isotropic phase (isotropic phase). It refers to the temperature below the temperature (Tiso).

By having the above steps, in the production method of the present invention, it is possible to realize anisotropic introduction into a highly efficient coating film. In addition, it is possible to manufacture a substrate with a liquid crystal alignment layer attached thereto with high efficiency.

<Step [IV]>

In the [IV] step, similarly to the substrate (first substrate) having a liquid crystal alignment film on the conductive film for transverse electric field driving obtained in [III], the conductive film obtained in the above [I'] to [III'] is not provided. A substrate (second substrate) with a non-removable liquid crystal aligning film is disposed opposite to each other through a liquid crystal so that both liquid crystal aligning films face each other, thereby producing a liquid crystal cell by a known method, and producing a transverse electric field driving type liquid crystal display element. It's fair. In the steps [I'] to [III'], in step [I], instead of the substrate having the conductive film for driving the transverse electric field, a substrate having no conductive film for driving the transverse electric field was used, in addition to the step [ It can be carried out in the same manner as in I] to [III]. Since the difference between the steps [I] to [III] and the steps [I'] to [III'] is only the presence or absence of the above-described conductive film, the explanation of the steps [I'] to [III'] is omitted.

As an example of the production of a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is inside, and the other A method of bonding the substrates in the room and sealing by injecting liquid crystal under reduced pressure, or a method of bonding and sealing the substrates after dropping the liquid crystal on the liquid crystal alignment film surface scattered with spacers. Can be illustrated. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a transverse electric field as the substrate on one side. The diameter of the spacer at this time is preferably 1 µm to 30 µm, more preferably 2 µm to 10 µm. This spacer diameter determines the distance between a pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

In the method of manufacturing a substrate with a coating film of the present invention, after forming a coating film by applying a polymer composition on a substrate, polarized ultraviolet rays are irradiated. Subsequently, by heating, high-efficiency anisotropy introduction into the side-chain type polymer film is realized, and a substrate with a liquid crystal alignment film having the ability to control the alignment of liquid crystals is produced.

In the coating film used in the present invention, the introduction of highly efficient anisotropic properties into the coating film is realized by using the principle of molecular rearrangement caused by self-organization based on photoreaction of the side chain and liquid crystallinity. In the production method of the present invention, in the case of a structure having a photo-crosslinkable group as a photoreactive group in the side chain type polymer, a coating film is formed on the substrate using the side chain type polymer, and then polarized ultraviolet rays are irradiated, and then, After heating, a liquid crystal display element is manufactured.

Hereinafter, an embodiment using a side-chain type polymer having a structure having a photo-crosslinkable group as a photoreactive group is the first embodiment, and an embodiment using a side-chain type polymer having a structure having a photo-freese potential group or a group causing isomerization as the photoreactive group. Is referred to as a second form and described.

1 schematically illustrates an anisotropic introduction treatment in a method for producing a liquid crystal aligning film using a side-chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first aspect of the present invention. It is an example diagram. 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 membrane after polarized light irradiation, and FIG. 1 (c) is a diagram schematically showing the state of the side-chain type polymer film after heating, particularly when the introduced anisotropy is small, that is, in the first aspect of the present invention, the amount of ultraviolet irradiation in step [II] is ΔA It is a schematic diagram in the case of being in the range of 1%-15% of the ultraviolet irradiation amount which maximizes.

FIG. 2 schematically illustrates an anisotropic introduction treatment in a method for producing a liquid crystal alignment film using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group in the first aspect of the present invention. It is an example diagram. Fig. 2(a) is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, Fig. 2(b) is a diagram schematically showing the state of the side chain polymer film after polarized light irradiation, and Fig. 2 (c) is a diagram schematically showing the state of the side-chain type polymer membrane after heating, particularly when the introduced anisotropy is large, that is, in the first aspect of the present invention, the ultraviolet irradiation amount in the [II] step is ΔA It is a schematic diagram in the case of being in the range of 15%-70% of the ultraviolet irradiation amount which makes maximum

Fig. 3 is a liquid crystal alignment film using a side-chain polymer having a structure having a photo-freeze potential group represented by the above-described formula (18) or a photo-isomerizable group as a photo-reactive group in a second aspect of the present invention. It is a drawing of one example schematically explaining the anisotropic introduction|transduction process in the manufacturing method of. 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 membrane after heating, particularly when the introduced anisotropy is small, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in step [II] is ΔA It is a schematic diagram in the case of being in the range of 1%-70% of the ultraviolet irradiation amount which maximizes.

