KR20190070331A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention relates to (A) a polymer composition containing a copolymer obtained from a monomer mixture comprising the following monomer (A-1) and monomer (A-2). The monomer (A-1) refers to a monomer having a cinnamoyl moiety, 2 to 4 benzene rings which do not constitute a cinnamoyl moiety, and a monomer having a polymerizable group. The monomer (A-2) A benzene ring which does not constitute a cinnamoyl moiety, and a monomer having a polymerizable group (the cinnamoyl moiety and the benzene ring may have a substituent). The present invention also provides a liquid crystal alignment film comprising a step of coating the composition on a substrate having a conductive film for transverse electric field driving to form a coating film, a step of irradiating the obtained coating film with polarized ultraviolet rays, and a step of heating the obtained coating film The present invention relates to a method of manufacturing a substrate. The liquid crystal aligning agent using the polymer composition according to the present invention is capable of imparting orientation control ability with high efficiency and having excellent burning property and capable of providing a transverse electric field driven liquid crystal display element.

Description

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

The present invention relates to a novel polymer composition, a liquid crystal alignment film using the same, and a method of producing a substrate having the alignment film. And a novel method for manufacturing a liquid crystal display element having excellent tilt angle characteristics.

BACKGROUND ART Liquid crystal display devices are known as lightweight, thin and low power consumption display devices, and recently, they have been used for a large-sized television application and have achieved remarkable development. The liquid crystal display element is constituted by sandwiching the liquid crystal layer by a pair of transparent substrates having electrodes, for example. In the liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that the liquid crystal is in a desired alignment state between the substrates.

That is, the liquid crystal alignment film is formed as a constituent member of the liquid crystal display element on the surface of the substrate which holds the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. In addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate, for example, the liquid crystal alignment film may be required to control the pretilt angle of the liquid crystal. The ability to control the orientation of the liquid crystal in the liquid crystal alignment film (hereinafter, referred to as orientation control ability) is given by subjecting the organic film constituting the liquid crystal alignment film to an alignment treatment.

Conventionally, a rubbing method is known as an alignment treatment method of 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 a cotton, nylon or polyester in a predetermined direction, To orient the liquid crystal. This rubbing method has been used in a manufacturing process of a conventional liquid crystal display element since a relatively stable liquid crystal alignment state can be realized easily. As an organic film used for a liquid crystal alignment film, a polyimide-based organic film having excellent reliability and electrical characteristics such as heat resistance 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 oscillation or static electricity is a problem in some cases. In addition, since the liquid crystal display element of recent years has a high precision and the surface of the liquid crystal alignment film can not be uniformly rubbed with the cloth due to the irregularity caused by the electrode or the switching active element for driving the liquid crystal on the corresponding substrate, There was no case.

Therefore, a photo alignment method has been actively studied as another alignment treatment method of the liquid crystal alignment film not rubbed.

There are various methods for the photo alignment method, but 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 oriented in accordance with the anisotropy.

As a main photoalignment method, a photoalignment method of a decomposition type is known. For example, polarized ultraviolet rays are irradiated to the polyimide film, and anisotropic decomposition is generated by utilizing the polarization direction dependency of ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide left without decomposition (see Patent Document 1).

A photo-alignment method by a photo-crosslinking type is also known. For example, polyvinyl cinnamate is used and polarized ultraviolet rays are irradiated to generate a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Further, the polarized ultraviolet rays are irradiated in the oblique direction to express the pretilt angle (see Non-Patent Document 1). When a side chain type polymer having coumarin in the side chain is used, a photo-crosslinking reaction is caused in the coumarin portion of the side chain parallel to the polarized light by irradiation with polarized ultraviolet light, and the liquid crystal is aligned in the direction parallel to the polarization direction Non-patent document 2).

As described above, in the alignment treatment method of the liquid crystal alignment film by the photo alignment method, rubbing is not required, and there is no possibility of generation of oscillation or static electricity. In addition, it is possible to perform orientation treatment on a substrate of a liquid crystal display element having irregularities on its surface, which is a preferred method of alignment treatment of a liquid crystal alignment film in an industrial production process. Furthermore, since the alignment method can control the alignment direction by ultraviolet rays, it is possible to compensate for the viewing angle dependency by forming a plurality of regions (alignment division) in which the alignment directions are different in the pixel.

On the other hand, the liquid crystal alignment film is also responsible for imparting a certain tilt angle (the pretilt angle) to the liquid crystal, and the application of the pretilt angle has become an important issue in the development of the liquid crystal alignment film (see Patent Documents 1 to 4 ).

Here, it is known that a copolymer obtained from a monomer having a cinnamate ester structure and two benzene rings on a side chain exhibits optical alignment (see Patent Document 5). However, this copolymer has low solubility, and when used as a varnish, a solvent such as chloroform which can not be industrially used has to be used and it has been difficult to apply it as a liquid crystal aligning agent.

Japanese Patent Application Laid-Open No. 02-223916 Japanese Laid-Open Patent Publication No. 04-281427 Japanese Laid-Open Patent Publication No. 05-043687 Japanese Patent Application Laid-Open No. 10-333153 Japanese Patent Application Laid-Open No. 2000-212310

 S. Kobayashi et al., Journal of Photopolymer Science and Technology, Vol. 8, No. 2, pp 25-262 (1995).  M. Shadt et al., Nature. Vol. 381, 212 (1996).

As described above, the photo alignment method does not require the rubbing process itself as compared with the conventionally used rubbing method as an alignment processing method of a liquid crystal display element, and thus has a great advantage. In contrast, in the photo alignment method, the alignment control ability can be controlled by changing the irradiation amount of the polarized light, as compared with the rubbing method in which the alignment control ability is made substantially constant by rubbing. However, in the photo alignment method, when it is desired to achieve the same degree of alignment control ability as in the case of the rubbing method, a large amount of polarized light is required to be irradiated, or stable alignment of the liquid crystal may not be realized.

