TWI684604B - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention relates to (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) having the following formula (b) [wherein, A, B, S, T, X, P , Q, l1, l2, l3, and b ¹ and b ² are as defined in the specification] a polymer composition of a side chain polymer and (C) an organic solvent. Moreover, this invention relates to the manufacturing method of the liquid crystal aligning film obtained from the composition, and the board|substrate which has a liquid crystal aligning film. According to the present invention, it is possible to provide a novel polymer composition capable of imparting orientation control energy at high efficiency and imparting excellent electric characteristics to a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element, and a horizontal electric field driving type liquid crystal display element using the same Use liquid crystal alignment film.

Description

Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

The present invention relates to a novel liquid crystal aligning agent, a liquid crystal aligning film obtained thereby, and a liquid crystal display device having the same. The liquid crystal display device obtained by the present invention has excellent electrical characteristics.

It is known that the liquid crystal display device is a light-weight, thin, and low-power consumption display device, which has been used in large-scale television applications in recent years and has developed significantly. The liquid crystal display element is constituted by, for example, a pair of transparent substrates provided with electrodes sandwiching a liquid crystal layer. In a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film, so that the liquid crystal can be brought into a desired alignment state between substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the surface of the substrate sandwiching the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. In the liquid crystal alignment film, the liquid crystal is expected to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the substrate in a certain direction such as a parallel direction. The ability to control the orientation of the liquid crystal in the liquid crystal alignment film (hereinafter referred to as the orientation control energy) can be controlled by the organic film constituting the liquid crystal alignment film. Line-oriented processing.

As an alignment treatment method of a liquid crystal alignment film to be given alignment control energy, a rubbing method from the past is known. The so-called rubbing method is to wipe the surface of the organic film such as polyvinyl alcohol, polyamide, or polyimide on the substrate with a cloth such as cotton, nylon, polyester in a certain direction (rubbing), in the wiping direction (rubbing Direction) method of aligning liquid crystals. This rubbing method can realize a simple and relatively stable liquid crystal alignment state, so it can be used in the manufacturing process of liquid crystal display devices in the past. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance and electrical characteristics can be selected.

However, the rubbing method of wiping the surface of the liquid crystal alignment film made of polyimide or the like may cause problems such as dust generation or static electricity. In addition, due to the high definition of the liquid crystal watch element in recent years, or the unevenness corresponding to the electrode on the substrate or the switch active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be wiped evenly with a cloth, and uniform liquid crystal alignment cannot be achieved.

Therefore, as another alignment treatment method of the liquid crystal alignment film without rubbing, the photo alignment method is being actively discussed.

There are various methods for the light alignment method. An anisotropy is formed in an organic film that constitutes a liquid crystal alignment film by linearly polarized light or collimated virtual image (Collimated) light, and the liquid crystal is aligned according to the anisotropy.

As the main orientation method, a decomposition-type light orientation method is known. In this method, for example, the polyimide film is irradiated with polarized ultraviolet rays, and the polarization direction dependence of ultraviolet absorption of the molecular structure is utilized to cause anisotropic decomposition. And the liquid crystal is oriented by the undecomposed residual polyimide (e.g. Refer to Patent Document 1).

As another photo-alignment method, a photo-crosslinking type or photo-isomerization type photo-alignment method is known. In the photo-crosslinking-type photo-alignment method, for example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays, and a dimerization reaction (crosslinking reaction) occurs at the double bond portion of two side chains parallel to the polarized light. On the other hand, the liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In the photo-isomerization-type photo-alignment method, when a side chain type polymer having azobenzene in the side chain is used, polarized ultraviolet rays are irradiated, and an isomerization reaction occurs in the azobenzene portion of the side chain parallel to the polarized light , The liquid crystal is oriented at a right angle to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, there is no need to go through rubbing, so there is no concern about dust generation or static electricity generation. The substrates with liquid crystal display elements having irregularities on the surface can also be subjected to orientation treatment, which has become an industrial orientation treatment method for liquid crystal orientation films suitable for production processes.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Patent No. 3893659

[Non-patent literature]

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

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

As described above, the optical alignment method is an alignment processing method as a liquid crystal display element. Compared with the rubbing method that has been used industrially in the past, it has a large advantage because it does not require a rubbing step. In contrast to the friction method in which the directional control energy can be made almost constant by friction, in the optical directional method, the directional control energy can be controlled by changing the amount of polarized light irradiation. However, in the light alignment method, in order to achieve the same degree of alignment control energy as in the friction method, a large amount of polarized light irradiation is required, and there may be cases where stable liquid crystal alignment cannot be achieved.

For example, in the decomposition-type light directing method described in the above-mentioned Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp of 500 W for 60 minutes, etc., which requires a long time and a large amount of ultraviolet irradiation. In addition, in the case of the dimerization type or photoisomerization type light directing method, a large amount of ultraviolet irradiation of a few J (Joules) to several tens of J is necessary.

Therefore, in the photo-alignment method, it is expected that the alignment process will be more efficient or the liquid crystal alignment will be stabilized, and that a liquid crystal alignment film or a liquid crystal alignment agent that can impart alignment control energy to the liquid crystal alignment film with high efficiency is expected.

The present invention is to provide a liquid crystal alignment film for liquid crystal display elements and liquid crystals with excellent electrical characteristics that impart orientation control energy at high efficiency The purpose of the display element. A further object of the present invention is to provide a liquid crystal aligning agent that can impart a liquid crystal alignment film with a high voltage retention rate.

The inventors of the present invention wanted to achieve the above-mentioned problems and conducted a detailed review, and found the following invention.

<1> A polymer composition containing (A) a photosensitive side chain type polymer having liquid crystallinity in a predetermined temperature range, (B) a polymer having a side chain represented by the following formula (b) ,

[In formula (b), A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl extension, hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other; P and Q are each independently selected from a divalent benzene ring, naphthalene ring , A biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and groups of these groups; however, X is -CH=CH-CO-O-, -O- When CO-CH=CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; l3 is 0 or 1; both l1 and l2 are At 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; the dotted line indicates that the bond can be a single bond or a double bond; b ¹ and b ² each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together can form a cyclic or chain saturated or unsaturated divalent hydrocarbon group having 2 to 5 carbon atoms. The hydrocarbon group formed by ¹ and b ² may be further substituted by the substituent b ³ , and b ³ represents the same or different 1 selected from the group consisting of hydroxy, carboxy, nitro, cyano, halogen, alkyl, and alkoxy. Or plural substituents. ] And (C) organic solvents.

<2> For the polymer composition of the above <1>, wherein the component (A) has a photosensitive side chain that can cause photocrosslinking, photoisomerization, or photofries rearrangement: good.

<3> In the polymer composition of the above <1> or <2>, it is preferable that L in the aforementioned formula (b) is an oxygen atom.

<4> The polymer composition according to any one of <1> to <3> above, wherein the component (A) and/or the component (B) further have a side chain represented by the following formula (0).

[In the formula, A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms , The hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH- CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other; P and Q are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl Base ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbon atoms, and groups formed by these combinations; however, X is -CH=CH-CO-O-, -O-CO-CH= When CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer of 0~2; when l1 and l2 are both 0, 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; G is selected from the following formulas (G-1), (G-2), (G-3) and (G- 4)

(In the formula, the dotted line represents a bonding bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, a C 1-3 alkyl group, and a phenyl group. When R ⁵⁰ is a plural number, they may be the same or different from each other, and t is 1. Integer of ~7, J represents O, S, NH, or NR ⁵¹ , and R ⁵¹ represents a group selected from the group consisting of alkyl having 1 to 3 carbons and phenyl)).

<5> The polymer composition according to any one of the above <1> to <4>, wherein the component (A) and/or the component (B) may further have the following side chain (b-2), and the side chain (b-2) is a group having a group selected from pyridyl, amide, and carbamate groups.

<6> For any of the polymer compositions of <1> to <5> above, the component (A) is one having any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6) Better.

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms. The hydrogen atom bonded to these may be substituted with a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms Rings, or the same or different 2 to 6 rings selected from these substituents are bonded through the bonding group B, and the hydrogen atoms bonded to these are each independently selected by -COOR ₀ (where , R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and an alkyl group having 1 to 5 carbon atoms Substituted by an alkyl group or an alkyloxy group having 1 to 5 carbon atoms; Y ₂ is selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms , And the groups formed by these combinations, the hydrogen atoms bonded to these are independently selected by -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, carbon number 1 ~5 alkyl, or C1-C5 alkyloxy substituted; R represents hydroxyl, C1-C6 alkoxy, or the same definition as Y ₁ ; X represents a single bond, -COO -, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X becomes 2 , X may be the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these are each independent by -NO ₂ , -CN, -CH= C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group; one of q1 and q2 is 1, the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations of these The base of the group formed; however, 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, P When the number of becomes 2 or more, P may be the same or different, and when the number of Q becomes 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0~2; l1 and l2 At the same time is 0, when T is a single bond, A also represents a single bond; l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, and combinations of these groups.

<7> For the polymer composition of the above <1> to <5>, the component (A) may have 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 an integer of 1-12; m represents an integer of 0-2, and m1, m2 represent 1-3 Integer; n represents an integer from 0 to 12 (however, when n=0, B is a single bond).

<8> The polymer composition according to any one of the above <1> to <5>, wherein the component (A) may have any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13) .

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

<9> For any of the above <1>~<5> polymer composition The product, wherein the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).

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

<10> In any of the polymer compositions of <1> to <5> above, the component (A) may have a photosensitive side chain represented by the following formula (16) or (17).

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

<11> In any of the polymer compositions of <1> to <5> above, the component (A) may have a photosensitive side chain represented by the following formula (18) or (19).

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

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyl group Oxy.

<12> In any of the polymer compositions of <1> to <5> above, the component (A) may have a photosensitive side chain represented by the following formula (20).

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

<13> The polymer composition according to any one of <1> to <12> above, wherein the component (A) may have any one kind of liquid crystal side selected from the group consisting of the following formulas (21) to (31) chain.

In the formula, A and B have the same definition as above; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbons having 5 to 8 carbon atoms , And the groups formed by these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 alkyloxy groups Substituted; R ₃ represents 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 contains heterocycles, alicyclic hydrocarbons having 5 to 8 carbon atoms, alkyl groups having 1 to 12 carbon atoms, or alkoxy groups having 1 to 12 carbon atoms; one of q1 and q2 is 1, and the other is 0; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in formulas (23) to (24), all m add up to 2 and for formulas (25) to (26), all m add up to 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen Contains heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkyloxy group; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, and -CH=N- , -CF ₂ -.

<14> A method for manufacturing a substrate having a liquid crystal alignment film, wherein the liquid crystal alignment film is a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element which is provided with alignment control energy obtained by the following steps, and the above <1> Step of forming the coating film by applying the polymer composition described in any one of <13> to a substrate having a conductive film for driving a transverse electric field; [II] irradiating the polarized light on the coating film obtained by [I] The step of ultraviolet rays; and [III] The step of heating the coating film obtained by [II].