FIG. 4 is a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photo-friction potential group represented by the above-described formula (19) as a photoreactive group in a second aspect of the present invention. It is a drawing of one example schematically explaining the introduction process of the anisotropy of. 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 membrane after heating, particularly when the introduced anisotropy is large, that is, in the second aspect of the present invention, the ultraviolet irradiation amount in the [II] step is ΔA It is a schematic diagram in the case of being in the range of 1%-70% of the ultraviolet irradiation amount which maximizes.

In the first aspect of the present invention, in the anisotropic introduction treatment to the coating film, when the ultraviolet irradiation amount in the [II] step is within the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, first A coating film 1 is formed on the substrate. As shown in Fig. 1(a), in the coating film 1 formed on the substrate, the side chains 2 have a structure in which they are arranged randomly. In accordance with the random arrangement of the side chains 2 of the coating film 1, the mesogenic components and the photosensitive members of the side chains 2 are also randomly oriented, and the coating film 1 is isotropic.

In the first aspect of the present invention, in the anisotropic introduction treatment to the coating film, when the ultraviolet irradiation amount in step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, first A coating film 3 is formed on the substrate. As shown in Fig. 2(a), in the coating film 3 formed on the substrate, the side chains 4 have a structure in which the side chains 4 are randomly arranged. In accordance with the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive members of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

In the second aspect of the present invention, in the treatment for introducing anisotropy into the coating film, a side chain polymer having a structure having a photo-isomerizable group or an optical fleece potential group represented by the above-described formula (18) is used. In the case of using a liquid crystal aligning film, when the ultraviolet irradiation amount of the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount maximizing ΔA, the coating film 5 is first formed on the substrate. As shown in Fig. 3(a), in the coating film 5 formed on the substrate, the side chains 6 have a structure in which the side chains 6 are randomly arranged. In accordance with the random arrangement of the side chains 6 of the coating film 5, the mesogenic components and the photosensitive members of the side chains 6 are also randomly oriented, and the side chain polymer film 5 is isotropic.

In the second aspect of the present invention, in the anisotropic introduction treatment to the coating film, a liquid crystal alignment film using a side chain polymer having a structure having a photo-freeze potential group represented by the above-described formula (19) is used. WHEREIN: In the case where the ultraviolet irradiation amount of the [II] step is in the range of 1% to 70% of the ultraviolet irradiation amount maximizing ΔA, the coating film 7 is first formed on the substrate. As shown in Fig. 4(a), in the coating film 7 formed on the substrate, the side chains 8 are arranged at random. In accordance with the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive members of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, the isotropic coating film 1 is polarized. Irradiate ultraviolet rays. Then, as shown in Fig. 1(b), among the side chains 2 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 2a having a photosensitive group preferentially undergoes photoreaction such as a dimerization reaction. Raises. As a result, the density of the side chain 2a subjected to the photoreaction is slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 1.

In the first aspect of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is within the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, the isotropic coating film 3 is polarized. Irradiate ultraviolet rays. Then, as shown in Fig. 2(b), among the side chains 4 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 4a having a photosensitive group preferentially undergoes a light reaction such as a dimerization reaction. Raises. As a result, the density of the side chain 4a subjected to the photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 3.

In the second aspect of the present embodiment, the amount of ultraviolet irradiation in step [II] using a liquid crystal alignment film using a side-chain polymer having a photo-isomerizable group or a structure having an optical fleece potential group represented by the above-described formula (18) In the case of being in the range of 1% to 70% of the ultraviolet irradiation dose in which ΔA is maximized, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Then, as shown in Fig. 3(b), among the side chains 6 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6a having a photosensitive group preferentially undergoes a photoreaction such as an optical fleece potential. Raises. As a result, the density of the side chain 6a subjected to the photoreaction slightly increases in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.

In the second aspect of the present embodiment, using a coating film using a side-chain polymer having a structure having an optical fleece potential group represented by the above-described formula (19), the ultraviolet irradiation amount in the [II] step, ΔA is maximized. In the case of being in the range of 1% to 70% of the ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Then, as shown in Fig. 4(b), among the side chains 8 arranged in a direction parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 8a having a photosensitive group preferentially undergoes photoreaction such as an optical fleece potential. Raises. As a result, the density of the side chain 8a subjected to the photoreaction increases in the polarization direction of the irradiated ultraviolet rays, and as a result, small anisotropy is imparted to the coating film 7.

