TW201923044A - Polymer composition and liquid crystal alignment film for liquid crystal display element using transverse electric field driving - Google Patents

Abstract

The invention provides a liquid crystal alignment film with excellent burn-in properties, to which an alignment control function has been imparted with high efficiency, an imparted polymer composition and a liquid crystal display element using transverse electric field driving. The present invention provides a polymer composition [I] that includes (A) a branched polymer and (B) an organic solvent, wherein (A) is a photosensitive branched polymer that exhibits crystallinity in a specific temperature range and has a side chain represented by formula (0), and further has a side chain (a) containing a group selected from the nitrogen-containing aromatic heterocyclic group, amide group, and urethane group. In formula (0), G is selected from the groups in formulae (G-1), (G-12), (G-3), and (G-4), wherein the dotted line represents a bonding bond, R50 represents hydrogen atom and so on, J represents O, S, HH or NR51, and R51 represents an alkyl group with carbon number 1~3, and so on. The invention also provides a method for producing a substrate that has a liquid crystal alignment film, which comprises the following steps: a step of forming a coating film by applying the composition to a substrate having a conductive film for driving a transverse electric field, a step of irradiating the obtained coating film with polarized UV rays, and a step of heating the obtained coating film.

Description

   Polymer composition and liquid crystal alignment film for lateral electric field drive type liquid crystal display element   

The present invention relates to a novel polymer composition, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element using the same, and a method for manufacturing a substrate having the same. Furthermore, a novel method for manufacturing a liquid crystal display element having excellent afterimage characteristics is provided.

Liquid crystal display elements are known as lightweight, thin, and low power consumption display devices, and have been used in large-scale display applications in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates including one of the electrodes. In addition, the liquid crystal display element uses an organic film made of an organic material as a liquid crystal alignment film so that the liquid crystal becomes a desired alignment state between the substrates.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the surface adjacent to the liquid crystal of the substrate holding the liquid crystal, and plays a role of aligning the liquid crystal alignment between the substrates in a certain direction. Furthermore, in addition to the role of the liquid crystal alignment film to align the liquid crystal in a certain direction, such as a direction parallel to the substrate, it is sometimes required to control the color of the pretilt angle of the liquid crystal. The ability to control liquid crystal alignment in such a liquid crystal alignment film (hereinafter referred to as alignment control ability) is imparted by performing an alignment treatment on an organic film constituting the liquid crystal alignment film.

A rubbing method has been known as an alignment processing method for a liquid crystal alignment film for imparting alignment control energy. The so-called rubbing method is to wipe (friction) the surface of an organic film such as polyvinyl alcohol, polyimide, or polyimide on a substrate with a cloth such as cotton, nylon, or polyester in a certain direction, so that the liquid crystal is wiped (friction) Direction). Since this rubbing method can realize the alignment state of liquid crystal simply and relatively stably, it has been used in the manufacturing process of conventional liquid crystal display elements. In addition, the organic film used for the liquid crystal alignment film is mainly a polyimide-based organic film having excellent reliability such as heat resistance or electrical characteristics.

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

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

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

The main photo-alignment method is known as a decomposition-type photo-alignment method. For example, the polyimide film is irradiated with polarized ultraviolet rays, and anisotropic decomposition is generated by the dependence of the polarized light direction of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is aligned by using polyimide remaining without being decomposed (see, for example, Patent Document 1).

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

As in the above example, the alignment processing method of the liquid crystal alignment film by the photo-alignment method does not require friction, and there is no concern of generating dust or static electricity. Moreover, even a substrate of a liquid crystal display element having an uneven surface can be subjected to an alignment treatment, and it becomes an alignment treatment method of a liquid crystal alignment film suitable for an industrial production process.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent No. 3893659

    [Non-patent literature]    

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

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

As described above, the photo-alignment method, as an alignment processing method for liquid crystal display elements, has a great advantage because it does not require a rubbing step as compared with the rubbing method used industrially in the past. Moreover, compared with a friction method that uses friction to make the liquid crystal control energy approximately constant, the light alignment method can change the amount of polarized light irradiation to control the alignment control energy. However, when the photo-alignment method achieves the same degree of alignment control performance as when the friction method is used, a large amount of polarized light irradiation is required, and stable liquid crystal alignment may not be achieved.

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

Therefore, in the photo-alignment method, it is required to achieve a high-efficiency or stable liquid crystal alignment of the alignment process, and a liquid crystal alignment film or a liquid crystal alignment agent capable of efficiently imparting a high alignment control ability to the liquid crystal alignment film is required.

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

In addition, the object of the present invention is to provide, in addition to the above objects, a lateral electric field drive type liquid crystal element having an improved voltage holding ratio and a liquid crystal alignment film for the element.

As a result of an intensive review conducted by the present inventors to achieve the above-mentioned problems, the following inventions were found.

<1> A polymer composition, [I] which contains (A) a side-chain type polymer and (B) an organic solvent, wherein (A) is a high-side-chain type that exhibits liquid crystallinity in a specific temperature range A molecule having a side chain represented by the following formula (0), and further having a side chain (a) having a group selected from a nitrogen-containing aromatic heterocyclic group, amidino group and a carbamate group,

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 the hydrogen atoms to which they are bonded may be substituted by halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms Group, and the hydrogen atoms to which they are bonded may be substituted by halo 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 is 2, X may be the same as or different from each other; P and Q are each independently a divalent benzene ring, naphthalene ring, Groups selected from the group consisting of biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbon atoms, and their combinations; however, X is -CH = CH-CO-O-, -O When -CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; l1 is 0 or 1, l2 is an integer from 0 to 2, when l1 and l2 are 0, T A is a single bond when it is a single bond; B is a single bond when l1 is 1, and T is a single bond; G is selected from the following formulae (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 plural, they may be the same as 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 an alkyl group having 1 to 3 carbon atoms and a phenyl group).

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

<3> In the above <1>, the component (A) has any one of the photosensitive side chains selected from the group consisting of the following formulae (1) to (6):

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

<4> In any one of the above <1> to <3>, the component (A) has a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms , And a group selected by a combination of these, and the hydrogen atoms to which they are bonded are each independently -NO ₂ , -CN, halo, alkyl having 1 to 5 carbons, or 1 to 5 carbons. 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, Benzene ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l represents an integer from 1 to 12, m represents an integer from 0 to 2, except that in formulas (25) to (26), the total of all m is 2 or more, and in formulas (27) to (28), the total of all m is 1 or more, m1, m2, and m3 each independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halo, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5 ~ 8 Alicyclic Hydrocarbons, and alkyl group, or an alkyl group; Z _1, Z ₂ represents a single _{bond, -CO -, - CH 2 O} -, - CH = N -, - CF 2 -.

<5> In any one of the above <1> to <4>, the composition further contains, as a component (D), a compound having an alkoxysilyl group and a urea structure substituted at the 1- and 3-positions.

<6> A method for manufacturing a substrate having the aforementioned liquid crystal alignment film, which comprises obtaining the liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control energy is given by having the following steps: [I] The step of applying the polymer composition of any of 1> to <5> on a substrate having a conductive film for driving a transverse electric field to form a coating film; [II] irradiating the coating film obtained in [I] with polarized light UV step; [III] step of heating the coating film obtained by [II].

<7> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by the manufacturing method of the above <6>.

<8> A lateral electric field drive type liquid crystal display device having the substrate as described in <7> above.

<9> A method for manufacturing a liquid crystal display element, which comprises obtaining a lateral electric field drive type liquid crystal display element by the following steps: a step of preparing a substrate (first substrate) as in the above <7>; obtaining a liquid crystal alignment film The step of the second substrate is to obtain a liquid crystal alignment film having an alignment control ability by the following steps: [I '] The polymer composition described in any one of the above <1> to <5> A step of applying a coating film on a second substrate to form a coating film; [II '] a step of irradiating polarized ultraviolet rays on the coating film obtained by [I']; and a step of heating the coating film obtained by [III '] [II'] And [IV] a step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other in such a manner that the liquid crystal alignment films of the first and second substrates face each other with the liquid crystal interposed therebetween.