For example, in the decomposition-type photo-alignment method described in Patent Document 1 described above, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output power of 500 W for 60 minutes, and a large amount of ultraviolet irradiation It becomes necessary. In addition, even in the case of the diminution type or the photo-isomerization type photo-alignment method, a large amount of ultraviolet light irradiation of several tens to several tens J may be required. In the photo-alignment method of photo-crosslinking type or photo-isomerization type, thermal stability and optical stability of alignment of liquid crystal are inferior, and therefore, when a liquid crystal display element is used, orientation defects and display burn- .

Therefore, in the photo alignment method, it is required to achieve high efficiency of alignment treatment and realization of stable liquid crystal alignment, and a liquid crystal alignment film and a liquid crystal alignment agent capable of highly imparting a high alignment control ability to the liquid crystal alignment film can be performed with high efficiency.

A twisted nematic liquid crystal display element and an OCB liquid crystal display element having a substrate having a liquid crystal alignment film for a liquid crystal display element and having excellent alignment control ability with high efficiency and excellent tilt angle characteristics are provided. do.

It is another object of the present invention to provide a twisted nematic liquid crystal display element and an OCB type liquid crystal display element having improved tilt angle characteristics, and a liquid crystal alignment film for the element, in addition to the aforementioned objects.

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above-described problems and, as a result, have found the following inventions.

(1) A polymer composition comprising a copolymer obtained from a monomer mixture comprising (A) the following monomer (A-1) and the monomer (A-2)

Monomer (A-1): a monomer having a cinnamoyl moiety, 2 to 4 benzene rings which do not constitute a cinnamoyl moiety, and a polymerizable group.

Monomer (A-2): A monomer having a cinnamoyl moiety, a benzene ring not constituting a cinnamoyl moiety, and a polymerizable group.

(The cinnamoyl moiety and the benzene ring may have substituents).

<2> The polymer composition according to <1>, wherein the polymerizable group of the monomer (A-1) and the monomer (A-2) is an acrylic group or a methacryl group.

<3> The positive resist composition according to <1>, wherein the component (A) is a monomer having a polymerizable group bonded to any one group selected from the group consisting of a group represented by the following formula (1) desirable.

[Chemical Formula 1]

Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , represents an -OCO-, -CONH- or -NH-CO-;

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

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

When T is a single bond, B also represents a single bond;

Y ₁ is a divalent benzene ring;

P ₁ , Q ₁ and Q ₂ are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;

R ₁ is a hydrogen atom, -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

The hydrogen atoms bonded to the benzene ring in each of Y ₁ , P ₁ , Q ₁ and Q ₂ are independently selected from the group consisting of -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an (alkyl having 1 to 5 carbon atoms) carbonyl group, Or an alkyloxy group having 1 to 5 carbon atoms;

X ₁ and X ₂ each independently represent a single bond, -O-, -COO- or -OCO-;

n1 and n2 are each independently 0, 1 or 2;

When the number of X ₁ to be 2, and X may be the same or different each other and _1, when the number of X ₂ is 2, X ₂ may be the same with each other and may be different;

When the number of Q ₁ is 2, may be the same or different with each other even if Q _1, when the number of Q ₂ be the two, and may be the same or different each other and Q _2;

In the monomer (A-1), the sum of the number of benzene rings other than Y ₁ is 2 to 4;

In the monomer (A-2), the total number of benzene rings other than Y ₁ is 1;

The dashed line represents the bond with the polymerizable group.

&Lt; 4 &gt; [I] A process for forming a coating film by applying the polymer composition according to any one of &lt; 1 &gt; to &lt; 3 &gt;

[II] a step of irradiating polarized ultraviolet rays from the oblique direction onto the coating film obtained in [I]; And

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

To obtain a liquid crystal alignment film for a twisted nematic liquid crystal display element and an OCB type liquid crystal display element to which orientation control ability is imparted.

&Lt; 5 &gt; A substrate having a twisted nematic liquid crystal display device and / or a liquid crystal alignment film for an OCB type liquid crystal display device manufactured by the manufacturing method described in the &lt; 4 &gt;

&Lt; 6 &gt; A twisted nematic liquid crystal display device and an OCB type liquid crystal display device having the substrate of the above &lt; 5 &gt;.

&Lt; 7 &gt; preparing a substrate (first substrate) of &lt; 5 &gt;

[I '] a step of applying a polymer composition described in any one of <1> to <4> on a second substrate to form a coating film;

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

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

To obtain a liquid crystal alignment film imparted with orientation control ability, thereby obtaining a second substrate having the liquid crystal alignment film; And

[IV] A step of obtaining a liquid crystal display element by arranging the first and second substrates so as to face each other so that the liquid crystal alignment layers of the first and second substrates are opposed to each other through the liquid crystal so that the exposure directions are orthogonal to each other;

To obtain a twisted nematic liquid crystal display element and an OCB type liquid crystal display element.

<8> A twisted nematic liquid crystal display device and an OCB-type liquid crystal display device manufactured by the method of <7>.

According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film having a high controllability of orientation and excellent tilt angle characteristics, a twisted nematic liquid crystal display device having the substrate, and an OCB type liquid crystal display device.

Since the twisted nematic liquid crystal display element and the OCB liquid crystal display element manufactured by the method of the present invention are given high-efficiency orientation control capability, the display characteristics are not hindered even if the liquid crystal display element is continuously driven for a long period of time.

The liquid crystal aligning agent used in the production method of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter, simply referred to as a side chain type polymer), and a liquid crystal aligning agent obtained by using the above liquid crystal aligning agent The coating film is a film having a photosensitive side chain type polymer capable of exhibiting liquid crystallinity. This coating film is subjected to orientation treatment by polarized irradiation without rubbing treatment. After the polarized light irradiation, the side chain type polymer film is heated to form a coating film (hereinafter, also referred to as a liquid crystal alignment film) imparted with orientation control ability. At this time, a slight anisotropy expressed by polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment can be realized as a liquid crystal alignment film, and a liquid crystal alignment film having high alignment control ability can be obtained.