<15> A substrate having a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element manufactured by the method of the above <14>.

<16> A horizontal electric field driving type liquid crystal display device characterized by having the substrate of the above <15>.

<17> A method of manufacturing a liquid crystal display device, which comprises the steps of obtaining a liquid crystal alignment film provided with alignment control energy, further obtaining a second substrate having the liquid crystal alignment film, and step [IV] to obtain a transverse electric field Driven liquid crystal display device; this step is the step of preparing the substrate (first substrate) of the above <15>; [I'] applying the polymerization described in any one of the above <1> to <13> on the second substrate The step of forming a coating film by forming a composition; [II'] the step of irradiating the polarized ultraviolet ray with the coating film obtained with [I']; and the step of heating the coating film obtained with [II'] with [III']; [IV] The first and second substrates are opposed to each other via liquid crystal, and the liquid crystal alignment films of the first and second substrates are opposed to obtain a liquid crystal display element Steps.

<18> A horizontal electric field driven liquid crystal display device manufactured by the method of <17> above.

With the present invention, orientation control energy can be imparted at high efficiency, and a liquid crystal alignment film for liquid crystal display elements and a liquid crystal display element having excellent electrical characteristics can be provided.

In addition, according to the present invention, when a specific polymer of the component (B) is contained in the polymer composition, a low-temperature firing can also provide a horizontal electric field driving type liquid crystal device with excellent voltage retention and use thereof Liquid crystal alignment film.

1‧‧‧Side chain polymer membrane

2. 2a‧‧‧Side chain

3‧‧‧Side chain polymer membrane

4. 4a‧‧‧Side chain

5‧‧‧Side chain polymer membrane

6, 6a‧‧‧Side chain

7‧‧‧Side chain polymer membrane

8, 8a‧‧‧ side chain

[Fig. 1] An example diagram illustrating an anisotropic introduction process in a method for manufacturing a liquid crystal alignment film used in the present invention in a mode, an anisotropy introduced using a crosslinkable organic group for a photosensitive side chain Figure for the hour.

[Fig. 2] An example of an example in which the anisotropic introduction process is described in the method for manufacturing the liquid crystal alignment film used in the present invention, and the anisotropy introduced by using a crosslinkable organic group for the photosensitive side chain For the big picture.

[Fig. 3] A method for manufacturing a liquid crystal alignment film used in the present invention In the figure, an example of the anisotropic introduction process will be described in a model. An organic group that causes Fries rearrangement or isomerization is used for the photosensitive side chain, and the figure of the introduced anisotropy is small.

[Fig. 4] An example diagram illustrating an anisotropic introduction process used in the method for manufacturing a liquid crystal alignment film of the present invention in a mode, using organics that cause Fries rearrangement or isomerization in a photosensitive side chain Base, the diagram when the imported anisotropy is large.

[Forms for carrying out the invention]

The inventors conducted detailed studies and obtained the following insights to complete the present invention.

The polymer composition used in the production method of the present invention is a photosensitive side chain type polymer having liquid crystallinity (hereinafter simply referred to as a side chain type polymer), and the coating film obtained by using the polymer composition is A film with a photosensitive side chain polymer that can express liquid crystallinity. The coating film does not need to be rubbed, and can be oriented by polarized light irradiation. After the polarized light is irradiated, the side chain type polymer film can be heated to form a coating film (hereinafter also referred to as a liquid crystal alignment film) that provides orientation control energy. At this time, the little anisotropy expressed by polarized light irradiation becomes a driving force, and the liquid crystal side chain type polymer itself is efficiently reoriented by self-organization. As a result, a high-efficiency alignment process can be realized as a liquid crystal alignment film, and a liquid crystal alignment film imparting high alignment control energy can be obtained.

Also, for the polymer composition in the present invention, add (A) The side chain type polymer of the component and the organic solvent of the (C) component, as the (B) component, a polymer having a repeating unit derived from the monomer represented by the above formula (b) is used. This can greatly improve the voltage retention rate, which is unexpected. The inventors considered this phenomenon as the point of addition of the (B) component, and also considered that the (A) component and the (B) component exert an interaction to dramatically improve the desired effect (and these are Those who have insights about the inventor of the mechanism of the present invention, but do not limit the inventor).

The embodiments of the present invention will be described in detail below.

<Polymer composition>

The polymer composition of the present invention is a polymer containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) a polymer having a side chain represented by the following formula (b),

[In formula (b), A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl extension, hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different; P and Q are each independently selected from a divalent benzene ring, naphthalene Rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and groups formed by these combinations; however, X is -CH=CH-CO-O-, -O- When CO-CH=CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; l3 is 0 or 1; l1 and l2 are both At 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; the dotted line indicates that the bond is a single bond or a double bond; b ¹ and b ² each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together can form a cyclic or chain carbon 2 to 5 ring-shaped saturated or unsaturated divalent hydrocarbon group. The hydrocarbon group formed by b ¹ and b ² may be further substituted by the substituent b ³ , and b ³ represents the same or different 1 selected from the group consisting of hydroxy, carboxy, nitro, cyano, halogen, alkyl and alkoxy. Or plural substituents] and (C) organic solvent.

<<(A) Side chain polymer>>

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

(A) The side-chain type polymer preferably reacts under light in the wavelength range of 250 nm to 400 nm, and preferably exhibits liquid crystallinity in the temperature range of 100°C to 300°C.

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

(A) The side chain type polymer has a mesogenic group because it shows liquid crystallinity in the temperature range of 100°C to 300°C.

(A) The side chain type polymer is bonded to the photosensitive side chain in the main chain, and is sensitive to light, and can undergo a cross-linking reaction, isomerization reaction, or photo-Freis rearrangement. The structure of the side chain having photosensitivity is not particularly limited, and a structure in which a cross-linking reaction is induced by light induction or photo-Freis rearrangement is preferable, and a structure that can cause a cross-linking reaction is preferable. At this time, even if exposed to external pressure such as heat, the orientation control performance achieved can be stably maintained for a long time. The structure of the photosensitive side chain type polymer capable of expressing liquid crystallinity is only required to satisfy such characteristics, and is not particularly limited. It is preferable that the side chain structure has a rigid mesogenic component. In this case, when the side chain type polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer is, for example, having a main chain and a side chain bonded thereto, and having the side chain as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azobenzene Mesogenic components and bonding at the apex The structure of the photosensitive group that induces light to produce a crosslinking reaction or isomerization reaction, or has a main chain and a side chain bonded to this, the side chain is also a mesogenic component, and can have a light The structure of the phenyl benzoate group in the Fries rearrangement reaction.

As a more specific example of the structure of the photosensitive side chain type polymer capable of expressing liquid crystal, it is selected from the group consisting of hydrocarbon, (meth)acrylate, itaconic acid ester, fumaric acid ester, maleic acid ester, α-extended The main chain composed of at least one group consisting of radical polymerizable groups such as methyl-γ-butyrolactone, styrene, vinyl group, maleimide, norbornene, and siloxanes is composed of: The structure of the side chain formed by at least one of the formulae (1) to (6) is preferable.

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms. The hydrogen atom bonded to these may be substituted with a halogen group; Y ₁ represents a group selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbons having 5 to 8 carbon atoms The ring, or the same or different 2 to 6 rings selected from these substituents, is bonded through the bonding group B and the group formed by bonding, and the hydrogen atoms bonded to these are each independently selected by -COOR ₀ (formula In which, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and a carbon number of 1 to 5 Alkyl, or C1-C5 alkyloxy substituted; Y ₂ is selected from divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, C5-8 alicyclic formula Hydrocarbons and the groups formed by these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen groups, carbon number Substituted by alkyl group of 1~5, or alkyloxy group of carbon number 1~5; R represents hydroxyl group, alkoxy group of carbon number 1~6, or the same definition as Y ₁ ; X represents single bond, -COO -, -OCO-, -N=N-, -CH=CH _- , -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X becomes 2 , X may be the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bound to these may be independently selected from -NO ₂ , -CN, -CH=C (CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group; one of q1 and q2 is 1, the other is 0 ; Q3 is 0 or 1; P and Q are each independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination Group base; however, 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 When it becomes 2 or more, P may be the same or different from each other, and when the number of Q becomes 2 or more, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; l1 and l2 are both At 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 selected from a divalent benzene ring, naphthalene ring, and Groups of phenyl ring, furan ring, pyrrole ring, and these combinations.

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

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

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

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

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

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

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).

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

In addition, the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).

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

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyl group Oxy.

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

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

In addition, the (A) side chain type polymer preferably has any one 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 selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5-8 The alicyclic hydrocarbons and the groups selected from these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 Substituted by an alkyloxy group; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl Base ring, furan ring, nitrogen containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms; l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in formulas (23) to (24), the total of all m is 2 or more, and for formulas (25) to (26), the total of all m is 1 or more, m1, m2, and m3 Each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5 ~8 alicyclic hydrocarbon, and alkyl group or alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

[Photoreactive side chain monomer]

The photoreactive side chain monomer is a monomer that forms a polymer having a photosensitive side chain at the polymer side chain portion when forming a polymer.

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

As a more specific example of the photoreactive side chain monomer, it is selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylidene-γ- A polymerizable group consisting of at least one group consisting of a radical polymerizable group such as butyrolactone, styrene, vinyl group, maleimide, norbornene, and a group of siloxane, and the above formula (1) The photosensitive side chain formed by at least one of (6) is preferably a photosensitive side chain formed by at least one of the above formulas (7) to (10), for example, by the above formula (11) to ( 13) At least one type of photosensitive side chain, the photosensitive side chain represented by the above formula (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the above formula (18) ) Or (19) is preferably a photosensitive side chain or a structure shown in the above formula (20).

[Liquid crystal 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 the mesogenic group included in the side chain, it may be a group such as biphenyl or phenyl benzoate which individually becomes a mesogenic structure, or it may be a mesogenic structure in which side chains such as benzoic acid are hydrogen bonded to each other Basis. The mesogenic group included in the side chain is preferably the following structure.

As a more specific example of the liquid crystal side chain monomer, it is selected from hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylidene-γ-butyrolactone At least one type of polymerizable group consisting of radical polymerizable groups such as esters, styrene, vinyl, maleimide, norbornene, and siloxanes and the above formulas (21) to (31) At least one of The structure of the formed side chain is better.

In the side chain type polymer of the component (A) of the present invention, the content of the photoreactive side chain is preferably 10 mol% to 100 mol%, and 15 mol% from the viewpoint of liquid crystal orientation ~95 mol% is better, and 20 mol% to 80 mol% is better.