<10> A lateral electric field drive type liquid crystal display device manufactured by the above <9>.

<11> A side chain polymer, as described in the above <1>.

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

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

In addition, according to the present invention, in addition to the above-mentioned effects, a lateral electric field drive type liquid crystal element capable of adsorbing ionic impurities in liquid crystals at the interface of the liquid crystal alignment film and having an improved voltage retention rate, and a liquid crystal alignment film used in the device can be provided.

As a result of intensive studies conducted by the present inventors, the following findings were obtained and the present invention has been completed.

The polymer composition used in the manufacturing method of the present invention has a photosensitive side chain polymer (hereinafter also referred to simply as a side chain polymer) capable of exhibiting liquid crystallinity, and the coating film obtained by using the aforementioned polymer composition has A film of a photosensitive side chain polymer exhibiting liquid crystallinity. This coating film was not subjected to rubbing treatment, but was subjected to alignment treatment by polarized light irradiation. In addition, after polarized light irradiation, the side chain polymer film is subjected to a step of heating to become a coating film (hereinafter also referred to as a liquid crystal alignment film) to which alignment control ability is given. At this time, the anisotropy exhibited only by polarized light irradiation becomes a driving force, so that the liquid crystal side chain polymer itself can be effectively realigned by self-organization. As a result, a highly efficient alignment process as a liquid crystal alignment film can be realized, and a liquid crystal alignment film to which a high alignment control ability is given can be obtained.

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

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

The method for manufacturing a substrate having a liquid crystal alignment film of the present invention has the following steps: [I] a step of coating a polymer composition on a substrate having a conductive film for driving a lateral electric field to form a coating film, the polymer composition The substance contains (A) and (B): (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a specific temperature range, and a chain detection type polymer further having a side chain represented by the above formula (0), (B) an organic solvent, [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet light; and [III] a step of heating the coating film obtained in [III].

Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that provides alignment control energy can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

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

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

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

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

    <Step [I]>    

Step [I] is to coat a polymer composition on a substrate having a conductive film for lateral electric field drive to form a coating film. The polymer composition contains a photosensitive side chain type that exhibits liquid crystallinity in a specific temperature range. A polymer, and further a side chain polymer having a side chain represented by the above formula (0), an organic solvent, and a first-order amine group and a nitrogen-containing aromatic heterocyclic ring if necessary in the molecule, and the above-mentioned 1 An amine compound having a secondary amine group bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and further containing an alkoxysilyl group and a urea structure substituted with 1- and 3-positions as the component (D) as necessary.

    <Substrate>    

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

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

    〈Conductive film for lateral electric field drive〉    

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

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

In the case of a reflective liquid crystal display device, the conductive film may be a material such as aluminum that can reflect light, but is not limited to these.

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

    <Polymer composition>    

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

The polymer composition used in the manufacturing method of the present invention contains (A) a photosensitive side-chain polymer exhibiting liquid crystallinity in a specific temperature range; (B) an organic solvent; and (C) in the molecule as necessary An amine compound having one primary amine group and a nitrogen-containing aromatic heterocyclic ring, and the aforementioned primary amine group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

    << (A) side chain polymer >>    

The component (A) is a photosensitive side-chain polymer that exhibits liquid crystallinity in a specific temperature range, has a side chain represented by the above formula (0), and further has a nitrogen-containing aromatic heterocyclic group and amidine. The side chain (a) of the group selected from the group consisting of an amino group and a urethane group.

(A) The side-chain polymer may be capable of reacting with light in a wavelength range of 250 nm to 400 nm and exhibiting liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

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

(A) The side chain polymer preferably has a mesogenic group for displaying liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

(A) The side chain polymer is a side chain having a photosensitive bond on the main chain, which can induce light to cause a crosslinking reaction, an isomerization reaction, or a photofurtes rearrangement. The structure of the photosensitive side chain is not particularly limited, but a structure that induces a cross-linking reaction or rearrangement of photophoris by induced light is preferable, and a cross-linking reaction is more preferable. In this case, even if exposed to external stress such as heat, the orientation control performance achieved can be stably maintained for a long time. The structure of the photosensitive side chain polymer film exhibiting liquid crystallinity is not particularly limited as long as it can satisfy the characteristics, but it is preferable to have a rigid mesogen component in the side chain structure. In this case, when the side chain polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

(A) A side chain polymer has a liquid crystal alignment film having a high reliability such as a voltage holding ratio (VHR) through having a base represented by the above formula (0). This reason is considered that when the liquid crystal alignment film is used, the group represented by the above formula (0) acts as a cross-linking agent to increase the film density and reduce the dissolution of ionic impurities into the liquid crystal.

In addition, (A) a side chain polymer having a side chain (a) having a group selected from a nitrogen-containing aromatic heterocyclic group, amidino group, and a urethane group can further improve the voltage holding ratio ( VHR). The reason is considered that these bases can trap ionic impurities.

The structure of the polymer may be, for example, a main chain and a side chain bonded thereto, and the side chain has biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, and azobenzene. Mesogenic components such as a base, and a photosensitive group bonded to the front end and inducing light to cause a crosslinking reaction or an isomerization reaction, or a structure having a main chain and a side chain bonded thereto, and The chain has a structure of a phenylbenzoate group which is also a mesogenic component and undergoes a photo-Furth rearrangement reaction.

More specific examples of the structure of the photosensitive side-chain polymer film exhibiting liquid crystallinity are preferably those having a hydrocarbon, (meth) acrylate, itaconic acid ester, fumaric acid ester, maleic acid ester, and α- A main chain composed of at least one selected from the group consisting of radical polymerizable groups such as methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and The structure of the side chain which consists of the base represented by said formula (0), and at least 1 sort (s) of following formula (1)-(6).

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

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

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

The side chain is preferably a photosensitive side chain selected from the group consisting of the following formulae (11) to (13).

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

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

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

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 described above.

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

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

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

The side chain 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 above.

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

In the formula, A, B, q1, and q2 have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and a lipid having 5 to 8 carbon atoms. Cyclic hydrocarbons, and groups selected from these groups, and the hydrogen atoms to which they are bonded are each independently -NO ₂ , -CN, halo, 1 to 5 carbon alkyl, or carbon 1 to 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene Ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; l represents 1 to 12 Integer, m represents an integer from 0 to 2, except that in formulas (25) to (26), the total of all m is 2 or more, and in formulas (27) to (28), the total of all m is 1 or more, m1 , M2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halo, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, And alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl groups or alkyloxy groups; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH = N-, -CF ₂ -.

    << Method for manufacturing photosensitive side chain polymer >>    

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

    [Monomer having a side chain represented by formula (0)]    

More specific examples of the monomer having a side chain represented by the aforementioned formula (0) are preferably those having a hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleate, α- A polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as methyl-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and The structure of the side chain represented by the above formula (0).

Specific examples of the monomer having an epoxy group among these monomers include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and allyl. Compounds such as glycidyl ether include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 3-vinyl-7-oxabicyclo [4.1. 0] heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

Specific examples of the monomer having a thiirane include, for example, those in which an epoxy structure of the above-mentioned monomer having an epoxy group is substituted with an episulfide structure.

Specific examples of the monomer having aziridine include those in which the epoxy structure of the monomer having an epoxy group is substituted with aziridine or 1-methylaziridine.

Examples of the monomer having an oxetanyl group include a (meth) acrylate having an oxetanyl group. Among these monomers, 3- (methacryloxymethyl) oxetane, 3- (acryloxymethyl) oxetane, and 3- (methacryloxymethyl) (Methyl) -3-ethyl-oxetane, 3- (propenyloxymethyl) -3-ethyl-oxetane, 3- (methacryloxymethyl)- 2-trifluoromethyloxetane, 3- (propenyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloxymethyl) -2- Phenyl-oxetane, 3- (propenyloxymethyl) -2-phenyl-oxetane, 2- (methacryloxymethyl) oxetane, 2 -(Propenyloxymethyl) oxetane, 2- (methacryloxymethyl) -4-trifluoromethyloxetane, 2- (propenyloxymethyl) 4-Trifluoromethyloxetane is preferred, and examples include 3- (methacryloxymethyl) -3-ethyl-oxetane, and 3- (propenyloxymethyl) ) -3-ethyl-oxetane.

