JP2015007702A - Method for manufacturing substrate having liquid crystal alignment layer for in-plane switching type liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an in-plane switching type liquid crystal display element having alignment controllability imparted with high efficiency and having excellent image persistence property.SOLUTION: A method for manufacturing a substrate having a liquid crystal alignment layer is provided, for obtaining a liquid crystal alignment layer for an in-plane switching type liquid crystal display element imparted with alignment controllability. The method includes steps of: [I] forming a coating film by applying a polymer composition comprising (A) a photosensitive side-chain polymer that exhibits liquid crystalline property in a predetermined temperature range and has a number average molecular weight of 4,000 or more and (B) an organic solvent on a substrate having a conductive film for in-plane switching; [II] irradiating the coating film obtained in step [I] with polarized ultraviolet rays; and [III] heating the coating film obtained in step [II].

Description

  The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element. More specifically, the present invention relates to a novel method for manufacturing a liquid crystal display device having excellent image sticking characteristics.

  The liquid crystal display element is known as a light, thin and low power consumption display device, and has been remarkably developed in recent years. The liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. In the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in 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 a surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. The liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.

  A rubbing method is conventionally known as an alignment treatment method for a liquid crystal alignment film for imparting alignment control ability. The rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction). This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements. As an organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.

  However, in the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, generation of dust or static electricity may be a problem. In addition, due to the high definition of the liquid crystal surface element in recent years and the unevenness caused by the corresponding electrodes on the substrate and the switching active element for driving the liquid crystal, the surface of the liquid crystal alignment film cannot be uniformly rubbed with a cloth. In some cases, alignment of the liquid crystal could not be realized.

  Therefore, a photo-alignment method has been actively studied as another alignment treatment method for a liquid crystal alignment film that is not rubbed.

  There are various photo alignment methods. Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

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

  In addition, photocrosslinking type and photoisomerization type photo-alignment methods are also known. For example, polyvinyl cinnamate is used and irradiated with polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). In addition, when a side chain polymer having azobenzene in the side chain is used, irradiation with polarized ultraviolet light causes an isomerization reaction at the azobenzene portion of the side chain parallel to the polarized light, and the liquid crystal is aligned in a direction perpendicular to the polarization direction. Align (for example, see Non-Patent Document 2).

  As in the above example, the liquid crystal alignment film alignment treatment method by the photo alignment method eliminates the need for rubbing, and there is no fear of generation of dust or static electricity. An alignment process can be performed even on a substrate of a liquid crystal display element having an uneven surface, which is a method for aligning a liquid crystal alignment film suitable for an industrial production process.

Japanese Patent No. 3893659

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

  As described above, the photo-alignment method does not require a rubbing process as compared with a rubbing method that has been industrially used as an alignment treatment method for liquid crystal display elements, and thus has a great advantage. And compared with the rubbing method in which the alignment control ability becomes almost constant by rubbing, the photo alignment method can control the alignment control ability by changing the irradiation amount of polarized light. However, in the photo-alignment method, in order to achieve the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required or stable liquid crystal alignment may not be realized. .

  For example, in the decomposition type photo-alignment method described in Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output of 500 W for 60 minutes. Become. Even in the case of a dimerization type or photoisomerization type photo-alignment method, a large amount of ultraviolet irradiation of about several J (joule) to several tens of J may be required. Furthermore, in the case of the photo-crosslinking type or photoisomerization type photo-alignment method, since the thermal stability and light stability of the liquid crystal alignment are inferior, there is a problem that alignment failure or display burn-in occurs when a liquid crystal display element is used. was there. In particular, in a horizontal electric field drive type liquid crystal display element, since liquid crystal molecules are switched in a plane, alignment misalignment of liquid crystal after liquid crystal driving is likely to occur, and display burn-in caused by AC driving is a major issue.

  Therefore, in the photo-alignment method, there is a demand for higher efficiency of alignment treatment and realization of stable liquid crystal alignment, and liquid crystal alignment films and liquid crystals that can impart high alignment control ability to the liquid crystal alignment film with high efficiency. There is a need for aligning agents.

  The present invention provides a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. With the goal.

As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> [I] (A) A photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range, and has a number average molecular weight of 4,000 or more, preferably 6,000 or more, more preferably 10 A step of forming a coating film by applying a polymer composition containing (B) an organic solvent on a substrate having a conductive film for driving a lateral electric field;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.

<2> In the above item <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofleece transition.
<3> In the above <1> or <2>, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently a single bond, 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. Is a group selected from However, when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

<4> In the above <1> or <2>, the component (A) may have any one photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

<5> In the above <1> or <2>, the component (A) preferably has any one photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m and R have the same definition as above.

<6> In the above <1> or <2>, the component (A) may have a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y ₁ , X, 1, m1, and m2 have the same definition as above.

<7> In the above <1> or <2>, the component (A) preferably has a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.

<8> In the above <1> or <2>, the component (A) preferably has 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 definition as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

<9> In the above <1> or <2>, the component (A) preferably has a photosensitive side chain represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definition as above.

<10> In any one of the above items <1> to <9>, the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Good.
In which A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z _{2 each} represents a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —.

<11> A substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display device manufactured according to any one of the above items <1> to <10>.
<12> A lateral electric field drive type liquid crystal display device having the substrate of <11> above.