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

&Lt; Manufacturing Method of Substrate Having Liquid Crystal Alignment Film &gt; &lt; Production Method of Liquid Crystal Display Element &

<< (A) Side chain type polymer >>

The component (A) is a copolymer (hereinafter also referred to as a side chain type polymer) obtained from a monomer mixture containing the following monomer (A-1) and the monomer (A-2).

Monomer (A-1): a monomer having a cinnamoyl moiety, 2 to 4 benzene rings which do not constitute a cinnamoyl moiety, and a polymerizable group.

Monomer (A-2): A monomer having a cinnamoyl moiety, a benzene ring not constituting a cinnamoyl moiety, and a polymerizable group.

(The cinnamoyl moiety and the benzene ring may have substituents).

Examples of the substituent include a methyl group, a methoxy group, a tertiary butyl group, an acetyl group, a fluorine group and a cyano group.

The side chain type polymer (A) has a side chain having photosensitivity to the main chain and is capable of reacting with light to cause a crosslinking reaction and an isomerization reaction. The structure of the side chain having photosensitivity is not particularly limited, but a structure that causes a crosslinking reaction in response to light is preferable. In this case, even when exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time.

More specific examples of the side chain polymer structure of the component (A) include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide , A radical polymerizable group such as norbornene, and a siloxane, and a side chain comprising at least one of the following formulas (1) and (2) .

(2)

Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , represents an -OCO-, -CONH- or -NH-CO-;

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

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

When T is a single bond, B also represents a single bond;

Y ₁ is a divalent benzene ring;

P ₁ , Q ₁ and Q ₂ are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;

R ₁ is a hydrogen atom, -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

The hydrogen atoms bonded to the benzene ring in each of Y ₁ , P ₁ , Q ₁ and Q ₂ are independently selected from the group consisting of -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an (alkyl having 1 to 5 carbon atoms) carbonyl group, Or an alkyloxy group having 1 to 5 carbon atoms;

X ₁ and X ₂ each independently represent a single bond, -O-, -COO- or -OCO-;

n1 and n2 are each independently 0, 1 or 2;

When the number of X ₁ to be 2, and X may be the same or different each other and _1, when the number of X ₂ is 2, X ₂ may be the same with each other and may be different;

When the number of Q ₁ is 2, may be the same or different with each other even if Q _1, when the number of Q ₂ be the two, and may be the same or different each other and Q _2;

In the monomer (A-1), the sum of the number of benzene rings other than Y ₁ is 2 to 4;

In the monomer (A-2), the total number of benzene rings other than Y ₁ is 1;

The dashed line represents the bond with the polymerizable group.

The content of the side chain derived from (A-1) in the total of the content of the side chain derived from (A-1) and the content of the side chain derived from (A-2) in the side chain polymer of the present invention, Is preferably 10% by mole to 90% by mole, more preferably 20% by mole to 80% by mole, still more preferably 30% by mole to 70% by mole in view of the liquid crystal alignability and solubility of the side chain type polymer.

The side chain type polymer of the present invention may contain other side chains other than the side chain derived from (A-1) and the side chain derived from (A-2), within the range that does not impair the effect of the present invention do. The content thereof is the remaining part when the total content of the photoreactive side chain and the liquid crystalline side chain does not reach 100%.

<< Preparation of Photosensitive Side Chain Polymer >>

The photosensitive side chain type polymer capable of exhibiting liquid crystallinity can be obtained by polymerizing a monomer mixture containing at least the monomer (A-1) and the monomer (A-2).

[Monomer (A-1) and Monomer (A-2)] [

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

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

More specific examples of the monomer (A-1) and the monomer (A-2) include hydrocarbons such as hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates,? -Methylene-? -Butyrolactones, , A polymerizable group composed of at least one kind selected from the group consisting of a radically polymerizable group such as maleimide and norbornene and a trialkoxysilyl group and a photosensitive side chain selected from the structures represented by the above formulas (1) and (2) Is preferable.

The polymerizable group is preferably selected from groups represented by the following formulas PG1 to PG8. Among them, an acrylic group or methacryl group represented by PG1 is preferable from the viewpoints of easy control of the polymerization reaction and stability of the polymer. In the formula, the broken line represents a bonding bond to the photosensitive side chain represented by the above formula (1) or (2).

(3)

(In the formula PG1, M ¹ is a hydrogen atom or a methyl group.)

Examples of the monomer (A-1) include monomers selected from the following formulas A-1-1 to A-1-7.

[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas A-1-1 to A-1-7, PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, s1 and s2 each independently represent the number of methylene groups, Is the natural number of.

Examples of the monomer (A-2) include monomers selected from the following formulas A-2-1 to A-2-14.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the formulas A-2-1 to A-2-14, PG represents a polymerizable group selected from the groups represented by the above formulas PG1 to PG8, s1 and s2 each independently represent the number of methylene groups, Is the natural number of.

Any of the monomers (A-1) and (A-2) is commercially available, and any of them can be produced by, for example, the method described in International Patent Application Publication No. WO2014 / 074785.

The side chain type polymer (A) can be obtained by the copolymerization reaction of the above-mentioned monomer (A-1) and the monomer (A-2). Further, it can be copolymerized with other monomers within a range that does not inhibit the liquid crystalline property.

When the polymerizable group of the monomers (A-1) and (A-2) is a radically polymerizable group, the other monomers include, for example, industrially available monomers capable of radical polymerization.

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

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

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 , 2-trifluoroethyl acrylate, tert-butyl acrylate, lauryl acrylate, palmitylacrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol Acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 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, anthrylmethyl methacrylate Methacrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate, Methoxyethyl methacrylate, methoxy triethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl Adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate To The.

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

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

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

The content of the photoreactive side chain represented by (A-1) and (A-2) in the side chain polymer of the present invention is preferably from 10 mol% to 100 mol% , More preferably from mol% to 100 mol%, still more preferably from 30 mol% to 100 mol%.

The method for producing the side chain type 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 cation polymerization, radical polymerization or anionic polymerization using a vinyl group of the (A-1) or (A-2) monomer. Of these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.