The monomer having a thietane is preferably, for example, a monomer having an oxetanyl group substituted with a thietyl group.

The monomer having an azetane group is preferably a monomer in which an oxetanyl group of an oxetanyl group is substituted with an azetyl group.

Among the above, from the viewpoints of availability and the like, a monomer having an epoxy group and a monomer having an oxetanyl group are more preferable, and a monomer having an epoxy group is more preferable. Among these, from the viewpoint of availability, glycidyl (meth) acrylate is preferred.

    [Monomer having side chain (a)]    

The polymer of the component (A) of the present application further has a side chain (a) having a group selected from a nitrogen-containing aromatic heterocyclic group, a fluorenyl group, and a urethane group. By containing this side chain (a), when it becomes a liquid crystal alignment film, the dissolution of ionic impurities can be reduced, and at the same time, the crosslinking reaction of the base represented by the formula (0) can be promoted, or a more durable liquid crystal alignment can be obtained. membrane. In the production of a polymer having a side chain (a), a monomer having a side chain (a) may be copolymerized.

The monomer having a side chain (a) preferably has a hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleate, α-methylene-γ-butyrolactone Polymerizable group consisting of at least one selected from the group consisting of radical polymerizable groups such as styrene, vinyl, maleimide, norbornene, and silane, and having a nitrogen-containing aromatic heterocyclic group The structure of the side chains of sulfonylamino and urethane groups. The ammonium and carbamate-based NH may also be substituted. Examples of the substituent which may be substituted include an alkyl group, an amino group protecting group, and a benzyl group.

The nitrogen-containing aromatic heterocyclic ring preferably contains at least one, preferably one to four, from the following formulas [20a], [20b], and [20c] (wherein Z ₂ is a carbon number of 1 to An aromatic cyclic hydrocarbon selected from the group consisting of a linear or branched alkyl group of 5).

Specific examples include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, and a purine ring. , Thiadiazole ring, pyrazine ring, pyrazoline ring, triazine ring, pyrazidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, perylene ring, phenanthroline ring, Indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocyclic rings may have a hetero atom-containing substituent.

Among these, for example, a pyridine ring is preferred.

Specific examples of the monomers having a nitrogen-containing aromatic heterocyclic group include 2- (2-pyridylcarbonyloxy) ethyl (meth) acrylate and 2- (3- Pyridylcarbonyloxy) ethyl, 2- (4-pyridylcarbonyloxy) ethyl (meth) acrylate, and the like.

Specific examples of the monomer having a sulfonylamino group or a urethane group include, for example, 2- (4-methylpiperidin-1-ylcarbonylamino) ethyl (meth) acrylate, 4- (6-methyl Acrylic acid oxyhexyloxy) benzoic acid N- (third butyloxycarbonyl) piperidin-4-yl ester, 4- (6-methacrylic acid oxyhexyloxy) benzoic acid 2- (third butyl Ethoxycarbonylamino) ethyl and the like.

    [Photoreactive side chain monomer]    

When a photoreactive side chain monomer is used to form a polymer, it is a monomer that can form a polymer having a photosensitive side chain in a side chain portion of the polymer.

The photoreactive group having a side chain preferably has the following structure and its derivative.

More specific examples of the photoreactive side chain monomer are preferably those having a hydrocarbon, (meth) acrylate, itaconic acid ester, fumaric acid ester, maleic acid ester, α-methylene-γ-butane A polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as esters, styrene, vinyl, maleimide, norbornene, and siloxane, and the formula (1) ~ The photosensitive side chain formed by at least one of (6) is preferably, for example, a photosensitive side chain formed by at least one of the above-mentioned formulas (7) to (10), and a photosensitive side chain formed by the above-mentioned formulas (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 The structure of the photosensitive side chain represented by (18) or (19), and the photosensitive side chain represented by the said Formula (20).

The present application provides novel compounds (1) to (11) represented by the following formulae (1) to (11) as photoreactive side chain monomers.

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

    [Liquid crystal side chain monomer]    

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

The mesogenic group on the side chain may be a group that becomes a mesogenic structure alone, such as biphenyl or phenyl phenyl benzoate, or a group that makes the side chains hydrogen-bond to a mesogenic structure, such as benzoic acid. The mesogenic group in the side chain preferably has the following structure.

More specific examples of the liquid crystalline side chain monomer are preferably those selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, and α-methylene-γ-butane. A polymerizable group composed of at least one selected from the group consisting of radical polymerizable groups such as lactone, styrene, vinyl, maleimide, norbornene, and siloxane, and the group consisting of the above formula (21) ~ (31) The structure of at least one side chain formed.

(A) The side chain polymer can be a combination of the photoreactive side chain monomer exhibiting liquid crystallinity, the monomer having a side chain represented by the aforementioned formula (0), and the monomer having a side chain (a). Obtained from polymerization. In addition, a photoreactive side chain monomer and a liquid crystal side chain monomer which do not exhibit liquid crystallinity, a monomer having a side chain represented by the aforementioned formula (0), and a monomer having a side chain (a) can be used. Copolymerization or coexistence of a photoreactive side chain monomer and a liquid crystal side chain monomer exhibiting liquid crystallinity, and a monomer having a side chain represented by the aforementioned formula (0) and a monomer having a side chain (a) Aggregated. Furthermore, it can be copolymerized with other monomers within a range that does not impair liquid crystal display performance.

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

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

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

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

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

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 maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The content of the side chain represented by the formula (0) in the side chain polymer of the present invention is preferably from 0.1 mol% to 20 mol% from the viewpoint of improving the reliability and the influence on the alignment of the liquid crystal. It is preferably 0.5 mol% to 10 mol%, and even more preferably 1 mol% to 5 mol%.

The content of the photoreactive side chain in the side chain polymer of the present invention is preferably from 20 mol% to 99.9 mol%, more preferably from 30 mol% to 95 mol%, from the viewpoint of good liquid crystal alignment. , And more preferably 40 mol% to 90 mol%.

The content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 80 mol% or less, more preferably 10 mol% to 70 mol%, and more preferably from the viewpoint of good liquid crystal alignment. 20 mol% to 60 mol%.

The content of the side chain (a) in the side chain polymer of the present invention is preferably 20 mol% or less, and more preferably 10 mol% or less, from the viewpoint of improving the reliability and the influence on the alignment of the liquid crystal. , And more preferably 5 mol% or less.

The side chain polymer of the present invention may contain a side chain other than the side chain represented by the formula (0), the photoreactive side chain, the liquid crystal side chain, and the side chain (a). When the content of the side chain, the photoreactive side chain, the liquid crystal side chain, and the side chain (a) represented by the above formula (0) is less than 100%, it is the remainder thereof.

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

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

A radical thermal polymerization initiator is a compound that generates a radical by heating above a decomposition temperature. Examples of the radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like), and difluorenyl peroxides (ethyl fluorenyl peroxide, Benzamyl peroxide, etc.), hydrogen peroxide (hydrogen peroxide, third butyl hydrogen peroxide, cumene hydrogen peroxide, etc.), dialkyl hydrogen peroxide (di-third butyl) Peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxy Tertiary butyl neodecanoate, tertiary butyl peroxypivalate, tertiary pentyl 2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, persulfate Ammonium sulfate, etc.), azo compounds (azobisisobutylimide, and 2,2'-bis (2-hydroxyethyl) azobisisobutylimide, etc.). This radical thermal polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The radical photopolymerization initiator is not particularly limited as long as the compound that initiates radical polymerization is irradiated with light. Examples of the radical photopolymerization initiator include benzophenone, Michael's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl Xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4'- Cumene acetone, 1-hydroxycyclohexylphenyl ketone, cumene benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy 2-Phenylacetophenone, Camphorquinone, Benzanthrone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopropyl Amyl ester, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4,4'-tri (third butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzylidene diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( 3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl)- 4,6-double (three (Chloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxy Styryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) ) -S-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole , 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-(4-ethoxycarbonylphenyl) -1,2'-bi Imidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2- Methyl-2-morpholinylpropanyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2, 4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra ( Third butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetrakis (thirdhexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4'-bis (methoxycarbonyl) -4,3'-bis (third butylperoxycarbonyl) Benzophenone, 4,4'-bis (methoxycarbonyl) -3,3'-bis (third butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzo Thiazol-2-ylidene) -1-naphthalene-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -ylidene) -1- (2- Benzamidine) ethyl ketone and the like. These compounds may be used alone or in combination of two or more.