<13> A step of preparing the substrate (first substrate) of <11>above;
[I ′] On the second substrate (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a number average molecular weight of 4,000 or more, preferably 6,000 or more, More preferably, a step of applying a polymer composition containing a side chain polymer that is 10,000 or more and (B) an organic solvent to form a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control ability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment films of the first and second substrates via liquid crystal The liquid crystal display element is obtained by disposing the first and second substrates so as to face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.

<14> A lateral electric field drive type liquid crystal display device manufactured according to the above <13>.
<15> (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a number average molecular weight of 4,000 or more, preferably 6,000 or more, more preferably 10,000 or more. A composition for producing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, comprising: a side chain type polymer as defined above; and (B) an organic solvent.

According to the present invention, there are provided a substrate having a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element which is provided with high efficiency and orientation control ability and has excellent image sticking characteristics, and a horizontal electric field drive type liquid crystal display element having the substrate. Can do.
Since the lateral electric field drive type liquid crystal display device manufactured by the method of the present invention is provided with the alignment control ability with high efficiency, the display characteristics are not impaired even when continuously driven for a long time.

It is a figure of one example which illustrates typically the introduction process of the anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention, using the crosslinkable organic group for the photosensitive side chain, and introduced the anisotropic It is a figure when property is small. It is a figure of one example which illustrates typically the introduction process of the anisotropy in the manufacturing method of the liquid crystal aligning film used for this invention, using the crosslinkable organic group for the photosensitive side chain, and introduced the anisotropic It is a figure when the property is large. It is a figure of one example which illustrates typically the introduction processing of anisotropy in the manufacturing method of the liquid crystal aligning film used for the present invention, using the organic group which causes fleece transition or isomerization to the photosensitive side chain, and is introduced. It is a figure in case the anisotropy made is small. It is a figure of one example which illustrates typically the introduction processing of anisotropy in the manufacturing method of the liquid crystal aligning film used for the present invention, using the organic group which causes fleece transition or isomerization to the photosensitive side chain, and is introduced. It is a figure in case the anisotropy made is large. It is a graph of S value (horizontal axis: DP (Degree of photoreaction) value) which shows the expression of anisotropy about the methacrylate polymer P1-P6 obtained in Example 2-Example 6 and Comparative Example 1. FIG.

As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition used in the production method of the present invention has a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter, also simply referred to as a side chain polymer), and the polymer composition The coating film obtained by using the product is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth a liquid crystal aligning film) to which the orientation control ability was provided through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as a liquid crystal alignment film, and a liquid crystal alignment film with high alignment control ability can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
<Manufacturing method of substrate having liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>
The method for producing a substrate having the liquid crystal alignment film of the present invention is as follows.
[I] (A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a number average molecular weight of 4,000 or more, preferably 6,000 or more, more preferably 10,000 or more. A step of applying a polymer composition containing a side chain polymer and (B) an organic solvent onto a substrate having a conductive film for driving a lateral electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element to which alignment control ability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

Further, by preparing a second substrate in addition to the obtained substrate (first substrate), a lateral electric field drive type liquid crystal display element can be obtained.
The second substrate is replaced with a substrate having no lateral electric field driving conductive film instead of a substrate having no lateral electric field driving conductive film, except that the above steps [I] to [III] (lateral electric field driving For the sake of convenience, the substrate having no conductive film is sometimes referred to as processes [I ′] to [III ′] in some cases for the sake of convenience. Two substrates can be obtained.

The manufacturing method of the horizontal electric field drive type liquid crystal display element is:
[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other with liquid crystal interposed therebetween;
Have Thereby, a horizontal electric field drive type liquid crystal display element can be obtained.

Hereinafter, each step [I] to [III] and [IV] of the production method of the present invention will be described.
<Process [I]>
In the step [I], a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range on a substrate having a conductive film for driving a lateral electric field and having a number average molecular weight of 4,000 or more, preferably Is coated with a polymer composition containing a side chain polymer and an organic solvent that is 6,000 or more, more preferably 10,000 or more.

<Board>
Although it does not specifically limit about a board | substrate, When the liquid crystal display element manufactured is a transmission type, it is preferable that a highly transparent board | substrate is used. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
In consideration of application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conductive film for driving lateral electric field>
The substrate has a conductive film for driving a lateral electric field.
Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide) when the liquid crystal display element is a transmission type.
In the case of a reflective liquid crystal display element, examples of the conductive film include a material that reflects light such as aluminum, but are not limited thereto.
As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<Polymer composition>
A polymer composition is applied on a substrate having a conductive film for driving a lateral electric field, particularly on the conductive film.
The polymer composition used in the production method of the present invention is (A) a photosensitive side-chain polymer that exhibits liquid crystallinity within a predetermined temperature range, and has a number average molecular weight of 4,000 or more. A side chain polymer; and (B) an organic solvent.
<< (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and has a number average molecular weight of 4,000 or more.
(A) The side chain polymer preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 100 ° C to 300 ° C.
The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 100 ° C to 300 ° C.

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

  The polymer structure has, for example, a main chain and a side chain bonded to the main chain, and the side chain includes a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group, and a tip. A structure having a photosensitive group bonded to a moiety, which undergoes a crosslinking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogenic component, and A structure having a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction can be obtained.

  More specific examples of the structure of the photosensitive side chain polymer film that can exhibit liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, It has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6) A structure is preferred.

In the formula, A, B, and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently a single bond, 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. Is a group selected from However, when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof.

The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y ₁ , X, Y ₂ and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).