The content of the liquid crystal side chain in the side chain type polymer of the component (A) of the present invention is preferably from 0 to 90 mol%, from 5 mol% to 85 mol from the viewpoint of liquid crystal orientation % Or less is better, and 20 mol% to 80 mol% or less is more preferable.

<<(B) ingredients>>

The polymer composition used in the present invention contains, as the component (B), a polymer having a side chain represented by the following formula (b).

In formula (b), A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-.

In formula (b), S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to these may be substituted with a halogen group.

In formula (b), T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to these may be substituted with a halogen group.

In formula (b), X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O -CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other.

In formula (b), P and Q are each independently selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these The selected group; however, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring.

In formula (b), l1 is 0 or 1.

l2 is an integer from 0 to 2.

l3 is 0 or 1.

When l1 and l2 are both 0, and T is a single bond, A also represents a single bond.

When l1 is 1, and T is a single bond, B is also expressed as a single bond.

The dotted line indicates that the bond can be a single bond or a double bond.

In formula (b), b ¹ and b ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together can form a cyclic or chain saturation of 2 to 5 carbon atoms Or unsaturated divalent hydrocarbon group, when the hydrocarbon group formed by b ¹ and b ² may be further substituted by the substituent b ³ , b ³ represents selected from the group consisting of hydroxyl, carboxyl, nitro, cyano, halogen, alkyl and The same or different 1 or plural substituents of the alkoxy group.

[Monomer with side chain represented by formula (b)]

(B) Component For the above-mentioned component (A), the exemplified monomers are not used [photoreactive side chain monomers], and are substituted with a monomer having a polymerizable group and a group represented by the above formula (b) for copolymerization The (co)polymer is preferred.

Therefore, the monomers copolymerizable with the monomer having a polymerizable group and the group represented by the above formula (b) include the "liquid crystal side chain monomer" and "other monomers" exemplified in the component (A) above. body".

In the side chain type polymer of the component (B) of the present invention, the content of the side chain represented by the above formula (b) is preferably 5 mol% to 100 mol% from the viewpoint of electrical characteristics. 30 mol% to 100 mol% is better, and 40 mol% to 100 mol% is better.

The content of the liquid crystal side chain in the side chain type polymer of the component (B) of the present invention is 95 mol% from the viewpoint of liquid crystal orientation The following is better, preferably 70 mol% or less, more preferably 60 mol% or less.

<specific copolymerization unit>

Either or both of the polymer of the component (A) and the polymer of the component (B) in the present invention may contain a specific copolymer for the purpose of further improving the characteristics. Examples of the specific copolymerization unit include the side chain represented by the following formula (0) and the following side chain (b-2).

[Side chain shown in formula (0)]

The side chain represented by formula (0) is shown below.

In the formula, A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms, The hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO -O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other; P and Q are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl Rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbons, and groups formed by these combinations; however, X is -CH=CH-CO-O-, -O-CO-CH=CH -When, -CH=CH- the bonding side of P or Q is an aromatic ring; l1 is 0 or 1; l2 is an integer of 0~2; when l1 and l2 are both 0, T is a single bond, A is also Represents a single bond; when 11 is 1, when T is a single bond, B is also represented as a single bond; G is selected from the following formulas (G-1), (G-2), (G-3) and (G- 4)

(In the formula, the dotted line represents a bonding bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, a C 1-3 alkyl group, and a phenyl group. When R ⁵⁰ is a plural number, they may be the same or different from each other, and t is 1. An integer of ~7, J represents O, S, NH, or NR ⁵¹ , and R ⁵¹ represents a group selected from the group consisting of alkyl having 1 to 3 carbons and phenyl).

More specific as a monomer having a side chain represented by the formula (0) Examples, selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylidene-γ-butyrolactone, styrene, vinyl, maleic acid A polymerizable group composed of at least one radical polymerizable group such as imine and norbornene and a group composed of siloxane and the structure having the side chain represented by the above formula (0) is preferable.

Among such monomers, specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and allyl Compounds such as glycidyl ethers, among which glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 3-vinyl-7- Oxadicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, etc.

As the monomer having thiirane, specific examples include those in which the epoxy structure of the monomer having the above epoxy group is substituted with thiirane.

Examples of the monomer having aziridine include, for example, those in which the epoxy structure of the monomer having the epoxy group is substituted with aziridine or 1-methylaziridine.

Examples of the monomer having an oxetane group include (meth)acrylates having an oxetane group. Among such monomers, 3-(methacryl oxymethyl) oxetane, 3-(acryl oxymethyl) oxetane, 3-(methacryl oxymethyl) Yl)-3-ethyl-oxetane, 3-(acryloxymethyl)-3-ethyl-oxetane, 3-(methacryloxymethyl)-2- Trifluoromethyloxetane, 3- (Acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(propyloyloxy) Methyl)-2-phenyl-oxetane, 2-(methacryloxymethyl)oxetane, 2-(propenyloxymethyl)oxetane, 2 -(Methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane are preferred, but also Examples include 3-(methacryloxymethyl)-3-ethyl-oxetane, 3-(propenyloxymethyl)-3-ethyl-oxetane, and the like.

As the monomer having a thietyl group, for example, a monomer in which an oxetanyl group-containing monomer is substituted with a thietyl group is preferred.

As the monomer having an azepanyl group, for example, a monomer in which an oxetane group of a monomer having an oxetane group is substituted with an azepanyl group is preferred.

Among the above, from the viewpoint of availability and the like, the monomer having an epoxy group and the monomer having an oxetane group are preferred, and the monomer having an epoxy group is preferred. Among them, glycidyl (meth)acrylate is preferred from the viewpoint of availability.

[Side chain (b-2)]

The side chain (b-2) is a side chain having a group selected from pyridyl, amide, and carbamate groups. By containing this side chain (b-2), as a liquid crystal alignment film, while reducing the dissolution of ionic impurities, it is used to promote the crosslinking reaction of the group represented by the above formula (0), or higher durability can be obtained LCD Directional film. To produce a polymer having a side chain (b-2), it is sufficient to copolymerize a monomer having a side chain (b-2).

As the monomer having the side chain (b-2), selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylidene-γ- A polymerizable group consisting of at least one radical polymerizable group such as butyrolactone, styrene, vinyl group, maleimide, norbornene, and a group consisting of siloxane, and having a pyridyl group, amide The structure of the side chain of the amino group and the carbamate group is preferred. The NH of the amide group and the carbamate group may not be substituted. Examples of the substituent at the time of substitution include an alkyl group, a protecting group for an amine group, and benzyl group.

Among such monomers, specific examples of the monomer having a pyridyl group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate and 2-(3-pyridylcarbonyloxy)ethyl. (Meth)acrylate, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, etc.

Examples of the monomer having an amide group or a carbamate group include 2-(4-methylpiperidin-1-ylcarbonylamino)ethyl (meth)acrylate, 4-( 6-methacryloyloxyhexyloxy) benzoic acid N-(third butyloxycarbonyl) piperidin-4-yl ester, 4-(6-methacryloyloxyhexyloxy) benzoic acid 2-( Third butyloxycarbonylamino) ethyl ester and the like.

<<Manufacturing Method of Polymer>>

The photosensitive side chain type polymer that can express liquid crystallinity of the component (A) or the component (B) can react by photopolymerization having the photosensitive side chain It is obtained by the monomer of the side chain and the monomer of the liquid crystal side chain.

(A) The side chain type polymer can be obtained by the polymerization reaction of the photoreactive side chain monomer expressing the above-mentioned liquid crystallinity. In addition, it can be copolymerized by a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerizing a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer Got. Moreover, the monomer which gives the said side chain (0) or the monomer which gives a side chain (b-2) can also be copolymerized.

(B) Component polymer The above-mentioned component (A) does not use the exemplified monomer [liquid crystal side chain monomer], but can be obtained by copolymerizing using the monomer represented by the above formula (b). It can also be copolymerized with the monomer imparting the side chain (b-2).

In addition, the component (A) and/or (B) can be copolymerized with other monomers without impairing the characteristics.

Examples of other monomers include free-radical polymerization monomers that are commercially available.

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

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

Examples of the acrylate compound include methacrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate Ester, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexane Acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methyl Oxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and, 8 -Ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, and anthracenyl methacrylate. Acrylate, anthracenyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, iso Borneyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate Ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tri Cyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, etc. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl) methyl (meth)acrylate, and (3-ethyl-3-oxetan (Meth)acrylate compounds having a cyclic ether group such as alkyl)methyl (meth)acrylate.

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

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

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

The manufacturing method of (A) component and the manufacturing method of (B) component are summarized below, and are also called the manufacturing method of the side chain type polymer of this embodiment. The method for producing the side chain polymer of the present embodiment is not particularly limited, and a method widely used in industry can be used. Specifically, it is manufactured by cationic polymerization, radical polymerization, or anion polymerization of the vinyl group of the liquid-crystalline side chain monomer or the photoreactive side chain monomer. Among these, radical polymerization is particularly preferred from the viewpoint of easy reaction control.

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

Radical thermal polymerization initiators are compounds that can generate free radicals by heating above the decomposition temperature. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide) Compounds, benzoyl peroxides, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxides, etc.), dialkyl peroxides (two -tert-butyl peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxydicyclohexane, etc.), alkyl full esters (Peroxyneodecanoic acid-tert-butyl Esters, tert-butyl peroxypivalate, tert-pentyl 2-ethylcyclohexane acid, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.) ), azo compounds (azobisisobutyronitrile, and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). In this way, the radical thermal polymerization initiator may be used alone or in combination of two or more.

The radical photopolymerization initiator may be only a compound that can initiate radical polymerization by light irradiation, and is not particularly limited. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl Xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylbenzeneacetone, 2-hydroxy-2-methyl-4 '-Isopropyl phenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy- 2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzene Methyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid iso Amyl ester, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6 -Trimethylbenzyl diphenylphosphine oxide, 2-(4'-methoxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'-dimethoxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyrene)-4,6-bis (Trichloromethyl)-s-triazine, 2-(2'-methoxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyl Oxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 4-〔pN,N-bis(ethoxycarbonylmethyl Radical)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1 ,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyrene)benzoxazole, 2-( p-dimethylaminostyrene) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-ran (4 -Ethoxycarbonylphenyl)-1,2'-bisimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-bisimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 3-(2-methyl-2-dimethylamino Propionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, 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'-bis(methoxy Carbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(t-butylperoxy (Carbonyl) benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H- Benzothiazole-2-ylidene)-1-naphthalene-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-( 2-Benzoyl) ethyl ketone, etc. These compounds may be used alone or in combination of two or more.

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

The organic solvent used for the polymerization reaction of the photosensitive side chain type polymer that expresses liquid crystallinity is only required to dissolve the generated polymer, and is not particularly limited. The specific examples include the following.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone Acetamide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetic acid Ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol di Methyl 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 mono Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n -Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, ethyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate , N-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, propylene Ethyl keto, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxy Propionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy- Examples of N,N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, and the like are mentioned.