Next, in the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is within the range of 1% to 15% of the ultraviolet irradiation amount maximizing ΔA, the coating film 1 after polarization irradiation is heated, , The liquid crystal state. Then, as shown in Fig. 1(c), in the coating film 1, the amount of the crosslinking reaction generated is different between the direction parallel to and perpendicular to the polarization direction of the irradiated ultraviolet rays. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet rays is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the polarization direction and the vertical direction of the irradiated ultraviolet rays is higher than that in the parallel direction, and the side chain 2 containing the mesogenic component is rearranged by self-organization in a direction parallel to the polarization direction of the irradiated ultraviolet rays. . As a result, the very small anisotropy of the coating film 1 caused by the photocrosslinking reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 1.

Similarly, in the first embodiment of the present embodiment, in the case where the ultraviolet irradiation amount in the [II] step is in the range of 15% to 70% of the ultraviolet irradiation amount maximizing ΔA, the coating film 3 after polarization irradiation is heated, , The liquid crystal state. Then, as shown in Fig. 2(c), in the side chain polymer film 3, the amount of the crosslinking reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the direction perpendicular to it. Therefore, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet rays, and the side chain 4 containing the mesogenic component is rearranged. As a result, the small anisotropy of the coating film 3 caused by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3.

Similarly, in the second embodiment of the present embodiment, using a coating film using a side-chain polymer having a photo-isomerizable group or a structure having an optical fleece potential group represented by the above-described formula (18), ultraviolet rays in the step [II] In the case where the irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 5 after polarization irradiation is heated to make it a liquid crystal state. Then, as shown in Fig. 3(c), in the coating film 5, the amount of the photo-freeze potential reaction generated is different between the direction parallel to and perpendicular to the polarization direction of the irradiated ultraviolet rays. In this case, since the liquid crystal alignment force of the photo fleece potential body generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet rays is stronger than the liquid crystal alignment force of the side chain before the reaction, the mesogenic component is self-organized in a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. The side chain (6) containing a re-orientation. As a result, the very small anisotropy of the coating film 5 caused by the photo fleece potential reaction is amplified by heat, and a greater anisotropy is imparted to the coating film 5.

Similarly, in the second embodiment of the present embodiment, using a coating film using a side-chain polymer having a structure having an optical fleece potential group represented by the above-described formula (19), the amount of ultraviolet irradiation in the step [II] is ΔA. In the case of being in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 7 after polarization irradiation is heated to make it a liquid crystal state. Then, as shown in Fig. 4(c), in the side chain polymer film 7, the amount of the photo-freeze potential reaction generated is different between the direction parallel to the polarization direction of the irradiated ultraviolet rays, and the direction perpendicular to it. Since the anchoring force of the optical fleece potential body 8a is stronger than that of the side chain 8 before dislocation, when a certain amount or more of the optical fleece potential body is generated, it self-organizes in a direction parallel to the polarization direction of the irradiated ultraviolet rays to the side containing the mesogenic component. Chain (8) reorients. As a result, the small anisotropy of the coating film 7 caused by the photo fleece potential reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can be formed into a liquid crystal alignment film excellent in alignment control ability by introducing anisotropy with high efficiency by sequentially performing irradiation of polarized ultraviolet rays and heat treatment on the coating film.

And, in the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, it is possible to realize highly efficient introduction of anisotropy into a coating film.

The optimal amount of polarized ultraviolet radiation for the introduction of highly efficient anisotropy into the coating film used in the present invention is polarized light in which the amount of the photosensitive group in the coating film undergoes a photocrosslinking reaction, a photoisomerization reaction, or a photofriction potential reaction. Corresponds to the irradiation amount of ultraviolet rays. As a result of irradiating polarized ultraviolet rays with respect to the coating film used in the present invention, if there are few photosensitive groups in the side chain for photocrosslinking reaction, photoisomerization reaction, or photofriction potential reaction, the amount of photoreaction is not sufficient. In that case, even if heated after that, sufficient self-organization does not proceed. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays on a structure having a photocrosslinkable group, when the photosensitive group of the side chain for crosslinking reaction becomes excessive, the crosslinking reaction between the side chains proceeds excessively. . In that case, the obtained film becomes rigid, and it may interfere with the progress of self-organization by subsequent heating. In addition, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet rays to the structure having a photo-freeze potential group, when the photosensitive group of the side chain reacting with the photo-freeze potential becomes excessive, the liquid crystal property of the coating film is excessively deteriorated. . In that case, the liquid crystallinity of the film obtained is also lowered, and it may interfere with the progress of self-assembly by subsequent heating. In addition, when polarized ultraviolet rays are irradiated to a structure having an optical fleece potential group, if the amount of ultraviolet rays is excessively irradiated, the side chain polymer is photodecomposed, and subsequent heating may hinder the progress of self-organization. have.

Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group of the side chain by irradiation with polarized ultraviolet rays is a photo-crosslinking reaction, a photoisomerization reaction, or a photo-freeze potential reaction is the photosensitive group of the side chain type polymer film. It is preferable to set it as 0.1 mol%-40 mol%, and it is more preferable to set it as 0.1 mol%-20 mol%. By setting the amount of the photosensitive group in the side chain to photoreact in such a range, self-organization in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy formation in the film becomes possible.

In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the amount of photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the side chain of the side chain type polymer film, or the photofriction potential reaction Optimize. In addition to the subsequent heat treatment, high-efficiency, anisotropic introduction into the coating film used in the present invention is realized. In that case, it is possible to implement the appropriate amount of polarized ultraviolet rays based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet rays and ultraviolet absorption in a vertical direction after irradiation with polarized ultraviolet rays are measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film, and the ultraviolet absorbance in the direction perpendicular to the polarization direction, is evaluated. Then, the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays to realize the same are obtained. In the manufacturing method of the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of a liquid crystal aligning film can be determined based on the amount of polarized ultraviolet radiation that realizes this ?Amax.

In the manufacturing method of the present invention, it is preferable to make the irradiation amount of polarized ultraviolet rays to the coating film used in the present invention in the range of 1% to 70% of the amount of polarized ultraviolet rays that realize ΔAmax, and 1% to 50% It is more preferable to fall within the range of. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays that realize ΔAmax is 0.1 to 20 moles of the total photosensitive group of the side chain polymer film. % Corresponds to the amount of polarized ultraviolet rays for photocrosslinking reaction.

From the above, in the production method of the present invention, in order to realize the introduction of highly efficient anisotropy into the coating film, it is preferable to set a suitable heating temperature as described above based on the liquid crystal temperature range of the side chain type polymer. . Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is from 100°C to 200°C, the heating temperature after irradiation with polarized ultraviolet rays is preferably from 90°C to 190°C. By doing so, in the coating film used in the present invention, greater anisotropy is imparted.

By doing so, the liquid crystal display device provided by the present invention exhibits high reliability against external stress such as light or heat.

As described above, the substrate for a transverse electric field drive type liquid crystal display element manufactured by the method of the present invention or a transverse electric field drive type liquid crystal display element having the substrate is excellent in reliability, and is suitable for a large screen and high-definition liquid crystal television, etc. Can be used.

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

Example

The abbreviations used in the examples are as follows.

(Methacrylic monomer)

[Formula 24]

MA1 was synthesized by the synthesis method described in Patent Document (WO2011/084546).

<Organic solvent>

THF: Tetrahydrofuran

NEP: N-ethyl-2-pyrrolidone

PB: Propylene glycol monobutyl ether

DIBC: 2,6-dimethyl-4-heptanol

<Polymerization initiator>

AIBN: 2,2'-azobisisobutyronitrile

<Polymer synthesis>

After MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g) and degassed with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and deaerated again. After this, it reacted at 50 degreeC for 30 hours, and obtained the polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1000 ml), and the obtained precipitate was filtered. This deposit was wash|cleaned with diethyl ether, and it dried under reduced pressure in 40 degreeC oven, and obtained the methacrylate polymer powder (A). The number average molecular weight of this polymer was 16000, and the weight average molecular weight was 32000.

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

<Example 1>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and it stirred and dissolved at room temperature for 5 hours. A liquid crystal aligning agent (A1) was obtained by adding and stirring PB (20.0 g) and DIBC (25.0 g) to this solution.

<Example 2>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and it stirred and dissolved at room temperature for 5 hours. A liquid crystal aligning agent (A2) was obtained by adding and stirring PB (10.0 g) and DIBC (35.0 g) to this solution.

<Example 3>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and it stirred and dissolved at room temperature for 5 hours. A liquid crystal aligning agent (A3) was obtained by adding and stirring DIBC (45.0 g) to this solution.

<Control 1>

NEP (49.0 g) was added to the obtained methacrylate polymer powder (A) (6.0 g), and it stirred and dissolved at room temperature for 5 hours. A liquid crystal aligning agent (control 1) was obtained by adding and stirring PB (45.0 g) to this solution.