The conditions such as the polymerization initiator for radical polymerization, the reaction temperature, the solvent and the like may be those known in the International Patent Application Publication No. WO2014 / 074785.

[Production method of polysiloxane]

When the polymer (A) used in the present invention is a polysiloxane, the method for obtaining the polysiloxane is not particularly limited. In the present invention, the monomer (A-1) and the monomer (A-2) are obtained by condensing an alkoxysilane mixture containing an monomer essentially consisting of a trialkoxysilyl group as a polymerizable group in an organic solvent. Usually, the polysiloxane is obtained as a solution in which such alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.

In the present invention, an alkoxysilane represented by the following formula (3) may be used in addition to the aforementioned monomer (A-1) and the monomer (A-2). Since the alkoxysilane represented by the formula (3) can impart various properties to the polysiloxane, one or more kinds of alkoxysilanes can be selected depending on the required characteristics.

(R ⁵ is a hydrogen atom, or a hetero atom, a halogen atom, an amino group, a glycidyl sidok group, mercapto group, isocyanate group or ureide group is, of the number of carbon atoms from 1 to 6 hydrocarbon group which may substituted, R ⁶ is An alkyl group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.)

R ⁵ of the alkoxysilane represented by the formula (3) is a hydrogen atom or an organic group having 1 to 6 carbon atoms (hereinafter, also referred to as a third organic group). Examples of the third organic group include aliphatic hydrocarbons; Ring structures such as aliphatic rings, aromatic rings and heterocyclic rings; Unsaturated bonds; And a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, or an organic group having 1 to 6 carbon atoms, which may have a branched structure. Furthermore, the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureide group, or the like.

Specific examples of the alkoxysilane represented by the formula (3) are shown below, but the invention is not limited thereto.

Specific examples of the alkoxysilane in the case where R ⁵ is a hydrogen atom in the alkoxysilane of the formula (3) include trimethoxysilane, triethoxysilane, tripropoxysilane and tributoxysilane .

Specific examples of the alkoxysilane in the case where R ⁵ is a tertiary organic group in the alkoxysilane of the formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, Triethoxysilane, triethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) , 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane , 3-isocyanate propyltriethoxysilane, trifluoropropyltrimethoxysilane, But are not limited to, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane,? -Ureidopropyltriethoxysilane,? -Urea,? - urea Isopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, and the like.

The polysiloxane to be used in the present invention is preferably an alkoxysilane represented by the above-mentioned formula (3) in an amount of 1 or more, preferably 1 to 3, in order to prevent adhesion of the polysiloxane to the substrate, Or may have a plurality of species.

In the alkoxysilane represented by the formula (3), the alkoxysilane wherein n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it is easily condensed with the alkoxysilane represented by the formula (1) and the formula (2).

As the alkoxysilane in which n is 0 in the formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetra Lt; / RTI &gt; is preferred.

As a method for polycondensation of polysiloxane, a method described in International Patent Application Publication No. WO2010 / 126108 can be used.

[Recovery of Polymer]

In the case of recovering the resulting polymer from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above-described reaction, the reaction solution may be put into a poor solvent to precipitate the polymer . Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or under normal pressure. Further, when the polymer precipitated and collected is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the side chain type polymer (A) of the present invention is preferably such that the weight average molecular weight measured by GPC (Gel Permeation Chromatography) Preferably from 2,000 to 1,000,000, and more preferably from 5,000 to 100,000.

<Organic solvent>

The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent dissolving the resin component. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- Dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, But are not limited to, hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol- Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl Methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used alone or in combination.

<Liquid Crystal Aligner>

A liquid crystal aligning agent is applied to the side of the substrate where the electrodes are formed.

The liquid crystal aligning agent of the present invention uses a polymer composition according to the present invention and contains (A) a copolymer obtained from a monomer mixture containing the monomer (A-1) and the monomer (A-2).

[Preparation of liquid crystal aligning agent]

The liquid crystal aligning agent used in the present invention is preferably prepared as a coating liquid so as to be suitable for formation of a liquid crystal alignment film. That is, the liquid crystal aligning agent used in the present invention is preferably prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component is a resin component including the side chain type polymer which is the component (A) described above. At this time, 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 liquid crystal aligning agent of the present invention, the above-mentioned resin component may be a side chain type polymer as a whole component (A), but other polymers other than these may be mixed within a range not inhibiting the liquid crystal aligning ability. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such other polymers include, for example, polymers other than the side-chain type polymer as the component (A), such as poly (meth) acrylate, polyamic acid and polyimide.

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

Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, 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 monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, 1-hexanol, n-pentane, n-pentane, n-octane, diethyl ether , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, Propoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, And a solvent having a low surface tension such as 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, .

These poor solvents may be used alone or in combination. When the above-mentioned solvent is used, the solvent is preferably 5% by mass to 80% by mass, more preferably 20% by mass, more preferably 20% by mass or less, such that the solubility of the solvent contained in the polymer composition is not significantly lowered. Mass% to 60 mass%.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, it is possible to use, for example, EFTAX (registered trademark) 301, EF303, EF352 (manufactured by Tohchem Products), Megapack (registered trademark) F171, F173, R- (Manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by AGC Seiyam Chemical Co., Ltd.) ) And the like. 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 by mass based on 100 parts by mass of the resin component contained in the polymer composition.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

In addition to the improvement in adhesion between the substrate and the liquid crystal alignment film, for the purpose of preventing deterioration of electric characteristics due to the backlight when the liquid crystal display device is constituted, additives such as phenol- Or may be contained in the alignment agent. Specific phenoplast-based additives are shown below, but are not limited to these structures.

[Chemical Formula 9]

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, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

In the case of using a compound improving the adhesion with the substrate, the amount of the compound used is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 100 parts by mass, relative to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

A photosensitizer may also be used as an additive. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- (alpha -naphthoylmethylene) -3 -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (p-naphthoylmethylene) - 3-methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- (4-biphenoylmethylene) Methyl-beta-naphthooxazoline, 2- (4-biphenoylmethylene) -3-methyl- beta -naphthoxazoline, 2- (p- fluorobenzoylmethylene) Nitroaniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroasnamphthylene), (2 - [(m-hydroxy- (2-naphthalene), 2-naphthalene, 2-naphthalene, 2-naphthalene, 2-naphthalene, Carboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocoumarin, and the like.