These organic solvents may be used alone or after being mixed. Moreover, even if it is a solvent that does not dissolve the generated polymer, it can be used by mixing with the above-mentioned organic solvent as long as the generated polymer is not precipitated.

In addition, for radical polymerization, oxygen in the organic solvent can cause a hindrance to the polymerization reaction, so it is better to use an organic solvent that can be degassed to some extent.

It can be selected from any temperature ranging from 30°C to 150°C during the free radical polymerization, and is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain high molecular weight polymers. If the concentration is too high, the viscosity of the reaction solution will be too high and it is difficult to stir uniformly, so the monomer concentration is 1 mass % To 50% by mass is better, preferably 5% to 30% by mass. After the initial reaction is carried out at a high concentration, an organic solvent can be added.

For the above-mentioned radical polymerization reaction, the ratio of the radical polymerization initiator will become smaller for the molecular weight of the polymer with more monomers, and the molecular weight of the resulting polymer will become larger when there is less, so the ratio of the radical initiator For the monomer to be polymerized, 0.1 mol% to 10 mol% is preferred. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of polymers]

When the reaction solution of the photosensitive chain type polymer which can express liquid crystallinity obtained by the above reaction is recovered, the reaction solution is poured into a weak solvent, and only these polymers may be precipitated. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl. Ether, methyl ethyl ether, water, etc. After the polymer precipitated by being put into a weak solvent is recovered by filtration, it can be dried under normal pressure or reduced pressure by constant temperature or heating. In addition, the polymer recovered by precipitation is dissolved in an organic solvent again, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the weak solvent at this time include alcohols, ketones, and hydrocarbons. When three or more kinds of weak solvents are selected and used, the efficiency of purification can be further improved.

The molecular weight of the (A) side chain type polymer of the present invention is the weight measured by GPC (Gel Permeation Chromatography) method considering the strength of the obtained coating film, the workability at the time of forming the coating film, and the uniformity of the coating film The average molecular weight is preferably 2,000 to 1,000,000, preferably 5,000 to 100,000.

The molecular weight of the (B) side chain polymer of the present invention is the weight measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, the workability when forming the coating film, and the uniformity of the coating film The average molecular weight is preferably 2,000 to 1,000,000, preferably 1,000 to 150,000.

When the side chain type polymer of the component (A) and/or (B) of the present invention further contains the side chain represented by formula (0), the content is derived from the viewpoint of improvement of reliability and influence on the orientation of liquid crystal Look, 20 mol% or less is better, 10 mol% or less is better, and 5 mol% or less is better.

The content of the side chain type polymer of the component (A) and/or (B) of the present invention when it further contains a side chain (b-2) is from the viewpoint of improvement of reliability and influence on the orientation of liquid crystal , More preferably 80 mol% or less, 60 mol% or less is more preferred, 40 mol% or less is more preferred.

The side chain type polymer of the component (A) and/or (B) of the present invention may contain a photoreactive side chain, a side chain represented by the above formula (b), a liquid crystal side chain, and the above formula (0) Side chains, side chains other than the above side chains (b-2). If the content is the component (A), the total content of the photoreactive side chain, the liquid crystal side chain, the side chain represented by the above formula (0), and the side chain (b-2) does not reach 100%. (B) component, when the total content of the side chain represented by the above formula (b), the liquid crystal side chain, the side chain represented by the above formula (0), and the side chain (b-2) does not reach 100%, Each is its residual part.

In addition, the proportion of these side chains can be controlled by adjusting the molar fraction of the monomers imparted to each side chain when producing side chain type polymers.

<<(C) Organic solvent>>

The organic solvent used in the polymer composition used in the present invention is only an organic solvent in which the resin component is dissolved, and is not particularly limited. The specific example The following examples can be cited.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N- Ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, 3-methoxy- N,N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, 1,3-diamine Methyl-imidazolinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate Propyl carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether 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 Examples include ethers. These can be used alone or in combination.

The polymer composition used in the present invention may contain components other than the components (A), (B), and (C). As this example, a solvent or a compound that improves the film thickness uniformity or surface smoothness when the polymer composition is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, etc., but it is not limited thereto.

Specific examples of the solvent (weak solvent) that can improve the uniformity of the film thickness or the surface smoothness include the following.

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-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 monopropyl ether Ester monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isopropyl Butyl 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 acetate, pyruvate methyl Ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methyl Oxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butan Oxy-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 Solvents with low surface tension, such as alkyl esters and isoamyl lactate.

These weak solvents may be one kind or a mixture of plural kinds. When using the above-mentioned solvent, if the solubility of the entire solvent contained in the polymer composition is not to be significantly reduced, it is preferably 5% by mass to 80% by mass of the entire solvent, preferably 20% by mass to 60% by mass %.

Examples of the compound that improves the uniformity of the film thickness or the smoothness of the surface include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants.

More specific examples include EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC), FLUORADFC430, FC431 (manufactured by Sumitomo 3M) , Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGCSeimi Chemical), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and preferably 0.01 to 1 part by mass for 100 parts by mass of the resin component contained in the polymer composition.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea C Trimethoxysilane, 3-ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 -Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9 -Triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyl Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethyl)-3 -Aminopropyltrimethoxysilane, N-bis(oxyethyl)-3-aminopropyltriethoxysilane, etc.

In addition to improving the adhesion between the substrate and the liquid crystal alignment film, and for the purpose of preventing the reduction of the electrical characteristics caused by the backlight when forming the liquid crystal display element, additives such as the following phenolic resin-based or epoxy-containing compounds may also be included In the polymer composition. Specifically, the phenolic resin-based additive is shown below, but it is not limited to this structure.

As a specific epoxy group-containing compound, ethylene glycol can be exemplified Diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,6-Hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2, 4-Hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexyl Alkanes, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When a compound that improves adhesion to the substrate is used, the amount used is preferably 0.1 to 30 parts by mass, preferably 1 part by mass for 100 parts by mass of the resin component contained in the polymer composition. 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

As an additive, a light sensitizer can be used. Colorless sensitizers and triplet sensitizers are preferred.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methyl coumarin, 7-hydroxy 4-methyl coumarin), and ketone coumarin. Element, carbonyl bis-coumarin, aromatic 2-hydroxyketone, and aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino group )-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzylacetoxymethyl-3-methyl-β- Naphthothiazoline, 2-(β-naphthylmethylidenemethyl)-3-methylbenzothiazoline, 2-(α-naphthylmethylidenemethyl)-3-methylbenzothiazoline, 2- (4-Biphenyl acetylidene methyl)-3-methylbenzothiazoline, 2-(β-naphthylmethylidene methyl)-3-methyl-β-naphthalene thiazoline, 2-(4- Phenylphenylmethyl)-3-methyl-β-naphthazoline, 2-(p-fluorobenzylmethyl)-3-methyl-β-naphthalenethiazoline), oxazoline (2- Benzoylidene-3-methyl-methyl-β-naphthoxazoline, 2-(β-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(α-naphthyl Acetylidenemethyl)-3-methylbenzoxazoline, 2-(4-biphenylacetylidenemethyl)-3-methylbenzoxazoline, 2-(β-naphthoylmethylidenemethyl) )-3-methyl-β-naphthoxazoline, 2-(4-biphenyl phenylmethylidene)-3-methyl-β-naphthooxazoline, 2-(p-fluorobenzoyl benzoyl Ketomethyl)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitro Acenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styrene]benzothiazole, benzoin alkyl ether, N-alkylated phthalide, acetophenone ketal (2 ,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopyran, azoindazine , Merlot Coumarin (ellocoumarin) and so on.

Preferably, they are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl dicoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Ketal.

[Preparation of polymer composition]

The polymer composition of the present invention contains the photosensitive side chain type polymer of component (A), the specific (co)polymer of component (B) and the organic solvent of component (C). The polymer composition of the present invention except (A) component, The component (B) and the component (C) may further contain a solvent or compound that can improve film thickness uniformity or surface smoothness when the polymer composition is applied, a compound that improves adhesion between the liquid crystal alignment film and the substrate, and the like. Without impairing the effects of the present invention, other additives may be included.

The mixing ratio of (A) component and (B) component is preferably 1:99~99:1 in mass ratio. More preferably, it is 10:90~90:10, and the best 20:80~80:20.

The method for preparing the polymer composition of the present invention is not particularly limited. Examples of the preparation method include a method in which a solution of (A) component dissolved in (C) solvent is mixed, and (B) component is mixed in a predetermined ratio to form a uniform solution, or an appropriate stage of the preparation method, The method of further adding and mixing other additives as necessary.

For the preparation of the polymer composition of the present invention, a solution of a specific copolymer obtained by polymerization in a solvent can be used directly. At this time, for example, component (B) is added to the solution of component (A) to form a uniform solution. In this case, the solvent may be further added for the purpose of concentration adjustment. In this case, the solvent used during the production of the component (A) may be the same as or different from the solvent used to adjust the concentration of the polymer composition.

In addition, the prepared polymer composition solution is preferably filtered using a filter having a pore size of about 0.2 μm and then used.

The polymer composition used in the present invention is preferably adjusted to a coating liquid suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is adjusted so that the resin component to be formed into the resin film is dissolved in Organic solvent solutions are preferred. Herein, the resin component is the resin component containing the photosensitive side chain type polymer capable of expressing liquid crystal as described above. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

For the polymer composition of this embodiment, the resin component may be only a photosensitive side chain type polymer capable of expressing the liquid crystallinity of the component (A) and a specific polymer of the component (B), but not to impair the liquid crystal performance Within the scope of energy and photosensitive performance, other polymers other than these can be mixed. At this time, 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.

Examples of such other polymers include polymers other than the above-mentioned (A) component or non-(B) component made of poly(meth)acrylate, polyamic acid, or polyimide.

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

A step of [I] applying the polymer composition of the present invention on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] a step of irradiating polarized ultraviolet rays on the coating film obtained with [I] ; And [III] the step of heating the coating film obtained by [II]; through the above steps, a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element endowed with orientation control energy can be obtained, and further the liquid crystal can be obtained To the film substrate.

In addition to the substrate (first substrate) obtained above, by preparing a second substrate, a horizontal electric field driving type liquid crystal display element can be obtained.

The second substrate is to replace the substrate with a conductive film for driving a transverse electric field, and in addition to the substrate without a conductive film for driving a transverse electric field, use the above steps [I] to [III] (because the The substrate of the conductive film may be abbreviated as steps [I'] to [III'] in this case for the sake of simplicity, and a second substrate having a liquid crystal alignment film imparting alignment control energy may be obtained.

The manufacturing method of the horizontal electric field driving type liquid crystal display element is to have [IV] the first and second substrates obtained above are placed across the liquid crystal to arrange the liquid crystal alignment films of the first and second substrates in a relative position and to be opposed The step of obtaining a liquid crystal display element afterwards; thereby, a liquid crystal display element driven by a horizontal electric field can be obtained.