The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m and R have the same definition as above.

The side chain may be 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 definition as above.

The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as 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 definition as above.
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represents an oxy group.

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 definition as above.

The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A, B, q1 and q2 have the same definition as above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z _{2 each} represents a single bond, —CO—, —CH ₂ O—, —CH═N—, or —CF ₂ —.

<< Production Method of Photosensitive Side Chain Polymer >>
The photosensitive side chain polymer capable of exhibiting the above liquid crystallinity can be obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain and the liquid crystalline side chain monomer.

[Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferred.

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

The present application provides novel compounds (1) to (11) represented by the following formulas (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 Represents 0 or 1; and Py represents a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group.

[Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.

  More specific examples of the liquid crystalline side chain monomer include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups. A structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.

  (A) The side chain polymer can be obtained by the polymerization reaction of the above-described photoreactive side chain monomer exhibiting liquid crystallinity. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. it can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and , Etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl 8 tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate. (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.

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

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

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent can be used. As the radical polymerization method, the reversible addition-cleavage chain transfer (RAFT) method is used to control the number average molecular weight of the (A) side chain polymer of the present invention, can do.
Examples of RAFT polymerization reagents include A) dithiobenzoate RAFT agents; B) trithiocarbonate RAFT agents; C) dithiocarbamate RAFT agents; D) xanthate RAFT agents. Specific examples of RAFT polymerization reagents include 2-cyano-2-propyldodecyl trithiocarbonate, 4-cyano-pentanolic acid dithiobenzoate, 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanol. Acid, 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanol, poly (ethylene glycol) methyl ether 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanoate, poly (ethylene glycol) ) Methyl ether (4-cyano-4-pentanoate dodecyl trithiocarbonate), 2-phenyl-2-propylbenzodithioate, 1- (methoxycarbonyl) ethylbenzodithioate, 2-cyano-2-propyl-4-cyano Benzodithioate, 4-cyano-4- (phenylcarbonothioylthio) pe Tanolic acid, 2-cyano-2-propylbenzodithioate, benzylbenzodithioate, ethyl 2-methyl-2- (phenylthiocarbonylthio) propionate, methyl-2-phenyl-2- (phenylthiocarbonothioylthio) Acetate, 4-cyano-4- (phenylcarbonothioylthio) pentanolic acid N-succinimidyl ester, ethyl 2- (phenylcarbonothioylthio) propionate, 2- (dodecylthiocarbonothioylthio) propionic acid, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, methyl 2- (dodecylthiocarbonothioylthio) -2-methylpropionate, 2- (dodecylthiocarbonothioylthio) -2-methyl Propionic acid N-hydroxysuccinimidyl ester, poly (ethylene glycol) methyl ether (2-methyl Dodecyl trithiocarbonate), poly (ethylene glycol) bis [2- (dodecylthiocarbonothioylthio) -2-methylpropionate], 2- (dodecylthiocarbonothioylthio) -2 -Methylpropionic acid 3-azido-1-propanol ester, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid pentafluorophenyl ester, poly (ethylene glycol) methyl ether (2-dodecylthiocarbonothioylthio) ) -2-methylpropionate, cyanomethyldodecyl trithiocarbonate, cyanomethylmethyl (phenyl) carbamodithioate, cyanomethyldiphenylcarbamodithioate, benzyl 1H-pyrrole-1-carbodithioate, bis (thiobenzoyl) ) Disulfide, bis (dodecylsulfanylthio) Carbonyl) disulfide, 1-succinimidyl-4-cyano-4- [N-methyl-N- (4-pyridyl) carbamothioylthio] pentanoate, 2-cyanopropan-2-yl N-methyl-N- (pyridine- 4-yl) carbamodithioate, cyanomethylmethyl (4-pyridyl) carbamodithioate, methyl 2-propionate methyl (4-pyridinyl) carbamodithioate, N, N'-dimethyl N, N'- Examples include, but are not limited to, di (4-pyridinyl) thiuram disulfide, preferably 2-cyano-2-propyldodecyl trithiocarbonate, 4-cyano-pentanolic acid dithiobenzoate, and the like.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydride peroxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy cyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Sanic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy 2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl]
2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4, 4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) 4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di ( Ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloro Methyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3 '-Carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimi Sol, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2, 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′bis (2,4-dibromophenyl) -4,4 ′, 5,5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3 -(2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2, 4-cyclopentadi N-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2, -(3-Methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1,3-benzothi Tetrazole -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.

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

  The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned.

These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.

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

  In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is It is preferable that it is 0.1 mol%-10 mol% with respect to the monomer to superpose | polymerize. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.

[Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

The molecular weight of the (A) side chain polymer of the present invention is measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and coating film uniformity. The weight average molecular weight is preferably 2000 to 1000000, more preferably 5000 to 200000.
The number average molecular weight of the (A) side chain polymer of the present invention is 4,000 or more, preferably 6,000 or more, more preferably 10,000 or more, and preferably 100,000 or less. . The number average molecular weight can be measured by the GPC method.

[Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain polymer capable of exhibiting the liquid crystallinity already described. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the resin component described above may be a photosensitive side chain polymer that can all exhibit the above-described liquid crystallinity, but does not impair the liquid crystal developing ability and the photosensitive performance. Other polymers may be mixed within the range. In that case, content of the other polymer in a resin component is 0.5 mass%-80 mass%, Preferably it is 1 mass%-50 mass%.
Examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.