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

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

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone Phenylamine, dimethylsulfenyl, tetramethylurea, pyridine, dimethylphosphonium, hexamethylphosphonium, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Pentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl lysinolysin, ethyl lysinolysin, methyl lysone acetic acid Ester, ethylcelluinoacetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether Ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoethyl ether Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Alcohol 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, propylene carbonate , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methyl Butyl oxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropaneamide, 3-ethoxy -N, N-dimethylpropaneamide, 3-butoxy-N, N-dimethylpropaneamide, and the like.

These organic solvents may be used alone or in combination. In addition, even if it is a solvent which does not dissolve the produced polymer, it can be mixed with the above-mentioned organic solvent and used within the range which does not precipitate the produced polymer.

In addition, since the oxygen in the organic solvent in the radical polymerization is a cause of hindering the polymerization reaction, it is preferred to use an organic solvent that is degassed to a degree capable of radical polymerization.

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

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator to the monomer is large, the molecular weight of the obtained polymer becomes small, and when the ratio is small, the molecular weight of the obtained polymer becomes large. The ratio is preferably 0.1 mol% to 10 mol% with respect to the monomer being polymerized. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

    [Recycling of polymers]    

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

When the molecular weight of the (A) side chain polymer of the present invention takes into consideration the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film, the weight average measured by GPC (gel permeation chromatography) method The molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

    [Modulation of polymer composition]    

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

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

Such other polymers include, for example, polymers made of poly (meth) acrylate, polyamic acid, polyimide, or the like, which are not photosensitive side-chain polymers that exhibit liquid crystallinity.

    <(C) Amine Compound>    

The polymer composition used in the present invention may have a specific amine compound as the component (C), specifically, a primary amine group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amine group may be bonded. Amine compounds for aliphatic or non-aromatic cyclic hydrocarbon groups. This compound is described as (B) component in WO2008 / 013285. By containing the amine compound, when used as a liquid crystal alignment film, the elution of ionic impurities can be reduced, and the crosslinking reaction of the base represented by the formula (0) can be promoted, or a liquid crystal alignment film having higher durability can be obtained.

The specific amine compound is not particularly limited as long as the polymer composition used in the present invention can exhibit the following effects i) and / or ii) when forming a liquid crystal alignment film. i) the ionic impurities in the liquid crystal are adsorbed at the interface of the liquid crystal alignment film, and / or ii) the enhanced electronic pressure retention rate is exerted.

The amount of the specific amine compound is not particularly limited as long as the above-mentioned effects can be exhibited, but it is 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass in 100 parts by mass of the polymer composition used in the present invention.

    〈(D) component〉    

The component (D) contained in the liquid crystal alignment agent of the present invention is a compound having an alkoxysilyl group, a urea structure substituted at the 1-position and the 3-position (hereinafter also referred to as a compound D).

The aforementioned compound may be a compound having one or more alkoxysilyl groups and one or more urea structures substituted at the 1 and 3 positions. Other structures are not particularly limited, but from the viewpoint of availability, A preferred example is a compound represented by the following formula (d).

In the formula, X ¹⁰² is an n-valent organic group containing an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, n is an integer of 1 to 6, R ¹⁰² represents a hydrogen atom or an alkyl group, and n is 2 or more , the other R ¹⁰² and R ¹⁰² together are alkylene, or n is from 6:01 to by also bonded to X ^102, X ¹⁰² and together form a ring structure, L represents 2 to 20 carbon atoms, alkyl of extension, R ¹⁰³ and R ^{104 are} each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, and q represents a natural number of 1 to 3.

R ¹⁰³ and R ¹⁰⁴ in formula (d) are each independently listed as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and second butyl. The viewpoint of sex is preferably methyl or ethyl.

L in the formula (d) is exemplified by an alkylene group having 2 to 20 carbon atoms. From the viewpoint of raw material availability, trimethylene is preferred.

In the formula (d), q is preferably 2 or 3, and most preferably 3.

N in the formula (d) is preferably 1, 2 or 3, and most preferably 1 or 2.

The compound (D) is the compound (2-1) in which X ¹⁰² is a divalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene group.

The compound represented by the formula (2-1) is obtained by reacting a diamine with 2.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-1) is preferably a structure selected from the following structural formula.

(D) The homomorphic system of the compound of the component X ¹⁰² is a divalent organic group, R ¹⁰² forms an alkylene group with each other, and L is a trimethylene compound (2-2).

The compound represented by the formula (2-2) as described above is obtained by reacting a cyclic compound containing two NHs with 2.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-2) is preferably a structure selected from the following structural formula. For convenience, it will be described as including a nitrogen atom in a ring.

(D) The isomorphism of the compound of the component X ¹⁰² is a divalent organic group, one of R ¹⁰² is a hydrogen atom, the other is a compound bonded to X ¹⁰² to form a ring, and L is a trimethylene compound (2-3 ).

The compound represented by the formula (2-3) is obtained by reacting a diamine with 2.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-3) is preferably a structure selected from the following structural formula. For convenience, it will be described as including a nitrogen atom in a ring.

(D) The isomorphism of the compound of the component X ¹⁰² is a trivalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene compound (2-4).

The compound represented by the formula (2-4) is obtained by reacting a triamine compound with 3.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-4) is preferably a structure selected from the following structural formula.

(D) The homomorphic system of the compound of the component X ¹⁰² is a monovalent organic group, R ¹⁰² is a hydrogen atom, and L is a trimethylene compound (2-5).

The compound represented by the formula (2-5) is obtained by reacting a monoamine with 1.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-5) is preferably a structure selected from the following structural formula.

(D) The isomorphism of the compound of the component X ¹⁰² is a monovalent organic group, R ¹⁰² and X ^{102 are} bonded to form a ring, and L is a trimethylene compound (2-6).

The compound represented by the formula (2-6) is obtained by reacting a cyclic compound containing one NH with 1.05 equivalents of a trialkoxysilylpropyl isocyanate.

X in the compound represented by formula (2-6) is preferably a structure selected from the following structural formula. For convenience, it will be described as including a nitrogen atom in a ring.

In addition, in the reaction between the amine and the isocyanate, the amount of the isocyanate compound used is only 0.98 equivalent times to 1.2 equivalent times relative to one group of the NH or NH ₂ group. More preferably, it is 1.0 equivalent to 1.05 equivalent.

The reaction solvent is not particularly limited as long as it is inert to the reaction. Examples include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; and halogenated hydrocarbons such as carbon tetrachloride, chloroform, and 1,2-dichloroethane. ; Ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile, propionitrile Carboxylic acid esters such as ethyl acetate and ethyl propionate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, Nitrogen-containing aprotic polar solvents such as 3-dimethyl-2-imidazolidone; Sulfur-containing aprotic polar solvents such as dimethylsulfinium and cyclobutane; pyridines such as pyridine and methylpyridine. These solvents can be used alone or in combination of two or more. Toluene, acetonitrile, ethyl acetate, and tetrahydrofuran are preferred, and acetonitrile and tetrahydrofuran are more preferred.

The use amount (reaction concentration) of the solvent is not particularly limited, but the reaction can also be performed without using a solvent, and when using a solvent, a solvent of 0.1 to 100 mass times with respect to the isocyanate compound can also be used. It is preferably 0.5 to 30 times the mass, more preferably 1 to 10 times the mass.