The steps of [I] to [III] and [IV] included in the manufacturing method of the present invention will be described below.

<Step [I]>

In step [I], a photosensitive side chain type polymer containing (A) component that can exhibit liquid crystallinity in a predetermined temperature range and (B) component are coated on a substrate having a conductive film for driving a transverse electric field A coating film is formed after the polymer composition of the specific polymer and the organic solvent of the component (C).

<substrate>

The substrate is not particularly limited, but when the manufactured liquid crystal display element is a transmissive type, it is preferable to use a substrate with high transparency. At this time, it is not particularly limited, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used.

In addition, considering the application to reflective liquid crystal display devices, opaque substrates such as silicon wafers can also be used.

<Conducting film for driving horizontal electric field>

The substrate is a conductive film with transverse electric field driving.

As the conductive film, when the liquid crystal display element is a transmissive type, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. can be produced, but it is not limited thereto.

In addition, in the case of a reflective liquid crystal display element, a material that reflects light such as aluminum can be used as the conductive film, but there is no limitation to this.

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

To the polymer composition, in addition to the above, within the scope of not impairing the effects of the present invention, a dielectric or conductive substance may be added for the purpose of changing the electrical characteristics such as the liquid crystal alignment film, dielectric permittivity, and conductivity, and further For the purpose of improving film hardness or density when used as a liquid crystal alignment film, a crosslinkable compound may be added.

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

The coating method in the industry is screen printing, offset printing, flexographic printing The brush or inkjet method is a general method. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method) or a spray method, etc., which can be used according to the purpose.

After coating the polymer composition on the substrate with the conductive film for driving the transverse electric field, the heating means, such as a hot plate, a thermal cycle type oven or an IR (infrared) type oven, is at 50 to 200°C, preferably 50 to 150 The coating film can be obtained after the solvent is evaporated at ℃. The drying temperature at this time is preferably lower than the temperature at which the liquid crystal phase of the side chain polymer is lower.

For the thickness of the coating film, the power consumption of the liquid crystal display element is too disadvantageous when it is too thick. When it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, 5 nm to 300 nm is better, preferably It is 10nm~150nm.

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

<Step [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, it is irradiated with ultraviolet rays that polarize the substrate through a polarizing plate from a certain direction. As the ultraviolet rays used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected by the type of coating film to be used via a filter or the like. For example, if you want to induce selective photocrosslinking reaction, you can choose to use ultraviolet light in the range of 290nm ~ 400nm. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized ultraviolet radiation depends on the coating film used. The amount of irradiation is the amount of polarized ultraviolet light that can achieve the difference of ΔA maximum value (hereinafter also referred to as ΔAmax) of the difference between the ultraviolet absorbance parallel to the polarized direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction in this coating film The range of 1% to 70% is better, and the range of 1% to 50% is better.

<Step [III]>

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

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

The heating temperature is preferably within a temperature range of a temperature at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystallinity expressing temperature). In the case of a film surface like a coating film, the liquid crystal display temperature on the surface of the coating film can be predicted to be lower than the liquid crystal display temperature in bulk observation when the photosensitive side chain type polymer can express liquid crystal. Therefore, the heating temperature is preferably within the temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after polarized ultraviolet irradiation is a temperature lower than the lower limit of the temperature range of the liquid crystal display temperature of the used side chain polymer by 10°C as the lower limit, which is more than the upper limit of the liquid crystal temperature range A temperature lower than 10°C is preferably the temperature in the upper range. When the heating temperature is lower than the above temperature range, the effect of increasing the anisotropy of heat in the coating film tends to be insufficient, If the heating temperature is higher than the above temperature range, the state of the coating film tends to be close to the isotropic liquid state (isotropic phase). At this time, it is difficult to reorient in one direction by self-organization.

Moreover, the liquid crystal display temperature is above the glass transition temperature (Tg) that causes the phase transition of the side chain type polymer or coating film surface from the solid phase to the liquid crystal phase, which is also referred to as causing the liquid crystal phase to the isotropic phase (etc. Square phase) The temperature below the isotropic phase transition temperature (Tiso).

By having the above steps, in the manufacturing method of the present invention, the anisotropy of the coating film can be introduced with high efficiency. In addition, the liquid crystal alignment film substrate can be manufactured efficiently.

<Step [IV]>

[IV] The step is to replace the substrate obtained by [III] with the liquid crystal alignment film on the conductive film for driving the transverse electric field (first substrate) in the same manner as the above [I'] to [III']. A substrate with a liquid crystal alignment film (second substrate) having a conductive film, through liquid crystal, the two liquid crystal alignment films are arranged in opposite directions in opposite directions, a liquid crystal cell is manufactured by a known method, and a horizontal electric field driven liquid crystal display element is manufactured Steps. In addition, in steps [I'] to [III'], in step [I], instead of a substrate having a conductive film for driving a transverse electric field, a substrate without the conductive film for driving a transverse electric field is used. 〕~〔III〕The same way. The difference between steps [I] to [III] and steps [I'] to [III'] is only the presence or absence of the above conductive film, so the description of steps [I'] to [III'] is omitted.

To cite the production of a liquid crystal cell or liquid crystal display element For example, the sealing method of preparing the above first and second substrates, spreading spacers on the liquid crystal alignment film of the unilateral substrate so that the liquid crystal alignment film surface is inside, bonding the other unilateral substrate, and injecting the liquid crystal under reduced pressure, Or a method in which liquid crystal is dropped on the surface of the liquid crystal alignment film where the spacers are dispersed, and the substrate is bonded and sealed. In this case, it is preferable to use a substrate having a comb-shaped electrode for driving a transverse electric field on a single-sided substrate. The diameter of the spacer at this time is preferably 1 μm to 30 μm, preferably 2 μm to 10 μm. The spacer diameter can determine the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer can be determined.

The method for manufacturing a coating film substrate of the present invention is to apply a polymer composition on a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, by heating, high-efficiency anisotropy of the side-chain polymer film is introduced, and a liquid crystal alignment film sub-substrate with liquid crystal alignment control capability is manufactured.

In the coating film used in the present invention, the principle of molecular reorientation caused by the photoreaction of the side chain and the self-organization based on liquid crystallinity is used to realize the introduction of highly efficient anisotropy into the coating film. In the manufacturing method of the present invention, when the side chain type polymer has a structure of a photo-crosslinkable group as the photoreactive group, the side chain type polymer is used to form a coating film on the substrate, and then the polarized ultraviolet light is irradiated, followed by After heating, a liquid crystal display element is produced.

Hereinafter, an embodiment using a side chain type polymer having a structure having a photo-crosslinkable group as a photo-reactive group is referred to as a first mode, and a photo-reactive group having a photo-fresh rearrangement group or isomerization is used as a photo-reactive group. The embodiment of the side chain type polymer of the base structure is called the second embodiment and will be described.

FIG. 1 shows the first form of the present invention as a light An example of the anisotropic introduction process in the method of manufacturing a liquid crystal alignment film using a side chain type polymer having a structure of a photocrosslinkable group as a reactive group is schematically described. 1(a) shows a schematic diagram of the state of the side chain polymer film before polarized light irradiation, FIG. 1(b) shows a schematic diagram of the state of the side chain polymer film after polarized light irradiation, and FIG. 1(c) shows after heating Mode diagram of the state of the side chain type polymer film, especially when the anisotropy introduced is small, that is, in the first aspect of the present invention, the ultraviolet irradiation amount ΔA of the [II] step is set at 1% of the maximum ultraviolet irradiation amount Pattern diagram when within ~15%.

FIG. 2 shows the anisotropic introduction process in the method for manufacturing a liquid crystal alignment film using a side chain type polymer having a structure of a photocrosslinkable group as the photoreactive group in the first aspect of the present invention. An example diagram for explanation. FIG. 2(a) shows a schematic diagram of the state of the side chain polymer film before polarized light irradiation, FIG. 2(b) shows a schematic diagram of the state of the side chain polymer film after polarized light irradiation, and FIG. 2(c) shows after heating The state schematic diagram of the side chain type polymer film, especially when the introduced anisotropy is large, that is, in the first aspect of the present invention, the ultraviolet irradiation amount of step [II] is set to ΔA at the maximum ultraviolet irradiation amount The pattern diagram in the range of 15%~70%.

FIG. 3 shows a side chain type polymer having a structure of a photoreis rearrangement group represented by the above formula (18) using a photoisomerizing group as the photoreactive group in the second aspect of the present invention An example of a schematic description of the anisotropic introduction process in the method of manufacturing a liquid crystal alignment film. Figure 3(a) shows the state mode of the side chain polymer film before polarized light irradiation Fig. 3(b) shows a schematic diagram of the state of the side-chain polymer film after polarized light irradiation, and Fig. 3(c) shows a schematic diagram of the state of the side-chain polymer film after heating, especially in the introduced anisotropy When it is small, that is, in the second aspect of the present invention, the ultraviolet irradiation amount in step [II] is a schematic diagram when ΔA is set within the range of 1% to 70% of the maximum ultraviolet irradiation amount.

4 shows a method for manufacturing a liquid crystal alignment film using a side chain type polymer having a structure of a photo-Frys rearrangement group represented by the above formula (19) as a photoreactive group in the second aspect of the present invention. An example of the anisotropic import process is explained in a model manner. 4(a) shows a schematic diagram of the state of the side chain polymer film before polarized light irradiation, FIG. 4(b) shows a schematic diagram of the state of the side chain polymer film after polarized light irradiation, and FIG. 4(c) shows after heating The state schematic diagram of the side chain type polymer film, especially when the introduced anisotropy is large, that is, for the second aspect of the present invention, the ultraviolet irradiation amount in step [II] is set to ΔA at the maximum ultraviolet irradiation The pattern diagram when the amount is in the range of 1%~70%.

According to the first aspect of the present invention, in the introduction process of the anisotropy of the coating film, the ultraviolet irradiation amount in the [II] step is set to ΔA within the range of 1% to 15% of the maximum ultraviolet irradiation amount First, the coating film 1 is formed on the substrate. As shown in FIG. 1(a), the coating film 1 formed on the substrate has a structure in which side chains 2 are arranged randomly. According to the random arrangement of the side chain 2 of the coating film 1, the mesogen component and the photosensitive group of the side chain 2 are also randomly oriented, and the coating film 1 is isotropic.

For the first aspect of the present invention, in the introduction treatment of the anisotropy of the coating film, the ultraviolet irradiation amount of [II] step is set to △A When it is set within the range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 is first formed on the substrate. As shown in FIG. 2(a), the coating film 3 formed on the substrate has a structure in which the side chains 4 are arranged randomly. According to the random arrangement of the side chains 4 with the coating film 3, the mesogen components and the photosensitive groups of the side chain 4 are also randomly oriented, and the coating film 2 is isotropic.