<Organic solvent>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, etc. Is mentioned. These may be used alone or in combination.

  The polymer composition used for this invention may contain components other than the said (A) and (B) component. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate. However, the present invention is not limited to this.

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.

  These poor solvents may be used alone or in combination. When using the solvent as described above, it is preferably 5% by mass to 80% by mass of the total solvent, more preferably so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. Is 20% by mass to 60% by mass.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane.

  Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, the addition of the following phenoplasts and epoxy group-containing compounds for the purpose of preventing the deterioration of electrical characteristics due to the backlight when the liquid crystal display element is constructed An agent may be contained in the polymer composition. Specific phenoplast additives are shown below, but are not limited to this structure.

  Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4 4'-diaminodiphenylmethane and the like.

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

A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino substituted Aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

  In the polymer composition, in addition to the above-described ones, a dielectric, a conductive substance, or the like for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, as long as the effects of the present invention are not impaired. Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and density of the liquid crystal alignment film.

The method for applying the polymer composition described above onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.

After the polymer composition is applied onto the substrate having the conductive film for driving the transverse electric field, it is 50 to 200 ° C., preferably 50 to 200 ° C. by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° C. to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.

<Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

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

<Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.

The heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk. The Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the chain polymer used, and 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range made into an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
The liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.

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

  By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board | substrate with a liquid crystal aligning film can be manufactured highly efficiently.

<Process [IV]>
The [IV] step is the same as [I ′] to [III ′] in the same manner as the substrate (first substrate) obtained in [III] and having a liquid crystal alignment film on the conductive film for driving a lateral electric field. The liquid crystal cell is obtained by a known method by arranging the liquid crystal alignment film-provided substrate (second substrate) obtained in the above step so that both liquid crystal alignment films face each other through the liquid crystal. To produce a lateral electric field drive type liquid crystal display element. The steps [I ′] to [III ′] are the same as the steps [I] except that a substrate having no lateral electric field driving conductive film is used instead of the substrate having the lateral electric field driving conductive film. It can carry out similarly to process [I]-[III]. Since the difference between the steps [I] to [III] and the steps [I ′] to [III ′] is only the presence or absence of the conductive film, the description of the steps [I ′] to [III ′] is omitted. To do.

  To give an example of the production of a liquid crystal cell or a liquid crystal display element, the first and second substrates described above are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. In this way, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. , Etc. can be illustrated. At this time, it is preferable to use a substrate having an electrode having a structure like a comb for driving a horizontal electric field as the substrate on one side. The spacer diameter at this time is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.

  Hereinafter, an embodiment using a side chain type polymer having a structure having a photocrosslinkable group as a photoreactive group is the first embodiment, a structure having a photofleece rearrangement group or a group causing isomerization as a photoreactive group An embodiment using the side chain type polymer will be referred to as a second embodiment.

  FIG. 1 schematically shows an anisotropic introduction process in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to. FIG. 1 (a) is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 1 (b) is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. FIG. 1 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention. In 1 form, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 1%-15% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 2 is a schematic illustration of anisotropy introduction treatment in a method for producing a liquid crystal alignment film using a side chain polymer having a structure having a photocrosslinkable group as a photoreactive group in the first embodiment of the present invention. It is a figure of one example demonstrated to. FIG. 2A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 2B is a schematic diagram showing the state of the side chain polymer film after irradiation with polarized light. FIG. 2 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is large, that is, the first aspect of the present invention. In 1 form, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 15%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 3 shows a side chain polymer having a structure having a photo-isomerizable group as a photoreactive group or a photo-Fleece rearrangement group represented by the above formula (18) in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction process of anisotropy in the manufacturing method of the used liquid crystal aligning film. FIG. 3A is a diagram schematically showing the state of the side chain polymer film before polarized light irradiation, and FIG. 3B is a schematic diagram of the state of the side chain polymer film after polarized light irradiation. FIG. 3 (c) is a diagram schematically showing the state of the side-chain polymer film after heating, and particularly when the introduced anisotropy is small, that is, the first aspect of the present invention. In 2 aspect, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  FIG. 4 shows the production of a liquid crystal alignment film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19) as a photoreactive group in the second embodiment of the present invention. It is a figure of one example which illustrates typically the introduction processing of anisotropy in a method. FIG. 4A is a diagram schematically showing the state of the side chain polymer film before irradiation with polarized light, and FIG. 4B is a schematic diagram of the state of the side chain polymer film after irradiation with polarized light. FIG. 4 (c) is a diagram schematically showing the state of the side-chain polymer film after heating. In particular, when the introduced anisotropy is large, that is, In 2 aspect, it is a schematic diagram in case the ultraviolet irradiation amount of a [II] process exists in the range of 1%-70% of the ultraviolet irradiation amount which makes (DELTA) A the maximum.

  In the first embodiment of the present invention, in the treatment for introducing anisotropy into the coating film, the ultraviolet irradiation amount in the step [II] is in the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA. In the case, first, the coating film 1 is formed on the substrate. As shown to Fig.1 (a), in the coating film 1 formed on the board | substrate, it has a structure where the side chain 2 arranges at random. According to the random arrangement of the side chain 2 of the coating film 1, the mesogenic component and the photosensitive group of the side chain 2 are also randomly oriented, and the coating film 1 is isotropic.