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

A method of manufacturing a substrate having a liquid crystal alignment film of the present invention includes:

[I] a step of coating a side-chain polymer (A) and a liquid crystal aligning agent containing an organic solvent on a substrate having a transparent electrode to form a coating film;

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

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

Respectively.

By this process, a liquid crystal alignment film for a 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.

In addition to the obtained substrate (first substrate), a liquid crystal display element can be obtained by preparing a second substrate.

The second substrate can obtain a second substrate having a liquid crystal alignment film to which orientation control ability is imparted by using the above-mentioned steps [I] to [III] on a second substrate having a transparent electrode.

A method of manufacturing a twisted nematic liquid crystal display element and an OCB type liquid crystal display element,

[IV] A step of obtaining the liquid crystal display element by arranging the first and second substrates obtained above so as to oppose each other through the liquid crystal so that the liquid crystal alignment layers of the first and second substrates are opposed to each other;

Respectively. Thus, a twisted nematic liquid crystal display device can be obtained.

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

&Lt; Process [I] &gt;

In Process [I], a coating film is formed by applying a side chain polymer (A) and a liquid crystal aligning agent containing an organic solvent onto a substrate having a liquid crystal driving electrode.

<Substrate>

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

As electrodes for liquid crystal driving, indium tin oxide (ITO) and indium zinc oxide (IZO) are preferably used. In a reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used for the electrode in this case.

As a method for forming an electrode on a substrate, a conventionally known method can be used.

The method of applying the above-described liquid crystal aligning agent on a substrate having an electrode for driving a liquid crystal is not particularly limited.

As a coating method, a method generally carried out by screen printing, offset printing, flexographic printing, inkjet printing or the like is generally used. Examples of other application methods include a dip method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spray method, and the like, depending on the purpose.

After the liquid crystal aligning agent is applied onto the substrate having the liquid crystal driving electrode, the liquid crystal aligning agent is heated to 50 to 230 DEG C, preferably 50 to 200 DEG C, by heating means such as a hot plate, a heat circulation type oven or an IR The solvent can be evaporated for 0.4 to 60 minutes, preferably 0.5 to 10 minutes, to obtain a coating film. The drying temperature at this time is preferably lower than the temperature range at which the side chain polymer of the side chain type polymer as component (A) exhibits liquid crystallinity (hereinafter referred to as liquid crystal temperature).

The thickness of the coating film is disadvantageous from the viewpoint of the power consumption of the liquid crystal display element if it is too thick, and the reliability of the liquid crystal display element is deteriorated when it is too thin. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 Nm to 150 nm.

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

&Lt; Process [II] &gt;

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

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The amount of irradiation is set such that the amount of the polarized ultraviolet light that realizes the maximum value of? A (hereinafter also referred to as? Amma), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction , More preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.

The irradiation direction of the polarized ultraviolet ray is usually 1 to 89 degrees with respect to the substrate, but preferably 10 to 80 degrees, and particularly preferably 20 to 70 degrees. When the angle is too small, there is a problem that the pretilt angle becomes small. When the angle is excessively large, there is a problem that the pretilt angle is high.

As a method of adjusting the irradiation direction at the above-mentioned angle, there are a method of tilting the substrate itself and a method of tilting the light source, but it is more preferable to tilt the light source itself from the viewpoint of throughput.

As the obtained pretilt angle, a pretilt angle suitable for the twisted nematic mode is preferably 1 deg. To 20 deg., More preferably 2 deg. To 15 deg..

Further, in the present invention, it is also possible to control the tilt angle by adjusting the irradiation amount, the irradiation time, or both of the step [II].

&Lt; Process [III] &gt;

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

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

The heating temperature is preferably within the temperature range of the temperature at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal forming temperature). In the case of a thin film surface such as a coating film, the liquid crystal temperature at the surface of the coating film is expected to be lower than the liquid crystal temperature when the side chain polymer (A) is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal forming temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet light is set to a temperature lower by 10 占 폚 than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer used and a temperature 10 占 폚 lower than the upper limit of the liquid crystal temperature range It is preferable that the temperature is in the range of the upper limit. If the heating temperature is lower than the above temperature range, the amplifying effect of anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is too high than the above temperature range, the state of the coating film becomes isotropic liquid state (isotropic phase) And in this case, it may become difficult to reorient in one direction by self-organization.

The liquid crystal display temperature is preferably not lower than the glass transition temperature (Tg) at which phase transition occurs from the solid phase to the liquid crystal phase of the side chain type polymer or coating film surface, and is the isotropic phase transition temperature (isotropic phase transition temperature (Tiso) or less.

In the present invention, it is also possible to control the tilt angle by adjusting the heating temperature, the heating time, or both of the step [III].

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 the above process, the production method of the present invention can realize introduction of anisotropy into the coating film with high efficiency. Then, a liquid crystal alignment film-attached substrate can be produced with high efficiency.

&Lt; Process [IV] &gt;

The step [IV] is a step of forming a liquid crystal alignment layer between the substrate obtained in the two [III] arrangements in which the liquid crystal alignment film of the substrate is disposed so as to face each other, the liquid crystal layer formed between the substrate and the liquid crystal layer, And a liquid crystal cell having the liquid crystal alignment film formed thereon. The liquid crystal display of the present invention may be a liquid crystal display device of a twisted nematic (TN) type, a vertical alignment (VA) type, an in-plane switching (IPS) Optically Compensated Bend), and the like.

In order to prepare a liquid crystal cell or a liquid crystal display element, the above-described first and second substrates are prepared, spacers are dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a substrate of another uniaxial layer is bonded to each other so that the exposure directions are orthogonal to each other and the liquid crystal is injected under reduced pressure and sealed or liquid crystal is dropped on the surface of the liquid crystal alignment film on which the spacer is dispersed and then the substrate is bonded and sealed And the like. The diameter of the spacer at this time is preferably 1 mu m to 30 mu m, more preferably 2 mu m to 10 mu m. This spacer diameter determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer.