Using the liquid crystal aligning agent obtained in the Example of this invention, the inkjet coatability of a liquid crystal aligning agent was evaluated. The conditions are as follows.

The liquid crystal aligning agent (A1) obtained in Example 1 of the present invention, the liquid crystal aligning agent (A2) obtained in Example 2, the liquid crystal aligning agent (A3) obtained in Example 3, and the liquid crystal aligning agent obtained in Control 1 (Control 1) Was filtered under pressure with a membrane filter having a pore diameter of 1 µm, and the inkjet coating property was evaluated.

As the inkjet applicator, HIS-200 (manufactured by Hitachi Plant Technology) was used. The coating was applied on an ITO (indium tin oxide) evaporated substrate washed with pure water and IPA (isopropyl alcohol), with a coating area of 80 × 72 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, and a coating speed of 40. Mm/sec, the time from application to temporary drying was 30 seconds, and the temporary drying was carried out on a hot plate at 70°C for 90 seconds.

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

The linearity evaluation of the end portion of the liquid crystal aligning film was performed by observing the liquid crystal aligning film at the right end portion with an optical microscope (ECLIPSE ME600 manufactured by Nikon Corporation) with respect to the printing direction. Specifically, the difference between (1) and (2) in FIG. 5 of the liquid crystal aligning film image obtained by observing it with a magnification of 25 times with an optical microscope, that is, the length A in FIG. 5 was measured. Here, (2) of FIG. 5 shows the end of the region reaching the maximum to the right when the liquid crystal alignment film at the right end with respect to the printing direction is observed with an optical microscope, while (1) of FIG. 5 is similarly to an optical microscope. When observed as, the end of the region reaching the minimum to the right is shown. At this time, images of all the liquid crystal alignment films were obtained at the same magnification. In the evaluation, the shorter the length of this A, the better the linearity of the edge portion of the liquid crystal aligning film.

The swelling evaluation of the end portion of the liquid crystal aligning film was performed by observing the liquid crystal aligning film at the right end portion with an optical microscope with respect to the printing direction. Specifically, the length of B in FIG. 6 of the liquid crystal aligning film image obtained by observing at a magnification of 25 with an optical microscope was measured. Here, FIG. 6 is a diagram schematically showing the swelling of the liquid crystal aligning film observed at the right end with respect to the printing direction from the oblique portion. In that case, images of all liquid crystal aligning films were made to be obtained at the same magnification. In the evaluation, the shorter the length of this B, the better the swelling at the edge of the liquid crystal aligning film.

The results are as shown in the table below. In Table 2, the length of A and the length of B of the liquid crystal aligning film obtained in an Example are shown. In addition, as for the ratio of the organic solvent in Table 1, since the solid content concentration was 6 mass %, the ratio of the mass occupied in the remaining 94%, which is the ratio of the solvent, was shown.

From the result, the liquid crystal aligning film by the liquid crystal aligning agent of Example (the present invention) had high linearity at the edge of the liquid crystal aligning film and the swelling at the edge of the liquid crystal aligning film was small.

Fig. 1
1: side chain type polymer membrane
2, 2a: side chain
Figure 2
3: side chain type polymer membrane
4, 4a: side chain
Figure 3
5: side chain type polymer membrane
6, 6a: side chain
Fig. 4
7: side chain type polymer membrane
8, 8a: side chain
Figure 5
9: liquid crystal alignment film
10: ITO (indium tin oxide) deposition substrate
Fig. 6
11: liquid crystal alignment film
12: ITO (indium tin oxide) deposition substrate

Claims (15)

(A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range,
(B) diisobutylcarbinol, and
(C) organic solvent
Polymer composition containing. The method of claim 1,
A polymer composition in which the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition. The method of claim 1,
(A) component is the following formula (1)-(6)
(In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO -O- or -O-CO-CH=CH- is represented;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be substituted with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
Y ₂ is 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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be substituted with -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ ;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen Group, a C1-C5 alkyl group, or a C1-C5 alkyloxy group;
For q1 and q2, one side 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 combinations thereof; provided , When X is -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 the number of P is 2 or more. In this case, P may be the same or different, and 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 both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, when T is a single bond, B also represents a single bond;
H and I are each independently a group selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.)
A polymer composition having any one photosensitive side chain selected from the group consisting of.
[Formula 1]