  In the first embodiment of the present invention, in the treatment for introducing anisotropy into the coating film, the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA. In the case, first, the coating film 3 is formed on the substrate. As shown in FIG. 2A, the coating film 3 formed on the substrate has a structure in which the side chains 4 are randomly arranged. According to the random arrangement of the side chains 4 of the coating film 3, the mesogenic components and the photosensitive groups of the side chains 4 are also randomly oriented, and the coating film 2 is isotropic.

  In the second embodiment of the present invention, a side chain type having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) in the treatment for introducing anisotropy into the coating film. In the case of using a liquid crystal alignment film using a polymer, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, on the substrate The coating film 5 is formed. As shown in FIG. 3A, the coating film 5 formed on the substrate has a structure in which the side chains 6 are randomly arranged. According to the random arrangement of the side chain 6 of the coating film 5, the mesogenic component and the photosensitive group of the side chain 6 are also randomly oriented, and the side chain type polymer film 5 is isotropic.

  In the second embodiment of the present invention, liquid crystal alignment using a side chain type polymer having a structure having a light Fleece rearrangement group represented by the above formula (19) in the treatment for introducing anisotropy into the coating film In the case of using a film, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, first, the coating film 7 is formed on the substrate. . As shown in FIG. 4A, the coating film 7 formed on the substrate has a structure in which the side chains 8 are arranged at random. According to the random arrangement of the side chains 8 of the coating film 7, the mesogenic components and the photosensitive groups of the side chains 8 are also randomly oriented, and the coating film 7 is isotropic.

  In the first embodiment of the present invention, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 1 is formed. On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 1B, the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 2a that has undergone photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet light, and as a result, very small anisotropy is imparted to the coating film 1.

  In the first embodiment, when the ultraviolet irradiation amount in the step [II] is in the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the isotropic coating film 3 is formed. On the other hand, polarized ultraviolet rays are irradiated. Then, as shown in FIG. 2B, the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to dimerization reaction or the like. Causes a photoreaction. As a result, the density of the side chain 4a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, a small anisotropy is imparted to the coating film 3.

  In the second embodiment of the present invention, using a liquid crystal alignment film using a photoisomerizable group or a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (18), [II] When the ultraviolet ray irradiation amount in the step is in the range of 1% to 70% of the ultraviolet ray irradiation amount that maximizes ΔA, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. Then, as shown in FIG. 3 (b), the photosensitive group of the side chain 6a having the photosensitive group among the side chains 6 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 6a subjected to photoreaction becomes slightly higher in the polarization direction of the irradiated ultraviolet rays, and as a result, very small anisotropy is imparted to the coating film 5.

  In the second embodiment of the present invention, the amount of ultraviolet irradiation in the step [II] is obtained using a coating film using a side chain polymer having a structure having a photo-Fleece rearrangement group represented by the above formula (19). Is within the range of 1% to 70% of the amount of UV irradiation that maximizes ΔA, the isotropic coating film 7 is irradiated with polarized UV light. Then, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having the photosensitive group among the side chains 8 arranged in a direction parallel to the polarization direction of the ultraviolet rays is preferentially subjected to light fleece rearrangement or the like. Causes a photoreaction. As a result, the density of the side chain 8a that has undergone photoreaction increases in the polarization direction of the irradiated ultraviolet light, and as a result, small anisotropy is imparted to the coating film 7.

  Next, in the first embodiment, in the case where the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 1 after polarized light irradiation Is heated to a liquid crystal state. Then, as shown in FIG.1 (c), in the coating film 1, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. In this case, since the amount of the crosslinking reaction generated in the direction parallel to the polarization direction of the irradiated ultraviolet ray is very small, this crosslinking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is higher than the liquid crystallinity in the parallel direction, and the side chain 2 containing the mesogenic component is reoriented by self-organizing in the direction parallel to the polarization direction of the irradiated ultraviolet light. As a result, the very small anisotropy of the coating film 1 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 1.

  Similarly, in the first embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 15% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film after polarized light irradiation 3 is heated to a liquid crystal state. Then, as shown in FIG. 2C, in the side chain type polymer film 3, the amount of the generated crosslinking reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet rays and the direction perpendicular thereto. Therefore, the side chain 4 containing the mesogenic component is reoriented by self-organizing in a direction parallel to the polarization direction of the irradiated ultraviolet light. As a result, the small anisotropy of the coating film 3 induced by the photocrosslinking reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 3.

  Similarly, in the second embodiment, a coating film using a side-chain polymer having a structure having a photo-isomerizable group or a photo-Fleece rearrangement group represented by the above formula (18) is used. Then, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 5 after the polarized light irradiation is heated to be in a liquid crystal state. Then, as shown in FIG.3 (c), in the coating film 5, the quantity of the produced | generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of irradiation ultraviolet rays, and a perpendicular | vertical direction. In this case, since the liquid crystal alignment force of the light fleece rearrangement generated in the direction perpendicular to the polarization direction of the irradiated ultraviolet light is stronger than the liquid crystal alignment force of the side chain before the reaction, it is self-organized in the direction perpendicular to the polarization direction of the irradiated ultraviolet light. The side chain 6 containing the mesogenic component is reoriented. As a result, the very small anisotropy of the coating film 5 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 5.