For the second aspect of the present invention, it is used in the anisotropic introduction process of the coating film, and the side of the structure having a photo-fresh rearrangement group shown in the above formula (18) is used. When the liquid crystal alignment film of the chain polymer is used, when the amount of ultraviolet irradiation in the [II] step is set to ΔA within the range of 1% to 70% of the maximum ultraviolet irradiation, the coating film 5 is first formed on the substrate. As shown in FIG. 3( a ), the coating film 5 formed on the substrate has a structure in which the side chains 6 are arranged randomly. According to the random arrangement of the side chains 6 of the coating film 5, the mesogenic components and photosensitive groups of the side chains 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

In the second aspect of the present invention, it is used in the introduction treatment of the anisotropy of the coating film, and the liquid crystal alignment using the side chain type polymer having the structure of the photo-Frys rearrangement group shown in the above formula (19) In the case of a film, when the amount of ultraviolet irradiation in the [II] step is set to ΔA within the range of 1% to 70% of the maximum amount of ultraviolet irradiation, the coating film 7 is first formed on the substrate. As shown in FIG. 4(a), the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged randomly. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and photosensitive groups of the side chain 8 are also randomly oriented, and the coating film 7 is isotropic.

In the first form of this embodiment, for the purple in step [II] When the external radiation dose is set within the range of 1% to 15% of the maximum ultraviolet radiation dose, the isotropic coating film 1 is irradiated with polarized ultraviolet rays. Therefore, as shown in FIG. 1(b), the photosensitive group of the side chain 2a having a photosensitive group among the side chains 2 arranged in parallel to the polarization direction of ultraviolet rays preferentially generates a photoreaction such as a dimerization reaction. As a result, the density of the side chain 2a that undergoes photoreaction is slightly increased in the polarization direction of ultraviolet irradiation, and as a result, very little anisotropy is imparted to the coating film 1.

In the first aspect of the present embodiment, when the ultraviolet irradiation amount in the [II] step is within the range of 15% to 70% of the maximum ultraviolet irradiation amount set to ΔA, the isotropic coating film 3 is irradiated with Polarized ultraviolet rays. Then, as shown in FIG. 2(b), the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in parallel to the polarization direction of ultraviolet rays preferentially generates a photoreaction such as a dimerization reaction. As a result, the density of the side chain 4a that undergoes photoreaction becomes higher in the polarization direction of ultraviolet irradiation, and as a result, the coating film 3 imparts less anisotropy.

Used in the second aspect of the present embodiment, a liquid crystal alignment film using a photo-isomerizable group or a side chain type polymer having a structure of a light fris rearrangement group represented by the above formula (18), step [II] When the ultraviolet irradiation amount is set in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Therefore, as shown in FIG. 3(b), among the side chains 6 arranged in parallel to the polarization direction of ultraviolet rays, the photosensitive group of the side chain 6a having a photosensitive group preferentially generates a photoreaction such as photo-fresh rearrangement. As a result, the density of the side chain 6a undergoing photoreaction slightly increased in the polarized direction of ultraviolet irradiation, and as a result, the coating film 5 Gives very little anisotropy.

Used in the second aspect of the present embodiment, a side chain type polymer coating film having a structure of photofresh rearrangement groups shown in the above formula (19) is used, and the amount of ultraviolet irradiation in step [II] is △A When it is set within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. Therefore, as shown in FIG. 4(b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in parallel to the polarization direction of the ultraviolet rays preferentially generates photoreactions such as photo-Freis rearrangement. As a result, the density of the side chain 8a that undergoes photoreaction becomes higher in the polarization direction of ultraviolet irradiation, and as a result, a small anisotropy is imparted to the coating film 7.

Next, in the first aspect of the present embodiment, when the ultraviolet irradiation amount in the [II] step is within a range of 1% to 15% of the maximum ultraviolet irradiation amount of ΔA, the coating film 1 after polarized light irradiation is heated to make It becomes the liquid crystal state. Thus, as shown in FIG. 1(c), in the coating film 1, the amount of cross-linking reaction generated differs between the parallel direction and the perpendicular direction to the polarization direction irradiated with ultraviolet rays. At this time, the amount of cross-linking reaction generated in the polarized direction and the parallel direction of ultraviolet irradiation is very small, so the cross-linking reaction site can be used as a plasticizer. Therefore, the liquid crystallinity in a direction perpendicular to the polarization direction of ultraviolet irradiation is higher than the liquid crystallinity in the parallel direction. In the direction parallel to the polarization direction of ultraviolet irradiation, the self-organized side chain 2 containing mesogenic components will Reorientation. As a result, the very small anisotropy of the coating film 1 caused by the photocrosslinking reaction is increased by heat, and the coating film 1 is given greater anisotropy.

Similarly, in the first form of this embodiment, the step [II] When the ultraviolet irradiation amount is set within the range of 15% to 70% of the maximum ultraviolet irradiation amount, the coating film 3 after polarized light irradiation is heated to bring it into a liquid crystal state. Then, as shown in FIG. 2(c), the amount of crosslinking reaction generated in the side chain type polymer film 3 is different between the parallel direction and the vertical direction parallel to the polarization direction of ultraviolet irradiation. Therefore, it is self-organized in a direction parallel to the polarized light direction irradiated with ultraviolet rays, and the side chain 4 containing the mesogen component is reoriented. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is increased by heat, and a large anisotropy is imparted to the coating film 3.

Similarly, it is used in the second aspect of the present embodiment, using a coating film of a side chain type polymer having a structure of a photo-reis rearrangement group represented by the above formula (18), [II] When the ultraviolet irradiation amount in the step is set within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 5 after the heating polarized light irradiation becomes a liquid crystal state. Thus, as shown in FIG. 3(c), in the coating film 5, the amount of light Fries rearrangement reaction differs between the parallel direction and the perpendicular direction to the polarization direction of the ultraviolet irradiation. At this time, the polarizing direction of the ultraviolet irradiation and the vertical direction produce light. The liquid crystal alignment force of the Fries rearrangement is stronger than that of the side chain before the reaction, so it is perpendicular to the polarization direction of the ultraviolet irradiation. On the self-organization, the side chain 6 containing mesogen component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photofresh rearrangement reaction is increased by heat, and a large anisotropy is imparted to the coating film 5.

Similarly, it is used in the second aspect of the present embodiment, using a coating film of a side chain type polymer having a structure of a photo-Frys rearrangement group represented by the above formula (19), and the ultraviolet irradiation amount in the [II] step is △ A is set to maximum In the range of 1% to 70% of the ultraviolet irradiation amount, the coating film 7 after heating polarized light irradiation becomes a liquid crystal state. Therefore, as shown in FIG. 4(c), in the side-chain type polymer film 7, the amount of light Fries rearrangement reaction generated is different between the parallel direction and the perpendicular direction to the polarization direction of ultraviolet irradiation. The anchoring force of the optical fris rearrangement 8(a) is stronger than that of the side chain 8 before transposition. Therefore, if a certain amount of optical fris rearrangement is generated to a certain degree or more, the direction of polarization with ultraviolet radiation It is self-organized in a parallel direction, and the side chain 8 containing mesogen is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photofresh rearrangement reaction is increased by heat, and a large anisotropy is imparted to the coating film 7.

Therefore, the coating film used in the method of the present invention can be efficiently introduced into the anisotropy by sequentially irradiating the coating film with polarized ultraviolet rays and heating, making it a liquid crystal alignment with excellent alignment control performance membrane.

Therefore, in the coating film used in the method of the present invention, the amount of polarized ultraviolet light irradiation to the coating film and the heating temperature in the heating process are optimized. Thereby, the anisotropic introduction of the coating film can be realized with high efficiency.

The optimal amount of polarized ultraviolet radiation used for the highly efficient anisotropic introduction of the coating film used in the present invention corresponds to the photosensitive film undergoing a photocrosslinking reaction or a photoisomerization reaction, or a photofray in the coating film. The amount of Sri Lankan rearrangement reaction is optimized by the amount of polarized ultraviolet radiation. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, if the photo-crosslinking reaction, photo-isomerization reaction, or photo-freis rearrangement reaction has fewer side chains, it will not Become a sufficient amount of light reaction. At this time, even if its After heating, it will not fully organize itself. On the other hand, in the coating film used in the present invention, for the structure having a photo-crosslinkable group, as a result of irradiating polarized ultraviolet rays, the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive, causing The cross-linking reaction between the side chains is excessive. At this time, the resulting film becomes rigid and becomes an obstacle to the progress of self-organization by subsequent heating. In addition, in the coating film used in the present invention, the structure having the photo-fresh rearrangement group is irradiated with polarized ultraviolet rays. As a result, if the photo-fries rearrangement reaction is carried out, the photosensitive group of the side chain becomes excessive. , The liquid crystallinity of the coating film will be excessively reduced. At this time, the liquid crystallinity of the resulting film also decreases, which becomes an obstacle to the progress of self-organization by subsequent heating. And for the structure with photo-Frys rearrangement group, when irradiated with polarized ultraviolet rays, if the amount of ultraviolet rays is too much, the side chain type polymer will be decomposed by light and become self-organized by subsequent heating. Obstacles.

Therefore, for the coating film used in the present invention, by the irradiation of polarized ultraviolet rays, the photosensitive group of the side chain undergoes a photo-crosslinking reaction or a photo-isomerization reaction, or an optimal amount of photo-Frys rearrangement reaction to have The photosensitive group of the side chain type polymer film has a molar ratio of 0.1 mol% to 40 mol%, preferably 0.1 mol% to 20 mol%. When the amount of the photosensitive group of the side chain undergoing the photoreaction is within such a range, subsequent self-organization of the heat treatment can be performed with high efficiency, and high-efficiency anisotropy in the film can be formed.

In the coating film used in the method of the present invention, the photo-crosslinking reaction or photo-isomerization of the photosensitive group in the side chain of the side chain type polymer film is optimized by optimizing the amount of polarized ultraviolet radiation Reaction, or photo fry The amount of Sri Lankan rearrangement reaction is optimized. Therefore, it is combined with the subsequent heat treatment to realize the efficient introduction of the anisotropy of the coating film used in the present invention. At this time, the amount of polarized ultraviolet light can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

That is, with respect to the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet and the ultraviolet absorption in the vertical direction after the irradiation of each polarized ultraviolet were measured. From the measurement result of ultraviolet absorption, ΔA of the difference between the ultraviolet absorbance of the coating film parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance of the vertical direction was evaluated. Therefore, for the coating film used in the present invention, the maximum value of ΔA (ΔAmax) to be achieved and the amount of polarized ultraviolet light to achieve this were obtained. In the manufacturing method of the present invention, the amount of polarized ultraviolet light that can be irradiated in the manufacture of the liquid crystal alignment film can be determined using the amount of polarized ultraviolet light irradiation that achieves this ΔAmax as a reference.