The reaction temperature is not particularly limited, but is, for example, -90 to 150 ° C, preferably -30 to 100 ° C, and more preferably 0 ° C to 80 ° C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

A catalyst can also be added to shorten the reaction time. Examples include dibutyltin dilaurate, dioctyltin bis (isooctylthioglycolate), and dibutyltin bis (isooctylthioglycolate). Organotin compounds, such as dibutyltin, dibutyltin diacetate; triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, N, N-dimethylcyclohexylamine , Pyridine, tetramethylbutanediamine, N-methylmorpholine, 1,4-diazabicyclo-2,2,2-octane, 1,8-diazabicyclo [5.4.0]- 7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and other amines; p-toluenesulfonic acid, methanesulfonic acid, fluorosulfuric acid and other organic sulfonic acids; sulfuric acid, phosphoric acid, persulfate Inorganic acids such as chloric acid; titanium compounds such as tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate; bismuth compounds such as bismuth (2-ethylhexanoate); and quaternary ammonium salts. These catalysts can be used alone or in combination of two or more. These catalysts are preferably liquid or those dissolved in a reaction solvent.

When adding the catalyst, the catalyst can be used in an amount of 0.005wt% to 100wt% relative to the total amount (mass) of the compound having an isocyanate group, preferably 0.5wt% to 10wt%, more preferably 0.1wt% ~ 5wt%. If an organic tin compound, a titanium compound, or a bismuth compound is used as the catalyst, it is preferably 0.005 wt% to 0.1 wt%.

This reaction can be carried out under normal pressure or pressure, and can be either batch or continuous.

Specific examples of the preferable (D) component include compounds represented by any of S1 to S4.

(D) When there are too many compounds of a component, liquid crystal orientation or a pretilt angle are affected, and when there are too few, the effect of this invention cannot be acquired. Therefore, the addition amount of the compound of the component (D) is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass relative to the polymer of the component (A).

    <Organic solvents>    

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples are listed below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N- Ethylpyrrolidone, N-vinylpyrrolidone, dimethyl fluorene, tetramethylurea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, 3-methoxy- N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-bis Methyl-imidazolinone, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, carbonate Propyl ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol third butyl ether, dipropylene glycol monomethyl ether, Diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol 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, tripropyl Glycol methyl ether and the like. 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) described above. Examples include solvents or compounds that improve film thickness uniformity or surface smoothness when coating a polymer composition, compounds that improve adhesion between a liquid crystal alignment film and a substrate, and the like, but are not limited thereto.

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

For example, isopropanol, methoxymethylpentanol, methyl lysin, ethyl lysin, butyl lysin, methyl lysin acetate, ethyl lysin acetate, butyl 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 third butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropylene Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether , Diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n- Octane, diethyl ether, milk Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methyl Butyloxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2 -Ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other organic solvents having low surface tension.

These weak solvents may be used singly or in combination. When using the above-mentioned solvent, it is preferred to be 5 to 80% by mass of the entire solvent, and more preferably 20 to 60% by mass so that the solubility of the entire solvent contained in the polymer composition is not significantly reduced. quality%.

Examples of compounds that improve the uniformity of the film thickness or the surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, and non-ionic surfactants.

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

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and the like shown below.

Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureido Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 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, acetic acid 9-trimethoxysilyl-3,6-diazanonyl ester, acetic acid 9 -Triethoxysilyl-3,6-diazanonyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethyl) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) Group) -3-aminopropyltriethoxysilane and the like.

Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, in order to prevent the decrease in electrical characteristics caused by the backlight when constituting a liquid crystal display element, the polymer composition may contain the following phenoplast-based or Additives for epoxy-containing compounds. Although a specific phenolic plastic additive is shown below, it is not limited to this structure.

Specific epoxy-containing compounds are exemplified by ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetrakis Glycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino) (Methyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

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

A photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred.

Photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, and carbonyl Dicoumarin, aromatic 2-hydroxy ketone, and aromatic 2-hydroxy ketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxydi Benzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethylene-3-methyl-β-naphthothiazoline, 2- (β-naphthylmethylene) -3-methylbenzothiazoline, 2- (α-naphthylmethylene) -3-methylbenzothiazoline, 2- (4-biphenolyl Methylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylene) -3-methyl-β-naphthylthiazoline, 2- (4-biphenolylmethylene) 3-methyl-β-naphthylthiazoline, 2- (p-fluorobenzylidenemethylene) -3-methyl-β-naphthylthiazoline), oxazoline (2-benzidine Methylidene-3-methyl-β-naphthyloxazoline, 2- (β-naphthylmethylene) -3-methylbenzoxazoline, 2- (α-naphthylmethylidene) (Methyl) -3-methylbenzooxazoline, 2- (4-biphenoxymethylene) -3-methylbenzooxazoline, 2- (β-naphthylmethylene) -3-methyl- -Naphthoxazoline, 2- (4-biphenoxymethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylidenemethylene) -3- Methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitrofluorene (5-nitrofluorene) ), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzamidine alkyl ether, N-alkylated phthalone, acetophenone ketal ( 2,2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopyran, azoindole Pyridine, furanocoumarin, etc.

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

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

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

The coating method is generally industrially performed by screen printing, lithography, flexographic printing, or inkjet. As for 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, and these can be used depending on the purpose.

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

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

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

    <Step (II)>    

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

The amount of polarized ultraviolet radiation is related to the coating film used. The amount of irradiation is preferably the amount of polarized ultraviolet rays in the coating film that achieves the difference between the ultraviolet absorbance in a direction parallel to the polarized ultraviolet rays and the ultraviolet absorbance in the vertical direction, that is, the maximum value of ΔA (hereinafter also referred to as △ Amax) Within the range of 1% to 70%, and more preferably within the range of 1% to 50%.

    <Step [III]>    

Step [III] is a coating film heated in step [II] by polarized ultraviolet light irradiation. By heating, an alignment control ability can be given to a coating film.

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

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

The liquid crystal display temperature refers to a glass transition temperature (Tg) or higher when the side chain polymer or the surface of the coating film is transferred from the solid phase to the liquid phase, which causes the liquid crystal phase to transfer to the isotropic phase ( Isotropic phase) The temperature below the isotropic phase transfer temperature (Tiso).

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

By having the above steps, the manufacturing method of the present invention can efficiently achieve anisotropic introduction of a coating film. Furthermore, a substrate with a liquid crystal alignment film can be manufactured efficiently.

    <Step [IV]>    

[IV] Step is to have the liquid crystal alignment film substrate (first substrate) on the conductive film for lateral electric field driving obtained in [III], and the same as those obtained in [I '] to [III'] above. A liquid crystal alignment film substrate (second substrate) with a conductive film is arranged so that the two liquid crystal alignment films face each other across the liquid crystal, and a liquid crystal cell is produced by a conventional method, and a lateral electric field-driven liquid crystal display element is produced. The steps. In addition, steps [I '] to [III'] are the same as step [I] except that in step [I], a substrate without the conductive film for lateral electric field drive is used instead of a substrate with a conductive film for lateral electric field drive. ] ~ [III] Do the same. Since the difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the above-mentioned conductive film, the description of steps [I '] to [III'] is omitted.

As an example of the production of a liquid crystal cell or a liquid crystal display element, the above-mentioned first and second substrates are prepared, and the spacers are dispersed on a liquid crystal alignment film of a substrate so that the liquid crystal alignment film surface becomes the inner side, and the other is bonded. A method of injecting liquid crystal into a substrate under reduced pressure and sealing, or a method of attaching a substrate and sealing after dropping liquid crystal on a liquid crystal alignment film surface on which a spacer is dispersed. At this time, as the one-sided substrate, a substrate having an electrode having a comb-like structure for driving a lateral electric field is preferably used. The diameter of the spacer at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer will determine the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The method for manufacturing a substrate with a coating film of the present invention is to apply a polymer composition on a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, by applying heating, anisotropy can be efficiently introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having an alignment control function for liquid crystals is manufactured.

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

Therefore, in the coating film used in the method of the present invention, by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment, a liquid crystal alignment film with high anisotropy introduction and excellent alignment control can be produced.

Furthermore, for the coating film used in the method of the present invention, the amount of polarized ultraviolet radiation to the coating film and the heating temperature of the heat treatment are optimized. Thereby, anisotropic introduction of a coating film can be achieved more efficiently.