  Similarly, in the second embodiment, a coating film using a side chain type polymer having a structure having a photofleece rearrangement group represented by the above formula (19) is used. When the ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount that maximizes ΔA, the coating film 7 after irradiation with polarized light is heated to a liquid crystal state. Then, as shown in FIG. 4 (c), in the side chain polymer film 7, the amount of the generated light fleece rearrangement reaction differs between the direction parallel to the polarization direction of the irradiated ultraviolet light and the direction perpendicular thereto. . Since the anchoring force of the optical fleece rearrangement 8 (a) is stronger than that of the side chain 8 before the rearrangement, when a certain amount or more of the optical fleece rearrangement occurs, it is self-assembled in a direction parallel to the polarization direction of the irradiated ultraviolet light. The side chain 8 containing the mesogenic component is reoriented. As a result, the small anisotropy of the coating film 7 induced by the photofleece rearrangement reaction is amplified by heat, and a larger anisotropy is imparted to the coating film 7.

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

  And in the coating film used for the method of this invention, the irradiation amount of the polarized ultraviolet-ray to a coating film, and the heating temperature in heat processing are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.

  The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film. Corresponds to the irradiation amount of polarized ultraviolet rays to optimize the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, if the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups on the side chain, the amount of photoreaction is not sufficient. . In that case, sufficient self-organization does not proceed even after heating. On the other hand, as a result of irradiating polarized ultraviolet rays to the structure having a photocrosslinkable group in the coating film used in the present invention, the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating. In addition, when the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.

  Therefore, in the coating film used in the present invention, the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferable to make it 0.1 mol%-40 mol% of the photosensitive group which has, and it is more preferable to set it as 0.1 mol%-20 mol%. By making the amount of the photo-reactive side chain photosensitive group within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and the formation of highly efficient anisotropy in the film is possible. Become.

  In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.

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

  In the production method of the present invention, the irradiation amount of polarized ultraviolet rays on the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet rays realizing ΔAmax. More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays realizing ΔAmax is 0. 0% of the entire photosensitive group of the side chain polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

  From the above, in the production method of the present invention, in order to achieve highly efficient anisotropy introduction into the coating film, a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. 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 irradiation with polarized ultraviolet light is desirably 90 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.

  By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.

  As described above, the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.

Abbreviations used in the examples are as follows.
(Methacrylic monomer)
The following MA3 was used. The MA3 was synthesized by a synthesis method described in non-patent literature (Macromolecules 2002, 35, 706-713).

(Organic solvent)
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve _CH 2 Cl _2: dichloromethane (polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile (RAFT agent)
CPDT: 2-cyano-2-propyldodecyl trithiocarbonate

[Measurement of phase transition temperature]
The liquid crystal phase transition temperature of the polymer obtained in the example was measured using differential scanning calorimetry (DSC) DSC3100SR (manufactured by Mac Science).

<Example 1>
MA3 (10.29 g, 20.0 mmol) was dissolved in NMP (94.1 g), deaerated with a diaphragm pump, and then AIBN (0.164 g, 1.0 mmol) was added to deaerate again. . Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain methacrylate polymer powder (C). The number average molecular weight of this polymer was 19000, and the weight average molecular weight was 39000.

The liquid crystal phase transition temperature of the obtained methacrylate polymer was 150 ° C to 300 ° C.
CH ₂ Cl ₂ (99.0 g) was added to the obtained methacrylate polymer powder (C) (1.0 g), and the mixture was stirred and dissolved at room temperature for 5 hours to obtain a liquid crystal aligning agent (C1).

[Production of liquid crystal cell]
Using the liquid crystal aligning agent (C1) obtained above, a liquid crystal cell was prepared according to the procedure shown below.
The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
The pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 μm, and the distance between the electrode elements is 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji.
Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
The liquid crystal aligning agent (C1) obtained above was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Subsequently, after irradiating 300 mJ / cm < ² > of ultraviolet rays of 313 nm through the polarizing plate to the coating-film surface, it heated for 10 minutes with a 180 degreeC hotplate, and obtained the board | substrate with a liquid crystal aligning film.

Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. A liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element is injected into the empty cell by a reduced pressure injection method by injecting liquid crystal MLC-2041 (Merck Co., Ltd.), sealing the injection port. Obtained.
When the alignment state of the liquid crystal cell was confirmed, alignment defects such as fluid alignment were not observed, and it was confirmed that the liquid crystal was aligned well.

<Example 2>
MA3 (10.3 g, 20.0 mmol) was dissolved in THF (94.0 g) and deaerated with a diaphragm pump, and then AIBN (0.098 g, 0.6 mmol) was added and deaerated again. . Thereafter, the mixture was reacted at 50 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (1000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder (P5). The number average molecular weight of this polymer was 39,000 and the weight average molecular weight was 81,000.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. No alignment failure such as fluid alignment was observed, and it was confirmed that the liquid crystal was well aligned.

<Example 3>
In Example 2, methacrylate polymer powder (P6) was obtained in the same manner as in Example 2, except that AIBN (0.036 g, 0.22 mmol) was used instead of AIBN (0.098 g, 0.6 mmol). The number average molecular weight of this polymer was 59,000, and the weight average molecular weight was 118,600.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. No alignment failure such as fluid alignment was observed, and it was confirmed that the liquid crystal was well aligned.