In the manufacturing method of the present invention, the amount of polarized ultraviolet light applied to the coating film of the present invention is preferably set within a range of 1% to 70% of the amount of polarized ultraviolet light to achieve ΔAmax, and is set at The range of 1%~50% is better. For the coating film used in the present invention, the irradiation amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light that achieves ΔAmax is equivalent to the total amount of photosensitive groups of the side chain type polymer film. 0.1 mol% to 20 mol% The amount of polarized ultraviolet light that undergoes the photocrosslinking reaction.

Based on the above, in the manufacturing method of the present invention, in order to achieve high-efficiency anisotropy of the coating film, the liquid of the side chain type polymer The crystal temperature range is used as a reference to determine the preferred heating temperature as described above. Therefore, for example, if the liquid crystal temperature range of the side chain polymer used in the present invention is 100°C to 200°C, the heating temperature after polarized ultraviolet irradiation is preferably set to 90°C to 190°C. With this, it is possible to impart greater anisotropy to the coating film used in the present invention.

As a result, the liquid crystal display device provided by the present invention exhibits high reliability against external pressure such as light or heat.

As described above, a substrate for a transverse electric field-driven liquid crystal display element manufactured by the method of the present invention or a transverse electric field-driven liquid crystal display element of the substrate has excellent reliability, and can be applied to a high-definition liquid crystal TV with a large screen, etc. .

The following examples illustrate the invention, but the invention is not limited to this example.

[Example]

The abbreviations used in the examples are shown below.

<methacrylic monomer>

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

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

MA3 (N-succinimide methacrylate) is manufactured by Tokyo Chemical Industry Co., Ltd.

MA9 (glycidyl methacrylate) and MA10 (hydroxybutyl acrylate glycidyl ether) indicate that they are commercially available.

<organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

<polymerization initiator>

AIBN: 2,2’-azobisisobutyronitrile

<Monomer Synthesis Example 1-1>

Synthesis of compound [MA4]

In a 500 mL four-necked flask, compound [B] (25.00 g, 142 mmol) and THF (180 g) were added, and the solution was cooled to 0°C while stirring under a nitrogen atmosphere, and then compound [A] (23.1 g, 149 mmol) The THF (20g) solution was dripped slowly while paying attention to the heat. After the end of instillation, return the reaction temperature to room temperature and The reaction was continued, and after the end of the reaction was confirmed by HPLC, the reaction solution was concentrated, and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain 45.9 g of compound [MA4] (yield 98%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 7.03 (2H, d), 6.85 (2H, d), 6.78 (1H, t), 6.56-6.54 (1H, m), 5.68-5.67 (1H, m), 4.11-4.09(2H,m), 3.62-3.59(2H,m), 3.43-3.41(4H,m), 2.20(3H,s),1.91-1.84(3H,m).

<Monomer Synthesis Example 1-2>

Synthesis of compound [MA5]

In a 300 mL four-necked flask, compound [C] (10.00 g, 43.4 mmol) and THF (60 g) were added, and after the solution was cooled to 0°C under stirring under a nitrogen atmosphere, compound [A] (7.07 g, 45.6 The solution of mmol) in THF (20g) was dripped slowly while paying attention to fever. After the end of the dropping, the reaction temperature was returned to room temperature and the reaction was continued. After the end of the reaction was confirmed by HPLC, the reaction solution was concentrated, and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain the compound [MA5 ] 15.3g (yield 92%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 7.51 (2H, d), 7.08 (2H, d), 6.82 (1H, t), 6.06-6.05 (1H, m), 5.67-5.62 (1H, m), 4.11(2H,t),3.46-3.44(4H,m),3.36-3.31(2H,m),3.31-3.24(4H,m),1.86(3H,s).

<Monomer Synthesis Example 1-3>

Synthesis of compound [MA6]

In a 500 mL four-necked flask, compound [D] (25.00 g, 139 mmol) and THF (160 g) were added, and the solution was cooled to 0°C under stirring under a nitrogen atmosphere, and then compound [A] (21.50 g, 138 mmol) The THF (40g) solution was dripped slowly while paying attention to its heat. After the end of the dropping, the reaction temperature was returned to room temperature and the reaction was continued. After the end of the reaction was confirmed by HPLC, the reaction solution was concentrated to obtain 46.5 g of compound [MA6] (yield 100%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 7.86-7.85(1H, m), 7.02-7.01(1H, m), 6.79(1H, t), 6.65-6.63(1H, m), 6.06- 6.02 (1H, m), 5.69-5.69 (1H, m), 4.10 (2H, t), 3.62-3.31 (10H, m), 1.88 (3H, s).

<Monomer Synthesis Example 1-4>

Synthesis of compound [MA7]

In a 500 mL four-necked flask, compound [E] (25.00 g, 136 mmol) and THF (160 g) were added, and the solution was cooled to 0°C while stirring under a nitrogen atmosphere, and then compound [A] (22.10 g, 142.5 mmol ) THF (40g) solution was slowly dropped while paying attention to heat. After the end of the dropping, the reaction temperature was returned to room temperature and the reaction was continued. After the end of the reaction was confirmed by HPLC, the reaction solution was concentrated, and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain compound [MA7 ] 42.9g (yield 93%).

¹ H-NMR (400MHz, DMSO-d6, δppm): 76.79-6.76 (1H, t), 6.06-6.05 (1H, m), 5.67-5.65 (1H, m), 4.67 (1H, t), 4.09 ( 2H, t), 3.80-3.22 (9H, m), 2.06-1.76 (10H, m).

<Monomer Synthesis Example 1-5>

Synthesis of compound [MA8]

In a 500 mL four-necked flask, compound [F] (30.00 g, 319 mmol) and THF (200 g) were added, and the solution was cooled to 0°C while stirring under a nitrogen atmosphere, and then compound [A] (51.92 g, 335 mmol) The THF (40g) solution was dripped slowly while paying attention to heat. After the end of the dropping, the reaction temperature was returned to room temperature and the reaction was continued. After the end of the reaction was confirmed by HPLC, the reaction solution was concentrated, and the precipitated solid was filtered and dried under reduced pressure at room temperature to obtain compound [MA8 ] 78.3g (yield 99%).

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.04 (1H, s), 8.30-8.28 (2H, m), 7.38-7.36 (2H, m), 6.54 (1H, t), 6.08-6.07 ( 1H, m), 5.71-5.70 (1H, m), 4.15 (2H, t), 3.43-3.39 (2H, m), 1.89 (3H, s).

<Polymethacrylic acid synthesis example 1>

After MA1 (1.99 g, 6.0 mmol) and MA2 (2.75 g, 9.0 mmol) were dissolved in THF (19.50 g) and degassed with a diaphragm pump, AIBN (0.12 g, 0.8 mmol) was added and degassed again. Thereafter, the reaction was carried out at 50°C for 18 hours to obtain a polymethacrylic acid solution. This polymer solution was dropped into methanol (500 ml), and the resulting precipitate was filtered. The precipitate was washed with isomethanol and dried under reduced pressure in a 40°C oven to obtain polymethacrylic acid powder.

NMP36.0g was added to the obtained powder 4.0g, and it stirred at room temperature for 3 hours. A polymethacrylic acid solution (M-1) having a solid content concentration of 10.0 wt% was obtained. At the end of stirring, the polymer was completely dissolved.

<Synthesis Example 2~11>

With the composition shown in Table 1, the polymer solutions of Synthesis Examples 2 to 11 were obtained by the same method as Synthesis Example 1. The polymethacrylic acid solution is 10.0 wt% of solid content in all NMP solvents.

<Examples 1 to 10 and Comparative Example 1>

The polymer solution and the solvent shown in Table 2 below were mixed to obtain a 6.0 wt% polymer solution.

<Examples 11 to 20 and Comparative Example 2>

The polymer solution and the solvent shown in Table 3 below were mixed to obtain a 6.0 wt% polymer solution.

<Examples 21 to 30 and Comparative Example 3>

The polymer solution and the solvent shown in Table 4 below were mixed to obtain a 6.0 wt% polymer solution.

[Fabrication of liquid crystal cell]

Using the liquid crystal aligning agent (A1) obtained in Example 1, the liquid crystal cell was manufactured by the procedure shown below. The substrate is a glass substrate having a size of 30 mm×40 mm and a thickness of 0.7 mm, and a comb-shaped pixel electrode formed by patterning an ITO film is used. The pixel electrode is a comb-like shape in which electrode elements having a zigzag shape with a curved central portion are arranged in plural. The width of each electrode element in the lateral direction is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrodes forming each pixel are The electrode elements having a curved zigzag shape in the center are arranged in plural, so the shape of each pixel is not rectangular, and is curved in the central portion in the same way as the electrode element, and has a shape similar to the bold zigzag. Each pixel is divided into upper and lower parts for the central curved part as a boundary, and has a first region on the upper side of the curved part and a second region on the lower side. When comparing the first region and the second region of each pixel, the formation direction of the electrode elements constituting these pixel electrodes becomes different. That is, when the orientation processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise direction) in the first area of the pixel, and in the second area of the pixel The electrode element of the pixel electrode is formed at an angle of -15° (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the liquid crystal rotating action (transverse electric field switch) in the substrate surface due to the voltage input between the pixel electrode and the counter electrode becomes opposite to each other Direction.

The liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the prepared substrate with the above electrode. Next, it was dried on a hot plate at 70°C for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, after irradiating 313 nm ultraviolet rays at 1 mJ/cm ² through a polarizing plate on the coating film surface, heating is performed on a 150°C hot plate for 10 minutes (primary firing), and the substrate cooled to room temperature is again at 150°C After heating the hot plate for 10 minutes (2 firings), a substrate with a liquid crystal alignment film was obtained. Similarly, the amount of ultraviolet radiation is 1mJ/cm ² ~10mJ/cm ² at 1mJ/cm ² intervals, 10mJ/cm ² ~100mJ/cm ² at 10mJ/cm ² intervals, and 100mJ/cm ² or more at 50mJ/ With cm ² interval, different substrates were made. In addition, for a glass substrate having a column spacer with a height of 4 μm where no electrode is formed as a counter substrate, a coating film is formed and an orientation treatment is applied in the same manner. A sealant (XN-1500T manufactured by Kyoritsu Chemical) was printed on the liquid crystal alignment film on one substrate. Next, after bonding the other substrate so as to face the liquid crystal alignment film surface with the alignment direction at 0°, the sealant is thermally hardened to produce cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the cells by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having an IPS (In-Planes Switching) mode liquid crystal display element.

Regarding the liquid crystal aligning agents (A2 to A33) obtained in Examples 2 to 30 and Comparative Examples 1 to 3, the liquid crystal cell was prepared by the same method as A1.