When the anisotropy is introduced into the coating film used in the present invention, the optimum amount of polarized ultraviolet light irradiation corresponds to the photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the coating film. The amount of the reaction is the most suitable for the amount of polarized ultraviolet radiation. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, when there are few photosensitive groups in the side chain that undergoes photocrosslinking reaction, photoisomerization reaction, or photofortes rearrangement reaction, a sufficient photoreaction amount cannot be obtained. . In this case, sufficient self-organization cannot be performed even after subsequent heating. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to a structure having a photo-crosslinkable group, when the photosensitive group of the side chain undergoing the crosslinking reaction is excessive, the cross-linking reaction between the side chains is excessive. get on. In this case, the obtained coating film becomes rigid, which may prevent subsequent self-organization by heating. In addition, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to a structure having a photoforte rearrangement base, when the photosensitive group of the side chain subjected to the photoforte rearrangement reaction becomes excessive, the coating film The liquid crystallinity is excessively reduced. In this case, the liquid crystallinity of the obtained film is also lowered, which may prevent subsequent self-organization by heating. In addition, when a structure having a light-Foth rearrangement base is irradiated with polarized ultraviolet light, when the amount of ultraviolet radiation is too much, the side chain polymer will photoly decompose, which hinders subsequent self-organization by heating. Happening.

Therefore, in the coating film used in the present invention, the optimum amount of the photo-crosslinking reaction or the photo-isomerization reaction or the photo-Furth rearrangement reaction of the photosensitive group of the side chain by irradiation of polarized ultraviolet rays is preferably The side chain polymer film has a photosensitive group of 0.1 mol% to 40 mol%, more preferably 0.1 mol% to 20 mol%. By making the amount of the photosensitive group of the side chain undergoing the photoreaction fall within this range, subsequent self-organization by heat treatment can be effectively performed, and anisotropy can be efficiently formed in the film.

The coating film used in the method of the present invention optimizes the irradiation amount of polarized ultraviolet light, so that the photocrosslinking reaction or photoisomerization reaction of the photosensitive group in the side chain of the side chain type polymer film, or the photophor The amount of Rice rearrangement reaction is optimized. Therefore, it is possible to efficiently introduce anisotropy into the coating film used in the present invention together with the subsequent heat treatment. In this case, the preferable amount of polarized ultraviolet rays can be evaluated based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

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

In the manufacturing method of the present invention, the irradiation amount of polarized ultraviolet rays to the coating film used in the present invention is preferably set within a range of 1% to 70% of the amount of polarized ultraviolet rays achieving ΔAmax, and more preferably 1% to 50. Within the range of%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays in the range of 1% to 50% of the amount of polarized ultraviolet rays that achieves ΔAmax is equivalent to 0.1 moles of the entire photosensitive group of the side chain polymer film. The amount of polarized ultraviolet light at which the light cross-linking reaction is carried out by ear% to 20 mole%.

From the above, according to the manufacturing method of the present invention, in order to achieve anisotropic introduction of the coating film, the liquid crystal temperature range of the side chain polymer is used as a reference, and the preferred heating temperature may be determined as described above. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C to 200 ° C, the heating temperature after polarized ultraviolet radiation is preferably set to 90 ° C to 190 ° C. In this way, a greater anisotropy is imparted to the coating film used in the present invention.

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

As described above, the substrate for a lateral electric field drive type liquid crystal display element manufactured by the method of the present invention or a lateral electric field drive type liquid crystal display element having the substrate becomes a person with excellent reliability, and can be used for large-screen and high-definition liquid crystals. TV, etc.

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

    [Example]    

The methacrylic monomers MA1, MA2, GMA, HBAGE, G1, and additives T1 of monomers having epoxy side chains used in the examples are shown below.

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

G1 was synthesized by the synthesis method described in Synthesis Example 1 below.

GMA (glycidyl methacrylate), HBAGE (hydroxybutyl acrylate glycidyl ether), and additive T1 (3-aminomethylpyridine) are commercially available.

    <Synthesis Example 1>    

Formation of specific glycidyl compounds (C1)

To a solution of carboxylic acid derivative (MA2) (MA2) (18.4 g, 60 mmol) in THF (tetrahydrofuran) (184 g) was added 2 drops of (COCl) ₂ (grass chloride) (11.4 g, 90 mmol) and DMF (dimethylformamidine). Amine), and reacted at room temperature for 2 hours. The solid obtained by concentrating the solution was dissolved in THF (350 g). This solution was added dropwise to a THF solution (88 g) of glycidol (8.89 g, 120 mmol) and triethylamine (13.4 g, 132 mmol) within 1 hour, and reacted for 18 hours. Subsequently, ethyl acetate (500 g) was added, and the organic phase was washed 3 times with water (300 g), and dried over magnesium sulfate. After removing magnesium sulfate by filtration, the crude product was obtained by concentration. The obtained crude product was subjected to silica gel chromatography using ethyl acetate and hexane to obtain C1 as a white solid (yield: 14.9 g, 69%).

Glycidyl derivative (C1): ¹ H-NMR (CDCl ₃ , δ ppm): 8.01 (d, 2H), 7.01 (d, 2H), 6.01 (s, 1H), 5.56 (s, 1H), 4.65-4.61 (m, 1H), 4.18-4.12 (m, 3H), 4.02 (t, 2H), 3.36-3.32 (m, 1H), 2.91-2.89 (m, 1H), 2.74-2.72 (m, 1H), 1.95 -1.94 (m, 3H), 1.86-1.79 (m, 2H), 1.76-1.69 (m, 2H), 1.57-1.44 (m, 4H).

    <Synthesis Example 2>         Synthesis of compound A1    

Compound [A] (63.42 g, 287 mmol), compound [B] (50.00 g, 406 mmol), EDC (N-ethyl-N '-(3-dimethylaminopropyl) carbodiimide hydrochloride Salt (93.43 g, 487 mmol), DMAP (4-dimethylaminopyridine) (4.96 g, 40.6 mmol), and THF (500 g) were added to a 1 L four-necked flask, and the reaction was performed at 23 ° C. The reaction was performed by HPLC Follow-up and confirm the completion of the reaction, pour the reaction solution into distilled water (3L), add ethyl acetate (1L), and remove the aqueous layer by liquid separation. Then, wash the organic layer twice with distilled water (1L). The organic layer was dried with magnesium sulfate, followed by filtration, and the solvent was distilled off with an evaporator to obtain 86.3 g of a compound [A1] as an oily compound (yield 92%).

¹ H-NMR (400 MHz, CDCl3, δ ppm): 8.81-8.79 (2H, dd), 7.86-7.85 (2H, dd), 6.16-6.14 (1H, m), 5.62-5.60 (1H, m), 4.63 4.61 (2H, m), 5.62-5.60 (2H, m), 4.63-4.61 (2H, m), 4.52-4.60 (2H, m), 1.97-1.95 (3H, m).

    <Synthesis Example 3>         Synthesis of compound A2    

A 500 ml four-necked flask was fed with 15.00 g of 1-methylpiperidine and 120 g of toluene, stirred at 5 ° C, and 30 g of toluene was added dropwise to dilute 24.40 g of 2-isocyanate ethyl methacrylate over 50 minutes. After the solution was stirred at room temperature for 3 hours. Next, the reaction solution was concentrated under reduced pressure in an evaporator to adjust to about half the weight, and then 75 g of heptane was added. Next, the crystals were suspended at 5 ° C. to precipitate the crystals, and the crystals were filtered under suction under reduced pressure, and then dried under reduced pressure to obtain 33.26 g of a compound [A2] (yield: 87%, properties: white crystals).

¹ H-NMR (400MHz) in d6-DMSO: 6.65ppm (m, 1H), 6.06ppm (s, 1H), 5.67ppm (s, 1H), 4.08ppm (t, J = 6.0Hz, 2H), 3.38 -3.15 ppm (m, 6H), 2.22 ppm (t, J = 4.8 Hz, 4H), 2.15 ppm (s, 3H), 1.88 ppm (s, 3H).