The obtained liquid crystal display element is preferably annealed for further orientation stability. The heating temperature is preferably 10 to 160 DEG C, more preferably 50 to 140 DEG C, which is the phase transition temperature of the liquid crystal.

In the method for producing a coated film-attached substrate of the present invention, a liquid crystal aligning agent is applied on a substrate to form a coated film, and then irradiated with polarized ultraviolet rays. Subsequently, by heating, introduction of high-efficiency anisotropy into the side-chain type polymer film is realized, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is produced.

In the coating film used in the present invention, the introduction of highly efficient anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by the light reaction of side chains and the self-organization based on liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinking group as a photoreactive group on a side chain type polymer, a coating film is formed on a substrate by using a side chain type polymer, then irradiated with polarized ultraviolet rays, After heating, a liquid crystal display element is manufactured.

Therefore, the coating film used in the method of the present invention can be made into a liquid crystal alignment film having anisotropy introduced at high efficiency and excellent in orientation control ability, by sequentially irradiating the coating film with polarized ultraviolet light and heat treatment.

In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film and the heating temperature in the heating treatment are optimized. As a result, introduction of anisotropy into the coating film, which is highly efficient, can be realized.

The irradiation amount of the polarized ultraviolet ray which is most suitable for introducing the high efficiency anisotropy into the coating film used in the present invention corresponds to the irradiation amount of the polarized ultraviolet ray which optimizes the amount of photo-crosslinking reaction or photoisomerization reaction of the photosensitive group in the coating film. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, when the number of photosensitive groups in the side chain to be subjected to the photo-crosslinking reaction or the photoisomerization reaction is small, a sufficient photoreaction amount is not obtained. In that case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, the structure having a photocrosslinkable group is irradiated with polarized ultraviolet rays. As a result, when the photosensitive group of the side chain to be crosslinked is excessive, the cross-linking reaction between the side chains becomes excessive. In such a case, the obtained film becomes rigid, which may interfere with the progress of self-organization by subsequent heating.

Therefore, in the coating film used in the present invention, the optimum amount of photo-crosslinking reaction or photo-isomerization reaction of the photosensitive group of the side chain by irradiation with polarized ultraviolet light is 0.1 mol% to 60 mol of the photosensitive group of the side chain- %, More preferably from 0.1 mol% to 40 mol%. By setting the amount of the photosensitive group of the photoreactive side chain within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and it becomes possible to form anisotropy with high efficiency in the film.

In the coating film used in the method of the present invention, by optimizing the amount of irradiation of polarized ultraviolet rays, the amount of photo-crosslinking reaction, optical isomerization reaction, or optical free-electric potential reaction of the photosensitive group in the side chain of the side- Optimize. In addition to the subsequent heat treatment, introduction of anisotropy into the coating film used in the present invention, which is highly efficient, is realized. In this case, the preferable amount of the polarized ultraviolet ray can be carried out based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, ultraviolet ray absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray after the polarized ultraviolet ray irradiation and ultraviolet ray absorption in the perpendicular direction are respectively measured. From the measurement results of ultraviolet absorption, ΔA which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction in the coating film is evaluated. Then, the maximum value DELTA Amax realized in the coating film used in the present invention (DELTA Amax) and the irradiation amount of the polarized ultraviolet ray to realize it are obtained. In the production method of the present invention, the amount of polarized ultraviolet ray to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of irradiated polarized ultraviolet ray realizing the DELTA Amx.

In the production method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of the polarized ultraviolet ray realizing DELTA Amma, And more preferably within the range. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray in the range of 1% to 50% of the amount of the polarized ultraviolet ray realizing DELTA Amma is preferably 0.1 mol% to 20 mol% of the entire photosensitive unit of the side- Is subjected to a photo-crosslinking reaction.

From the above, in the production method of the present invention, it is preferable to set the above-mentioned preferable heating temperature based on the liquid crystal temperature range of the side chain type polymer in order to realize introduction of high efficiency anisotropy into the coating film . Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 100 ° C to 200 ° C, it is preferable to set the temperature for heating after the polarized ultraviolet irradiation to 90 ° C to 190 ° C. By doing so, a 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 stress such as light or heat.

As described above, the substrate for the twisted nematic liquid crystal display element manufactured by the method of the present invention or the liquid crystal display element having the substrate, the substrate for the OCB type liquid crystal display element, or the liquid crystal display element having the substrate has excellent reliability And can be preferably used for a liquid crystal television with a large screen and a high precision. It is also useful for liquid crystal antennas, light control elements, and the like.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example

The abbreviations used in the examples are as follows.

&Lt; Methacrylate monomer &gt;

[Chemical formula 10]

MA-1 was synthesized by the synthetic method described in non-patent document (Macromolecules 2002, 35, 706-713).

MA-2 was synthesized by the synthetic method described in British Patent GB2306470B.

MA-3 was synthesized by the synthetic method described in non-patent document (Macromolecules 2007, 40, 6355-6360).

MA-4 was synthesized by the synthetic method described in International Patent Application Publication WO2014 / 054785 pamphlet.

MA-5 was synthesized by the synthetic method described in the patent document (JP-A-9-118717).

MA-6 was purchased from Tokyo Chemical Industry Co., Ltd. and used.

MA-7 was purchased from Tokyo Chemical Industry Co., Ltd. and used.

MA-8 was purchased from Tokyo Chemical Industry Co., Ltd. and used.

MA-9 was purchased from Sigma-Aldrich Japan.

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

BCA: butyl cellosolve acetate

CHN: Cyclohexanone

GBL:? -Butyl lactone

PGME: Propylene glycol monomethyl ether

PGMEA: Propylene glycol monomethyl ether acetate

<Polymerization Initiator>

AIBN: 2,2'-azobisisobutyronitrile

&Lt; Synthesis Example 1: Methacrylic polymer &

After dissolving MA-1 (21 g; 40 mmol) and MA-2 (26 g; 60 mmol) in THF (270 g) and degassing with a diaphragm pump, AIBN And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P1.