(Directional observation)

The liquid crystal cell is manufactured in the above-mentioned method. Thereafter, reorientation treatment was performed in an oven at 120°C for 60 minutes. After that, the polarizing plate was passed through a polarizing microscope in the state of Cross Nicol and observed.

Rotate the liquid crystal cell and display a black state without bright spots or poor alignment as a good condition. The irradiation dose of ultraviolet rays is as described above. The results of observing the orientation of the different substrates are shown in Table 5 and Table 6 for the balance of the irradiation dose with good orientation.

(Voltage retention rate (VHR) evaluation)

The evaluation of VHR is that in the obtained liquid crystal cell, a voltage of 5V is input for 60 μs at a temperature of 70° C. The electric power after 1667 ms is measured Voltage, and see how much the voltage is maintained as the voltage retention rate.

In addition, for the measurement of the voltage retention rate, a voltage retention rate measurement device VHR-1 manufactured by Toyo Teknika Corporation was used.

Using the liquid crystal aligning agent (B1) obtained in Comparative Example 1, a liquid crystal cell was manufactured in the same manner as in the case of using the above-mentioned liquid crystal aligning agent (A1), and VHR was evaluated in the same manner.

As shown in Tables 5, 6, and 7, according to Examples 1 to 30 of the present invention, under the common (A) component, Comparative Example 1 with no (B) component Under the comparison of 2, 3, it is judged that the voltage retention rate (VHR) becomes higher.

Claims (17)

A polymer composition characterized by containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity at a temperature range of 100°C to 300°C, and (B) having a side chain represented by the following formula (b) The polymer:

[In formula (b), A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or 1 to 12 carbon atoms Alkyl extension, hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH =CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other; P and Q are each independently selected from a divalent benzene ring, naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbon atoms, and groups formed by these combinations; however, X is -CH=CH-CO-O-, -O-CO When -CH=CH-, the P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer from 0 to 2; l3 is 0 or 1; l1 and 12 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; the dotted line indicates that the bond can be a single bond or a double bond; b ¹ and b ² each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and b ¹ and b ² together can form a cyclic or chain carbon 2 to 5 saturated or unsaturated divalent hydrocarbon group having 2 to 5 carbon atoms. The hydrocarbon group formed by b ¹ and b ² may be further substituted by the substituent b ³ , and b ³ represents the same or different ones selected from the group consisting of hydroxy, carboxy, nitro, cyano, halogen, alkyl and alkoxy. 1 or plural substituents] and (C) organic solvent. The polymer composition according to claim 1, wherein the aforementioned (A) component is one having a photosensitive side chain that can cause photocrosslinking, photoisomerization, or photofries rearrangement. The polymer composition according to claim 1 or 2, wherein the aforementioned (A) component and/or the aforementioned (B) component further have a side chain represented by the following formula (0);

[In the formula, A and B each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms , The hydrogen atoms bonded to these can be substituted with halogen groups; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH- CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or different from each other; P and Q are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl Base ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbon atoms, and groups formed by these combinations; however, X is -CH=CH-CO-O-, -O-CO-CH= When CH-, P or Q on the bonding side of -CH=CH- is an aromatic ring; l1 is 0 or 1; l2 is an integer of 0~2; when l1 and 12 are both 0, T is a single bond, A Also represents a single bond; when l1 is 1, when T is a single bond, B is also represented as a single bond; G is selected from the following formulas (G-1), (G-2), (G-3) and (G -4)

(In the formula, the dotted line represents a bonding bond, R ⁵⁰ represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a phenyl group. When R ⁵⁰ is a plural number, they may be the same or different from each other, and t represents 1 An integer of ~7, J represents O, S, NH, or NR ⁵¹ , and R ⁵¹ represents a group selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group)]. The polymer composition according to claim 1 or 2, wherein the aforementioned (A) component and/or the aforementioned (B) component may further have the following side chain (b-2), and the side chain (b-2) is selected From pyridyl, amide and carbamate groups. The polymer composition according to claim 1 or 2, wherein the component (A) has any photosensitive side chain selected from the group consisting of the following formulas (1) to (6); (wherein, A, B and D independently represent single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O- CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms bonded to these may be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms, bonded to These hydrogen atoms may be substituted with halogen groups; Y ₁ represents a ring selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or selected from The same or different 2 to 6 rings of these substituents are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently represented by -COOR ₀ (where R ₀ represents Hydrogen atom or alkyl group with 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or carbon Substituted by alkyloxy groups of 1 to 5; Y ₂ is selected from divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons of carbon number 5 to 8, and these combinations The groups in which the hydrogen atoms bonded to these groups are independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen groups, and alkyl groups with 1 to 5 carbon atoms , Or substituted by an alkyloxy group having 1 to 5 carbon atoms; R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ; X represents a single bond, -COO-, -OCO- , -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X can be Are the same or different; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these are independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy; one of q1 and q2 is 1, the other is 0; q3 is 0 or 1; P and Q are each independently selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and these combinations; but , 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 when the number of P becomes 2 or more, P can be the same or different from each other. When the number of Q becomes 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and 12 are both 0, T is A single bond, A also represents a single bond; l1 is 1, when T is a single bond, B is also represented as a single bond; H and I are independently selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan Ring, pyrrole ring, and the base of these combinations);

The polymer composition according to claim 1 or 2, wherein the component (A) can have any photosensitive side chain selected from the group consisting of the following formulas (7) to (10); (wherein, A, B and D independently represent single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O- CO-CH=CH-; Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or selected from these substituents The same or different 2 to 6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently -COOR ₀ (where R ₀ represents a hydrogen atom or carbon Alkyl group with 1 to 5), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, alkyl group with 1 to 5 carbons, or carbon number with 1 to 5 Substituted by an alkyloxy group; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X can be the same or different; 1 represents an integer of 1-12; m represents an integer of 0-2, m1, m2 represent 1~3 Integer; n represents an integer from 0 to 12 (but when n=0, B is a single bond); Y ₂ is selected from divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon number 5~ 8 alicyclic hydrocarbons, and the groups formed by these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen Substituted by a 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 );

The polymer composition according to claim 1 or 2, wherein the component (A) may have any photosensitive side chain selected from the group consisting of the following formulas (11) to (13); (wherein, each A independently represents Single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH- ; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH= When the number of CH-, X becomes 2, X may be the same or different from each other; l represents an integer of 1-12, m represents an integer of 0-2, m2 represents an integer of 1-3; R represents selected from monovalent benzene Rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbon rings having 5 to 8 carbon atoms, or 2 to 6 rings of the same or different ones selected from these substituents are bonded The bonding group B is a group for bonding, and the hydrogen atoms bonded to these may be independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN,- CH=C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group substituted, or represents hydroxy or C 1-6 Alkoxy);

The polymer composition according to claim 1 or 2, wherein the component (A) may have a photosensitive side chain represented by the following formula (14) or (15); (wherein, each A independently represents a single bond, -O- , -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y ₁ means selected from Monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon ring having 5 to 8 carbon atoms, or 2 to 6 rings selected from the same or different ones of these substituents A group formed by bonding through a bonding group B, and each hydrogen atom bonded to these can independently be -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy; X represents a single bond , -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, X When the number becomes 2, X may be the same or different from each other; l represents an integer from 1 to 12, m1, m2 represent an integer from 1 to 3);

The polymer composition according to claim 1 or 2, wherein the component (A) may have a photosensitive side chain represented by the following formula (16) or (17); (wherein, A represents a single bond, -O-,- CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; X represents a single bond, -COO -, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, the number of X becomes 2 , X may be the same or different from each other; l represents an integer of 1-12, m represents an integer of 0-2);

The polymer composition according to claim 1 or 2, wherein the component (A) has any photosensitive side chain selected from the group consisting of the following formula (18) or (19); (wherein, each of A and B Independent means single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH= CH-; Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from these substituents The difference is that 2 to 6 rings are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently -COOR ₀ (where R ₀ represents a hydrogen atom or a carbon number 1 to 5 Alkyl), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyl oxygen Substituted by a group; one of q1 and q2 is 1, the other is 0; l represents an integer from 1 to 12, m1, m2 represent an integer from 1 to 3; R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH =C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group);

The polymer composition according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (20); (wherein, A represents a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O-, or -O-CO-CH=CH-; Y ₁ represents selected from monovalent benzene ring, naphthalene Rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbon rings having 5 to 8 carbon atoms, or 2 to 6 rings of the same or different ones selected from these substituents via the bonding group B The group formed by bonding, the hydrogen atoms bonded to these can be independently -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH =C(CN) ₂ , -CH=CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy; X represents a single bond, -COO-,- OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X becomes 2, X They can be the same or different from each other; l represents an integer from 1 to 12, m represents an integer from 0 to 2);

The polymer composition according to claim 1 or 2, wherein the component (A) is any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31); (wherein, A and B have The same definition as above; Y ₃ is selected from the group consisting of monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and these combinations The hydrogen atoms bonded to these groups can be independently substituted by -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 alkyloxy groups; R ₃ represents 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 heterocyclic ring, carbon number 5-8 alicyclic hydrocarbons, C 1-12 alkyl groups, or C 1-12 alkoxy groups; one of q1 and q2 is 1, the other is 0; l represents an integer of 1-12, m represents an integer of 0 to 2, but in formulas (23) to (24), all m totals 2 or more, and for formulas (25) to (26), all m totals 1 or more, and m1, m2, and m3 each Independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5 to 8 alicyclic hydrocarbon, and, alkyl, or alkyloxy; Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -);

A method for manufacturing a substrate having a liquid crystal alignment film, characterized in that the liquid crystal alignment film is a liquid crystal alignment film for a transverse electric field driven liquid crystal display element endowed with orientation control energy obtained by the following steps; The step of coating the polymer composition of any one of 12 on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] the step of irradiating polarized ultraviolet rays on the coating film obtained with [I]; And [III] the step of heating the coating film obtained by [II]. A substrate characterized by having a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element manufactured by the method of claim 13. A horizontal electric field driving type liquid crystal display element characterized by having a substrate as in claim 14. A method for manufacturing a liquid crystal display device, characterized by having the following steps of obtaining a liquid crystal alignment film to which alignment control energy is provided, further obtaining a second substrate having the liquid crystal alignment film, and step [IV] to obtain a horizontal electric field driving type Liquid crystal display device; this step is the step of preparing the substrate (first substrate) as in claim 14; [I'] is formed by coating the polymer composition as in any one of claims 1 to 12 on the second substrate The step of coating the film; [II'] the step of irradiating the polarized ultraviolet light on the coating film obtained with [I']; and [III'] the step of heating the coating film obtained with [II']; [IV] The liquid crystal aligns the first and second substrates to the first The step of obtaining the liquid crystal display element by making the liquid crystal alignment films of the first and second substrates relative. A horizontal electric field driven liquid crystal display device manufactured by the method according to claim 16.

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