    <Synthesis Example 4>         Synthesis of compound A3    

Add carboxylic acid derivative [MA2] (86.39 g, 282 mmol), compound [C] (50.00 g, 310 mmol), EDC (64.87 g, 338 mmol), DMAP (3.45 g, 28.2 mmol), THF (900 g), and add The reaction was carried out at 23 ° C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into distilled water (4 L), ethyl acetate (1 L) was added, and the aqueous layer was removed by a liquid separation operation. Subsequently, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried with magnesium sulfate. It was then filtered, and the solvent was distilled off with an evaporator to obtain 121.7 g of a compound [A3] as an oily compound (yield 96%).

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 7.92 (2H, d), 7.01 (2H, d), 7.06 (1H, t), 6.01 (1H, m), 5.65 (1H, m), 4.17 (2H, t), 4.08 (2H, t), 4.05-4.02 (2H, m), 3.29-3.26 (2H, m), 1.86 (3H, s), 1.75-1.72 (2H, m), 1.65-1.62 (2H, m), 1.50-1.36 (17H, m).

    <Synthesis Example 5>         Synthesis of compound A4    

Add carboxylic acid derivative [MA2] (69.17g, 286mmol), compound [D] (50.00g, 248mmol), EDC (51.95g, 271mmol), DMAP (2.76g, 22.58mmol), THF (700g), and add The reaction was carried out at 23 ° C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into distilled water (4 L), ethyl acetate (1 L) was added, and the aqueous layer was removed by liquid separation. Subsequently, the organic layer was washed twice with distilled water (1 L), and then the organic layer was dried with magnesium sulfate. Subsequently, it was filtered, and the solvent was distilled off by an evaporator to obtain 100.9 g of a compound [A4] as an oily compound (yield 91%).

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 7.91 (2H, d), 6.92 (2H, d), 6.01 (1H, s), 5.65 (1H, s), 4.14-4.06 (2H, m) , 3.67-3.60 (2H, m), 3.34-3.27 (1H, m), 2.98-2.93 (1H, m), 1.87 (3H, s), 1.79-1.38 (24H, m).

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

(Organic solvents)

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: butyl cellolysin

PB: propylene glycol monobutyl ether

(Polymerization initiator)

AIBN: 2,2’-azobisisobutyronitrile

    <Synthesis of Compound S1>    

20.00 g of 4,4'-diaminodiphenylamine and 300 g of THF were fed into a 2 L four-necked flask, and 100 g of THF diluted 50.90 g of diluted triethoxysilylpropyl isocyanate were added dropwise within 30 minutes under ice-cooling stirring. The resulting solution was stirred at room temperature for 18 hours. Subsequently, the reaction solution was concentrated under reduced pressure to remove about half of THF. Next, 720 g of acetonitrile was added at room temperature, and after stirring for 30 minutes, stirring was suspended at 5 ° C. The crystals thus precipitated were filtered under reduced pressure and dried under reduced pressure to obtain 60.70 g of a compound S1 (yield: 87%, property: white solid).

¹ H-NMR (400MHz) in d6-DMSO: 8.10ppm (s, 2H), 7.61ppm (s, 1H), 7.20ppm (d, J = 7.6Hz, 4H), 6.87ppm (d, J = 7.6Hz , 4H), 6.04-6.00ppm (m, 2H), 3.75ppm (q, J = 6.8Hz, 12H), 3.34ppm (s, 2H), 3.06-3.00ppm (m, 4H), 1.50-1.42ppm ( m, 4H), 1.14ppm (t, J = 6.8Hz, 18H), 0.58-0.52ppm (m, 4H).

    <Synthesis of Compound S2>    

A 300 ml four-necked flask was fed with 4.00 g of 1,4-diaminobenzene and 60 g of THF, and under ice-cooled stirring, 20 g of THF was diluted dropwise with 18.76 g of triethoxysilylpropyl isocyanate within 1.5 hours. After the solution was stirred at room temperature for 18 hours. Subsequently, the crystals precipitated from the reaction solution were filtered under reduced pressure and transferred to another 300 mL four-necked flask. Next, 100 g of acetonitrile was added thereto, and then the stirring was suspended at room temperature. The crystals thus precipitated were filtered under reduced pressure and dried under reduced pressure to obtain 18.98 g of compound S2 (yield: 85%, property: white solid).

¹ H-NMR (400MHz) in CDCl ₃ : 7.60-7.47ppm (br, 2H), 6.51ppm (s, 4H), 6.46-6.30ppm (br, 2H), 3.81ppm (q, J = 6.8Hz, 12H ), 3.24-3.10 ppm (m, 4H), 1.70-1.57 ppm (m, 4H), 1.22 ppm (t, J = 6.8 Hz, 18H), 0.67-0.62 ppm (m, 4H).

    <Polymer Synthesis Example 11>    

After dissolving MA1 (3.98g), MA2 (5.51g), GMA (0.04g), A1 (0.07g) in THF (40.0g) and degassing with a diaphragm pump, add AIBN (0.24g) and repeat Outgassing. Subsequently, it was reacted at 60 ° C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (300 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P11.

    <Polymer Synthesis Examples 12 to 21>    

The composition shown in Table 1 was synthesized by the same method as in Polymer Synthesis Example 11.

[Table 1]

    <Example 11>    

N-ethyl-2-pyrrolidone (NEP) (5.1g) was added to the methacrylate polymer powder P11 (0.4g) obtained in Polymer Synthesis 11, and stirred at room temperature for 1 hour to dissolve it. . PB (4.5 g) was added to this solution and stirred to obtain a polymer solution T11. The polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

    <Examples 12 to 25>    

The liquid crystal alignment agent having the composition shown in Table 2 was adjusted by the same method as in Example 11 to obtain the liquid crystal alignment agents T12 to T25 of Examples 12 to 25.

[Table 2]

    <Control Polymer Synthesis Example 1>    

MA1 (3.98 g) and MA2 (5.51 g) were dissolved in THF (40.0 g), and after degassing with a diaphragm pump, AIBN (0.24 g) was added and degassed again. Subsequently, it was reacted at 60 ° C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (300 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure to obtain methacrylate polymer powder CP1.

    <Comparative polymer synthesis examples 2 to 4>    

The composition shown in Table 3 was synthesized in the same manner as in Polymer Control Polymer Synthesis Example 1.

    <Comparative Example 11>    

NEP (5.1 g) was added to the methacrylate polymer powder CP1 (0.4 g) obtained in Comparative Polymer Synthesis Example 1, and stirred at room temperature for 1 hour to dissolve. To this solution, PB (4.5 g) was added and stirred to obtain a polymer solution CT11. The polymer solution is directly used as a liquid crystal alignment agent for forming a liquid crystal alignment film.

    〈Comparative Examples 12 to 16〉    

The liquid crystal alignment agent having the composition shown in Table 4 was adjusted by the same method as that of Comparative Example 11, and the liquid crystal alignment agents CT12 to CT16 of Comparative Examples 12 to 16 were obtained.

[Table 4]

    〈Production of liquid crystal cell〉    

The liquid crystal alignment agent (T11) obtained in Example 11 was filtered with a 0.45 μm filter, and then spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70 ° C for 90 seconds to form a liquid crystal with a film thickness of 100 nm. Alignment film. Next, the coated film surface was irradiated with ultraviolet light of 313 nm of 15 mJ / cm ² through a polarizing plate, and then heated on a heating plate at 140 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Prepare two substrates with a liquid crystal alignment film, set a 6 μm spacer on the liquid crystal alignment film surface of one of the substrates, and combine them so that the rubbing directions of the two substrates are parallel. After leaving the liquid crystal injection port, seal the periphery. Empty cells with a cell gap of 4 μm were prepared. Liquid crystal MLC-3019 (manufactured by Merck Co., Ltd.) was injected into the air cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell in which liquid crystals were aligned in parallel.

The liquid crystal alignment agents T12 to T25 obtained in Examples 12 to 25 and the liquid crystal alignment agents CT11 to CT16 obtained in Comparative Examples 11 to 16 were also used to prepare liquid crystal cells.