<Example 4>
Degassing was performed by dissolving MA3 (3.7 g, 7.2 mmol), CPDT (252 mg, 0.73 mmol), and AIBN (46 mg, 0.28 mmol) in THF (30 ml). Then, after heating at 55 ° C. for 1 day, the solution was poured into diethyl ether to obtain a light yellow polymer. The polymer was purified three times by reprecipitation from chloroform to diethyl ether to obtain a polymer (2.6 g, yield 64 wt%). The obtained polymer was dissolved in chloroform together with n-butylamine, and after stirring, the resulting solution was poured into diethyl ether to obtain a colorless methacrylate polymer (P2). The polymer (P2) was purified twice by reprecipitation from chloroform to diethyl ether.
The number average molecular weight of this polymer (P2) was 4,600, and the weight average molecular weight was 6,600.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. No alignment failure such as fluid alignment was observed, and it was confirmed that the liquid crystal was well aligned.

<Example 5>
The CPDT / MA3 / AIBN molar ratio in Example 4 was changed from Example 4 (0.73 / 7.2 / 0.28) to Example 5 (0.064 / 1.3 / 0.025). A methacrylate polymer (P3) was obtained in the same manner as in Example 4 except that.
The number average molecular weight of this polymer (P3) was 10,200, and the weight average molecular weight was 12,000.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. No alignment failure such as fluid alignment was observed, and it was confirmed that the liquid crystal was well aligned.

<Example 6>
The molar ratio of CPDT / MA3 / AIBN in Example 4 was changed from Example 4 (0.73 / 7.2 / 0.28) to Example 6 (0.067 / 4 / 0.026). A methacrylate polymer (P4) was obtained in the same manner as in Example 4.
The number average molecular weight of this polymer (P4) was 18,200, and the weight average molecular weight was 22,200.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. No alignment failure such as fluid alignment was observed, and it was confirmed that the liquid crystal was well aligned.

<Comparative Example 1>
The molar ratio of CPDT / MA3 / AIBN in Example 4 was changed from Example 4 (0.73 / 7.2 / 0.28) to Comparative Example 1 (1.4 / 7 / 0.56). A methacrylate polymer (P1) was obtained in the same manner as in Example 4.
The number average molecular weight of this polymer (P1) was 3,100, and the weight average molecular weight was 4,800.
Using this polymer powder, a liquid crystal aligning agent was prepared in the same manner as in Example 1, and using the liquid crystal aligning agent, a liquid crystal cell was prepared in the same manner as in Example 1, and the alignment state was confirmed. Defective orientation such as fluid orientation was observed.
In addition, the synthesis scheme of the methacrylate polymers P1 to P6 of Examples 2 to 6 and Comparative Example 1 is shown below.

<< Anisotropy expression >>
It was measured whether or not anisotropy was developed for the methacrylate polymers P1 to P6 obtained in Examples 2 to 6 and Comparative Example 1.
<Measurement sample>
A methylene chloride solution (1 w / w%) of each methacrylate polymer was prepared, the solution was spin-coated on a quartz substrate, and dried on a hot plate at 70 ° C. for 90 seconds to obtain a polymer film (0.1-0. 2 μm) was obtained.
After irradiating the polymer film with ultraviolet rays of 314 nm from 3 mJ / cm ² to 3 J / cm ² through the polarizing plate (the photoreactive amount of the photoreactive side chain of the polymers P1 to P6 is up to 40 mol%) Corresponding), the S value and DP (Degree of photoreaction) value at a wavelength of 314 nm were determined by heating on a hot plate at 180 ° C. for 10 minutes, and the anisotropy was examined.

The S _λ value at the wavelength λ is a measure for measuring the anisotropy. Specifically, A s _(in the direction perpendicular to the electric field vector of the polarized ultraviolet light, the absorbance at a given wavelength lambda) in and A _{p (A s} values the same wavelength lambda, in a direction parallel to the electric field vector of the polarized ultraviolet (Absorbance) is obtained by the following equation. Incidentally, the magnitude of the measured values of the measurements and A _p of A _s, obtained by dividing into the following i) or ii).

  The DP value is an indicator of the progress of the reaction due to a change in absorbance of UV absorption. Specifically, when the cinnamoyl group in the film is not reacted at all, the UV absorption state (before light irradiation) at a certain wavelength indicated by the cinnamoyl group is set to 0%, and after the light irradiation, UV indicating the cinnamoyl group. It is a value converted with 100% as the state where absorption is completely lost.

FIG. 5 is a graph showing the anisotropy of the methacrylate polymers P1 to P6 obtained in Examples 2 to 6 and Comparative Example 1. In FIG. 5, the vertical axis indicates the S value at a wavelength of 314 nm, and the horizontal axis indicates the DP value.
As can be seen from FIG. 5, the maximum S value for P3 to P6 exceeds 0.7. It can also be seen that the maximum value of S value for P2 exceeds 0.2. On the other hand, it can be seen that the maximum S value for P1 is about 0.1. Generally, it is said that when the maximum value of S value exceeds 0.2, anisotropy appears. From this, it can be seen that the methacrylate polymers P2 to P6 (number average molecular weight 4,600 to 59,000) of Examples 2 to 6 exhibit anisotropy. In particular, the methacrylate polymers P3 to P6 of Examples 2-3 and 5-6 (number average molecular weights 10,200-59,000) have S values exceeding 0.7, and anisotropy is exhibited. It can be seen that is remarkable. On the other hand, in the methacrylate polymer P1 (number average molecular weight 3,100) of Comparative Example 1, the maximum value of S is about 0.1, indicating that anisotropy does not appear.