Methacrylate polymer powders P2 and P3 were prepared in the same manner as in Synthesis Example 1 with respect to Synthesis Examples 2 and 3 under the conditions shown in Table 1.

&Lt; Synthesis Example 4: Methacrylic polymer &

After dissolving MA-3 (23 g; 40 mmol) and MA-2 (26 g; 60 mmol) in THF (282 g) and degassing with a diaphragm pump, AIBN And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P4.

A methacrylate polymer powder P5 was prepared in the same manner as in Synthetic Example 4 with respect to Synthesis Example 5 under the conditions shown in Table 1.

&Lt; Synthesis Example 6: Methacrylic polymer &

After dissolving MA-3 (23 g; 40 mmol) and MA-4 (31 g; 60 mmol) in THF (310 g) and degassing with a diaphragm pump, AIBN And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P6.

A methacrylate polymer powder P7 was prepared in the same manner as in Synthesis Example 6 with respect to Synthesis Example 7 under the conditions shown in Table 1.

&Lt; Synthesis Example 8: Methacrylic polymer &

MA-1 (21 g; 40 mmol), MA-2 (13 g; 30 mmol) and MA-4 (9 g; 30 mmol) were dissolved in THF (246 g) , And AIBN (0.5 g: 3 mmol) were added, followed by degassing. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P8.

A methacrylate polymer powder P9 was produced in the same manner as in Synthetic Example 8 with respect to Synthesis Example 9 under the conditions shown in Table 1.

&Lt; Synthesis Example 10: Methacrylic polymer &

After dissolving MA-1 (21 g; 40 mmol), MA-2 (26 g; 60 mmol) and MA-5 (2 g; 20 mmol) in THF (280 g) , And AIBN (0.5 g: 3 mmol) were added, followed by degassing. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P10.

A methacrylate polymer powder P11 was also produced in Synthesis Example 11 under the conditions shown in Table 1, using the same method as in Synthesis Example 10.

&Lt; Synthesis Example 12: Methacrylic polymer &

MA-1 (21 g; 40 mmol), MA-2 (26 g; 60 mmol) and MA-7 (3 g; 10 mmol) were dissolved in THF (283 g) , And AIBN (0.5 g: 3 mmol) were added, followed by degassing. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P12.

Methacrylate polymer powders P13 and 14 were prepared using the same method except that MA-7 and MA-9 in Synthesis Example 12 were used instead of MA-8 and MA-9, respectively, in Synthesis Examples 13 and 14 under the conditions shown in Table 1 .

&Lt; Synthesis Example 15: methacrylic polymer &

MA-3 (34 g; 60 mmol), MA-2 (9 g; 20 mmol) and MA-5 (6 g; 20 mmol) were dissolved in THF (282 g) , And AIBN (0.5 g: 3 mmol) were added, followed by degassing. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P15.

&Lt; Synthesis Example 16: Methacrylic polymer &

After dissolving MA-1 (21 g; 40 mmol) and MA-5 (6 g; 60 mmol) in THF (154 g) and degassing with a diaphragm pump, AIBN And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P16.

A methacrylate polymer powder P17 was produced in the same manner as in Synthesis Example 16 with respect to Synthesis Example 17 under the conditions shown in Table 1.

&Lt; Synthesis Example 18: Methacrylic polymer &

After dissolving MA-3 (46 g; 80 mmol) and MA-5 (6 g; 20 mmol) in THF (297 g) and degassing with a diaphragm pump, AIBN And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P18.

&Lt; Synthesis Example 19: Methacrylic polymer &

MA-2 (44 g, 100 mmol) was dissolved in THF (251 g) and AIBN (0.5 g, 3 mmol) was added after degassing with a diaphragm pump. Thereafter, the reaction was carried out at 60 DEG C for 6 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to methanol (2000 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder P19.

A methacrylate polymer powder P21 was prepared in the same manner as in Synthetic Example 20 except that MA-2 of Synthesis Example 19 was replaced with MA-3 under the conditions shown in Table 1.

&Lt; Production of liquid crystal aligning agent: A1 &gt;

NMP (11.4 g) was added to the methacrylate polymer powder P1 (0.6 g) obtained in Synthesis Example 1 and dissolved by stirring at room temperature for 1 hour. To this solution, BCS (3.0 g) was added to obtain a polymer solution (A1) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

A liquid crystal aligning agent was prepared in the same manner as in the liquid crystal aligning agent A1 for the liquid crystal aligning agents A2, A3, A5, A11, A12 and A16 to A20 under the conditions shown in Table 1.

&Lt; Production of liquid crystal aligning agent: B1 &gt;

NMP (11.4 g) was added to the methacrylate polymer powder P16 (0.6 g) obtained in Synthesis Example 1 and dissolved by stirring at room temperature for 1 hour. To this solution, BCS (3.0 g) was added to obtain a polymer solution (B1) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

With respect to the liquid crystal aligning agents B2, B4 and B5 under the conditions shown in Table 1, a liquid crystal aligning agent was also produced by the same method as that of the liquid crystal aligning agent B1.

&Lt; Production of liquid crystal aligning agent: A4 &gt;

NMP (9.9 g) was added to the methacrylate polymer powder P3 (0.6 g) obtained in Synthesis Example 1 and dissolved by stirring at room temperature for 1 hour. To this solution, BCA (4.5 g) was added to obtain a polymer solution (A4) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

A liquid crystal aligning agent was prepared in the same manner as in the liquid crystal aligning agent A4 for the liquid crystal aligning agents A6, A7 and A13 under the conditions shown in Table 1.

&Lt; Production of liquid crystal aligning agent: A8 &gt;

CHN (11.4 g) was added to the methacrylate polymer powder P5 (0.6 g) obtained in the above Synthesis Example 1 and dissolved by stirring at a temperature of 50 캜 for 1 hour while being warmed. To this solution, PGME (3.0 g) was added to obtain a polymer solution (A8) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

A liquid crystal aligning agent was prepared in the same manner as in the liquid crystal aligning agent A9 except that PGME of the liquid crystal aligning agent A8 was replaced by PGMEA under the conditions shown in Table 1.