    〈Residual image evaluation〉    

The prepared IPS mode liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal, and the backlight is turned on without applying a voltage so that the brightness of transmitted light is minimized. Adjust the configuration angle of the LCD cell. Next, the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the pixel becomes the darkest to the angle at which the first region is the darkest is calculated as the initial alignment azimuth. Next, in an oven at 60 ° C, an AC voltage of 16 V _{pp for} 168 hours was applied at a frequency of 30 Hz. Subsequently, the state between the pixel electrode and the counter electrode of the liquid crystal cell is short-circuited, and it is left to stand at room temperature for 1 hour. After being left to stand, the orientation azimuth is measured in the same manner, and the difference between the orientation azimuths before and after the AC drive is calculated as the angle Δ (degrees). The measurement was performed similarly in other examples. As a result, the angle Δ was 0.1 or less in all Examples. After irradiating ultraviolet light to the side-chain polymer mold exhibiting liquid crystallinity, it is heated in the liquid crystal display temperature range, and due to self-organization, the liquid crystal alignment energy is efficiently provided in the polymer as a whole, so it is hardly observed after long-term AC driving. Azimuth offset.

    <VHR evaluation>    

The evaluation of VHR is to apply a 1V voltage of 60 μs to the obtained liquid crystal cell at a temperature of 70 ° C., and measure the voltage after 16.67 ms, and calculate to what extent the voltage can be maintained as the voltage retention rate. The VHR measured immediately after the liquid crystal cell was prepared was set to VHR1, and the VHR measured after the VHR1 was measured on the backlight for one week was set to VHR2. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Technology Co., Ltd.

The results of the VHR of the liquid crystal alignment agents of Examples 11 to 25 and Comparative Examples 11 to 16 are shown in Table 5.

As can be seen from Table 5, in Examples 11 to 25, the monomers having an epoxy group and the monomers having an amidino group were copolymerized, as compared with the control in which the monomers having an amidino group were not copolymerized. In cases 11-16, VHR1 was further increased. It also suppresses the reduction of VHR (VHR2) caused by backlight aging.

Claims (10)

A polymer composition, [I] containing (A) a side chain polymer and (B) an organic solvent, wherein (A) is a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range and has A side chain represented by the following formula (0) and further having a side chain (a) having a group selected from a nitrogen-containing aromatic heterocyclic group, a fluorenylamino group, and a carbamate group, (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 the hydrogen atoms to which they are bonded may be replaced by halogen groups; T is a single bond or 1 to 12 carbon atoms. Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted by halo 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 is 2, X may be the same as or different from each other; P and Q are each independently a divalent benzene ring and a naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbons, and groups selected from them; however, X is -CH = CH-CO-O-,- When O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; l1 is 0 or 1, l2 is an integer from 0 to 2, and l1 and l2 are both 0, A is a single bond when T is a single bond; B is a single bond when l1 is 1, and B is a single bond when T is a single bond; G is selected from the following formulae (G-1), (G-2), and (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 plural, they may be the same as 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 an alkyl group having 1 to 3 carbon atoms and a phenyl group)).     The polymer composition according to claim 1, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photo-Fries rearrangement.     For example, the polymer composition of claim 1, wherein the component (A) has any one of the photosensitive side chains selected from the group consisting of the following formulae (1) to (6): (Wherein A, B, and D each independently represent a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O -, Or -O-CO-CH = CH-; S is an alkylene group with 1 to 12 carbon atoms, and the hydrogen atoms to which they are bonded can also be replaced with halogen groups; T is a single bond or 1 to 12 carbon atoms Hydrogenated alkyl groups, and the hydrogen atoms to which they are bonded may be substituted by halogen groups; Y ₁ represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and a lipid having 5 to 8 carbon atoms. Rings selected by cyclic hydrocarbons, or the same or different 2 to 6 rings selected by these substituents, are bonded through a bonding group B, and the hydrogen atoms to which they are bonded can also be independently passed through. -COOR ₀ (where R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, carbon alkyl of 1 to 5, or an alkyl group having a carbon number of 1 to 5 substituents; the Y ₂ by the divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, of 5 to 8 carbon atoms The alicyclic hydrocarbons, and the groups selected by their combination, and the hydrogen atoms to which they are bonded may each independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl with 1 to 5 carbons, or alkane with 1 to 5 carbons Oxy group substitution; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ; Cou represents a coumarin-6-yl group or a coumarin-7-yl group; The hydrogen atom of the junction can also independently pass -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Alkyloxy substitution; q1 and q2 are either 1 or 0; q3 is 0 or 1; X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH -, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X is 2, X may be the same as or different from each other; P and Q are each independently A group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof; however, X is -CH When = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; l1 is 0 or 1, and l2 is an integer from 0 to 2. When l1 and l2 are 0, A is a single bond when T is a single bond; B is a single bond when l1 is 1 and T is a single bond; H and I are each independently a divalent benzene ring and naphthalene Ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof). The polymer composition according to any one of claims 1 to 3, wherein the component (A) has a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): (Wherein A and B have the same definitions as above; Y ₃ is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms , And a group selected by a combination of these, and the hydrogen atoms to which they are bonded are each independently -NO ₂ , -CN, halo, alkyl having 1 to 5 carbons, or 1 to 5 carbons. 5 alkyloxy substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halo, monovalent benzene ring, naphthalene ring, Benzene ring, furan ring, nitrogen-containing heterocyclic ring, alicyclic hydrocarbon with 5-8 carbons, alkyl group with 1-12 carbons, or alkoxy group with 1-12 carbons; q1 and q2 are 1 The other is 0; l is an integer from 1 to 12, and m is an integer from 0 to 2. However, in formulas (25) to (26), the total of all m is 2 or more, and formulas (27) to (28) Among them, the total of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a A benzene ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O -, -CH = N-, -CF _2- ).     A method for manufacturing a substrate with a liquid crystal alignment film is to obtain a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element that is provided with alignment control energy by having the following steps: [I] will be as requested in items 1 to 4 The step of applying the composition of any one to a substrate having a conductive film for lateral electric field drive to form a coating film; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; [III] heating [II] The steps of the obtained coating film.         A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element manufactured by the method as claimed in claim 5.         A lateral electric field drive type liquid crystal display element having a substrate as claimed in claim 6.         A method for manufacturing a liquid crystal display element, which comprises obtaining a lateral electric field drive type liquid crystal display element by the following steps: a step of preparing a substrate (first substrate) as claimed in claim 6; obtaining a second substrate having a liquid crystal alignment film This step is to obtain a liquid crystal alignment film to which an alignment control ability is given by having the following steps: [I '] forming a polymer composition as described in any one of claims 1 to 4 on a second substrate to form Step of coating film; [II '] Step of irradiating polarized ultraviolet light to coating film obtained by [I']; and [III '] Step of heating coating film obtained in [II']; and [IV] to separate A method in which the liquid crystal aligns the liquid crystal alignment films of the first and second substrates, and arranges the first and second substrates to face each other to obtain a liquid crystal display element.         A lateral electric field driving type liquid crystal display element is manufactured by a method as claimed in claim 8.     A side chain polymer, which is a photosensitive side chain polymer exhibiting liquid crystallinity in a specific temperature range, has a side chain represented by the following formula (0), and further has a nitrogen-containing aromatic heterocyclic ring. (A), the side chain (a) of the selected group of (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 the hydrogen atoms to which they are bonded may be replaced by halogen groups; T is a single bond or 1 to 12 carbon atoms. Alkyl groups, and the hydrogen atoms to which they are bonded may be substituted by halo 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 is 2, X may be the same as or different from each other; P and Q are each independently a divalent benzene ring and a naphthalene ring , Biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbons having 5 to 8 carbons, and groups selected from them; however, X is -CH = CH-CO-O-,- When O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring; l1 is 0 or 1, l2 is an integer from 0 to 2, and l1 and l2 are both 0, A is a single bond when T is a single bond; B is a single bond when l1 is 1, and B is a single bond when T is a single bond; G is selected from the following formulae (G-1), (G-2), and (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 plural, they may be the same as 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 an alkyl group having 1 to 3 carbon atoms and a phenyl group)).