FIG.
1 Side chain polymer membrane 2, 2a Side chain Fig. 2
3 Side chain polymer membrane 4, 4a Side chain Fig. 3
5 Side chain polymer membrane 6, 6a Side chain Fig. 4
7 Side chain polymer membrane 8, 8a Side chain

Claims (15)

[I] (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and having a number average molecular weight of 4,000 or more, and (B) an organic solvent. Applying the polymer composition to the substrate having a conductive film for driving a transverse electric field to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
The manufacturing method of the board | substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements by which orientation control ability was provided by having.   The method according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition. The component (A) is represented by the following formulas (1) to (6)
(In the formula, A, B and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO; Represents —O— or —O—CO—CH═CH—;
S is an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced by a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded thereto may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
Cou represents coumarin-6-yl group or a coumarin-7-yl group, _-NO 2 are each a hydrogen atom bonded to them _{independently, -CN, -CH = C (CN} ) 2, -CH = CH- May be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently a single bond, 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. Is a group selected from However, when X is —CH═CH—CO—O— or —O—CO—CH═CH—, P or Q on the side to which —CH═CH— is bonded is an aromatic ring;
H and I are each independently a group selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and combinations thereof. )
The method of Claim 1 or 2 which has any one sort of photosensitive side chain chosen from the group which consists of.

The component (A) is represented by the following formulas (7) to (10)
(In the formula, A, B and D are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO; Represents —O— or —O—CO—CH═CH—;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (provided that when n = 0, B is a single bond);
Y ₂ is a group selected from the group consisting of a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, The hydrogen atoms bonded to each independently represent —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ).
The method of Claim 1 or 2 which has any one sort of photosensitive side chain chosen from the group which consists of.

The component (A) is represented by the following formulas (11) to (13)
(In the formula, each A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or a phase selected from those substituents. A group in which different 2 to 6 rings are bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently -COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5). represents an alkyl _{group), - NO 2, -CN,} -CH = C (CN) 2, -CH = CH-CN, a halogen group, an alkyl group of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms (It may be substituted with an oxy group, or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms)
The method of Claim 1 or 2 which has any one sort of photosensitive side chain chosen from the group which consists of.

(A) component is the following formula (14) or (15)
(In the formula, each A is independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O—, Or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3)
The method of Claim 1 or 2 which has the photosensitive side chain represented by these.

The component (A) is represented by the following formula (16) or (17) (wherein A is a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—). , -CH = CH-CO-O-, or -O-CO-CH = CH-;
X is a single bond, —COO—, —OCO—, —N═N—, —C═C—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
l represents an integer of 1 to 12, and m represents an integer of 0 to 2)
The method of Claim 1 or 2 which has the photosensitive side chain represented by these.

(A) component is a following formula (18) or (19)
(In the formula, A and B are each independently a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—O; -Represents-or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, and m1 and m2 represent an integer of 1 to 3;
R ₁ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. The method according to claim 1 or 2, which has any one kind of photosensitive side chain selected from the group consisting of (which represents an oxy group).

The component (A) is represented by the following formula (20) (wherein A represents a single bond, —O—, —CH ₂ —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH). = CH-CO-O- or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from those substituents. 2 to 6 different rings are groups bonded through a bonding group B, and the hydrogen atoms bonded to them are each independently —COOR ₀ (wherein R ₀ is a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group), —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. May be substituted with an alkyloxy group;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, —CH═CH—CO—O—, or —O—CO—CH═. Represents CH-;
The method according to claim 1 or 2, wherein l represents an integer of 1 to 12, and m represents an integer of 0 to 2.

(A) component is following formula (21)-(31) (In formula, A and B have the same definition as the above;
Y ₃ is a group selected from the group consisting of a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. And each hydrogen atom bonded thereto may be independently substituted with —NO ₂ , —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ is a hydrogen atom, —NO ₂ , —CN, —CH═C (CN) ₂ , —CH═CH—CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing A heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formulas (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28 ), The sum of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;
R ₂ is a hydrogen atom, —NO ₂ , —CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ each have a liquid crystalline side chain selected from the group consisting of a single bond, —CO—, —CH ₂ O—, —CH═N—, and —CF ₂ —. Item 10. The method according to any one of Items 1 to 9.

  The board | substrate which has the liquid crystal aligning film for horizontal electric field drive type liquid crystal display elements manufactured by the method as described in any one of Claims 1-10.   A lateral electric field drive type liquid crystal display device comprising the substrate according to claim 11. Preparing a substrate (first substrate) according to claim 11;
[I ′] On the second substrate (A) A side chain polymer having a number average molecular weight of 4,000 or more, which is a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, And (B) a step of applying a polymer composition containing an organic solvent to form a coating film;
[II ′] a step of irradiating the coating film obtained in [I ′] with polarized ultraviolet rays; and [III ′] a step of heating the coating film obtained in [II ′];
Obtaining a liquid crystal alignment film imparted with alignment control capability by having a second substrate having the liquid crystal alignment film; and [IV] liquid crystal alignment of the first and second substrates via liquid crystal A step of obtaining a liquid crystal display element by arranging the first and second substrates to face each other so that the films face each other;
A method for producing a liquid crystal display element, comprising obtaining a lateral electric field drive type liquid crystal display element.   A lateral electric field drive type liquid crystal display device manufactured by the method according to claim 13. (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range and having a number average molecular weight of 4,000 or more, and (B) an organic solvent. A composition for producing a liquid crystal alignment film for a horizontal electric field drive type liquid crystal display element.

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