The method according to any one of claims 1 to 3,
(A) component is the following formula (7)-(10)
(In the formula, A, B, D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO -O- or -O-CO-CH=CH- is represented;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
l represents the integer of 1-12;
m represents the integer of 0-2, m1 and m2 represent the integer of 1-3;
n represents the integer of 0-12 (however, when n=0, B is a single bond);
Y ₂ is 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 combinations thereof, and a hydrogen atom bonded to them is Each independently may be substituted with -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁ )
A polymer composition having any one photosensitive side chain selected from the group consisting of.
[Formula 2]

The method according to any one of claims 1 to 3,
(A) component is the following formulas (11) to (13)
(In the formula, A is each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, Or -O-CO-CH=CH- is shown;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
l represents the integer of 1 to 12, m represents the integer of 0 to 2, and m2 represents the integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents It is a group formed by bonding through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN , -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms, or a hydroxyl group or a carbon number of 1 to 6 Represents an alkoxy group)
A polymer composition having any one photosensitive side chain selected from the group consisting of.
[Formula 3]

The method according to any one of claims 1 to 3,
(A) component is the following formula (14) or (15)
(In the formula, A is each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, Or -O-CO-CH=CH- is shown;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
l represents the integer of 1 to 12, m1 and m2 represent the integer of 1 to 3)
A polymer composition having a photosensitive side chain represented by.
[Formula 4]

The method according to any one of claims 1 to 3,
(A) component is the following formula (16) or (17) (in the formula, A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- or -O-CO-CH=CH- is represented;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
l represents the integer of 1-12, m represents the integer of 0-2)
A polymer composition having a photosensitive side chain represented by.
[Formula 5]

The method according to any one of claims 1 to 3,
(A) component is the following formula (18) or (19)
(In the formula, A and B are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH- is represented;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
For q1 and q2, one side is 1 and the other is 0;
l represents the integer of 1 to 12, m1 and m2 represent the integer of 1 to 3;
R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms)
A polymer composition having any one photosensitive side chain selected from the group consisting of.
[Formula 6]

The method according to any one of claims 1 to 3,
(A) component is the following formula (20)
(In the formula, A is a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O- CO-CH=CH- is shown;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or different 2 to 6 rings selected from their substituents Is a group formed by bonding via a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (in the formula, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ ,- CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH -Is represented, and when the number of X is 2, X may be the same or different;
l represents the integer of 1-12, m represents the integer of 0-2)
A polymer composition having a photosensitive side chain represented by.
[Formula 7]

The method according to any one of claims 1 to 3,
(A) component is the following formulas (21) to (31)
(In the formula, A and B have the same definition as 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, and bonded to them Each hydrogen atom may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing heterogeneous A ring, a C5-C8 alicyclic hydrocarbon, a C1-C12 alkyl group, or a C1-C12 alkoxy group is shown;
For q1 and q2, one side is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) In WHEREIN: The sum of all m is 1 or more, and m1, m2, and m3 each independently represent an integer of 1-3;
R ₂ is 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 heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group, Or an alkyloxy group;
Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -)
A polymer composition having any one kind of liquid crystal side chain selected from the group consisting of.
[Formula 8]

[I] Step of forming a coating film by applying the polymer composition according to claim 1 on a substrate having a conductive film for driving a transverse electric field;
[II] The step of irradiating the polarized ultraviolet rays to the coating film obtained in [I];
[III] Step of heating the coating film obtained in [II];
A method for producing a substrate having the liquid crystal alignment film, wherein the liquid crystal alignment film for a transverse electric field drive type liquid crystal display element to which the alignment control ability is provided is obtained. A substrate having a liquid crystal alignment film for a transverse electric field drive type liquid crystal display element manufactured by the method according to claim 11. A transverse electric field drive type liquid crystal display device comprising the substrate according to claim 12. Step of preparing the substrate (first substrate) according to claim 12;
[I'] Step of forming a coating film by applying the polymer composition according to claim 1 on a second substrate;
[II'] A step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; And
[III'] Step of heating the coating film obtained in [II'];
The process of obtaining the 2nd substrate which has the said liquid crystal aligning film to obtain the liquid crystal aligning film to which the alignment control ability was given by having; And
[IV] Step of obtaining a liquid crystal display element by arranging the first and second substrates opposite to each other so that the liquid crystal alignment films of the first and second substrates face each other through a liquid crystal;
By having a transverse electric field drive type liquid crystal display element, the manufacturing method of the liquid crystal display element. A transverse electric field drive type liquid crystal display device manufactured by the method according to claim 14.

Images