&Lt; Production of liquid crystal aligning agent: A10 &gt;

CHN (15.0 g) was added to the methacrylate polymer powder P5 (0.6 g) obtained in Synthesis Example 1 and dissolved by stirring at a temperature of 50 占 폚 for 1 hour to obtain a polymer solution (A10 ). This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

A liquid crystal aligning agent was prepared in the same manner as in the liquid crystal aligning agent A10 for the liquid crystal aligning agents A15 and A21 under the conditions shown in Table 1.

&Lt; Production of liquid crystal aligning agent: A14 &gt;

NMP (5.4 g) was added to the methacrylate polymer powder P9 (0.6 g) obtained in Synthesis Example 1, and dissolved by stirring at room temperature for 1 hour. To this solution, GBL (4.5 g) and BCA (4.5 g) were added to obtain a polymer solution (A14) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

A liquid crystal aligning agent was prepared in the same manner as in the liquid crystal aligning agent B3 except that the BCA of the liquid crystal aligning agent A14 was replaced with BCS under the conditions shown in Table 1.

<Fabrication of substrate for measurement of in-plane order parameter>

Using the liquid crystal aligning agent thus obtained, a substrate for measuring the light reactivity was manufactured in the following order. The substrate used was a quartz substrate having a size of 40 mm x 40 mm and a thickness of 1.0 mm. The liquid crystal aligning agent A1 was filtered with a filter having a filter hole diameter of 1.0 mu m, spin-coated on a quartz substrate, dried on a hot plate at 70 DEG C for 90 seconds, and a liquid crystal alignment film having a thickness of 100 nm was formed.

(Example 1)

Ultraviolet rays of 313 nm were irradiated with 80 mJ / cm 2 through a polarizer on the coated film surface, and then heated on a hot plate at 120 캜 for 20 minutes to obtain a substrate with a liquid crystal alignment film completed with photoreaction.

In the same manner as in Example 1, substrates for measurement of in-plane orientation degree were also produced in Examples 2 to 21 and Comparative Examples 1 to 5 under the conditions shown in Table 2. [

&Lt; Measurement of planar orientation degree &gt;

In order to measure the optical anisotropy of the liquid crystal alignment film using the liquid crystal alignment film-attached substrate prepared above, the in-plane orientation degree S was calculated from the following equation from the absorbance of the polarized light. The highest value was used for the calculated value.

For measurement of the absorbance, an ultraviolet-visible near-infrared spectrophotometer U-3100PC manufactured by Shimadzu Corporation was used.

Here, A _para represents the absorbance in the parallel direction with respect to the irradiated polarized UV direction, and A _per represents the absorbance in the vertical direction with respect to the irradiated polarized UV direction. A _large is the absorbance of the larger value by comparing the absorbance in the parallel direction and the vertical direction, and A _small is the absorbance of the smaller value by comparing the absorbance in the parallel direction and the vertical direction. And the closer the absolute value of the in-plane orientation degree is to 1, the more uniform the orientation state is.

As shown in Table 2, when the liquid crystal aligning agents of Examples 1 to 21 were used, it was found that the alignment degree in the parallel direction with respect to the polarized UV direction was high. The reason for not aligning in the parallel direction in Comparative Examples 1 and 2 is that the introduction amount of the photosensitive group is small and the orientation by isomerization is superior to the dimerization.

&Lt; Production of liquid crystal cell &

The liquid crystal aligning agent A1 was filtered with a filter of 0.45 占 퐉, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 占 폚 for 90 seconds, and a liquid crystal alignment film with a thickness of 100 nm was formed.

(Example 15)

The coating film was tilted at an angle of 40 占 and irradiated with ultraviolet rays of 313 nm through a polarizing plate at a substrate of 80 mJ / cm2 and then heated on a hot plate at 140 占 폚 for 20 minutes to obtain a substrate with a liquid crystal alignment film. Two such liquid crystal alignment film-attached substrates were prepared, spacers having a size of 4 mu m were provided on the liquid crystal alignment film surface of one of the substrates, and the two substrates were combined so that their rubbing directions became parallel. To prepare a public cell having a cell gap of 4 탆. The liquid crystal MLC-2003 (manufactured by Merck Co., Ltd.) was injected into the vacant cell by a reduced pressure injection method and the injection port was sealed to obtain an anti-parallel liquid crystal cell. After heating at a temperature of 120 캜 for 30 minutes, the pretilt angle of the liquid crystal cell was measured.

A liquid crystal cell was manufactured by using the same method as in Example 1 for Examples 16 to 42 and Comparative Examples 6 to 10 under the conditions shown in Table 3, and the pretilt angle was measured.

As shown in Table 3, when the liquid crystal aligning agents of Examples 22 to 42 were used, it was possible to obtain a liquid crystal pretilt angle preferable for the twisted nematic mode. The reason why the pretilt angle is not expressed in Comparative Examples 6 and 7 is that the tilt is not expressed in the uniaxial direction. In Comparative Example 9, a satisfactory tilt angle was exhibited, but the obtained liquid crystal alignment film was opaque. In Comparative Example 10, a desirable tilt angle was not expressed in the twisted nematic mode.

Using the liquid crystal aligning agent A10, a substrate for measurement of in-plane orientation degree was produced under the conditions described in Table 4, using the same method as in Example 1. [ As a result of measuring the degree of orientation and the tilt angle in accordance with the above example, it was found that the pretilt angle can be controlled by the polarized ultraviolet irradiation amount and the principal firing conditions as shown in Table 4. [

&Lt; Production of liquid crystal aligning agent: A22 &gt;

NMP (8.4 g) was added to the methacrylate polymer powder P15 (0.6 g) obtained in Synthesis Example 15 and dissolved by stirring at room temperature for 1 hour. To this solution, BCS (6.0 g) was added to obtain a polymer solution (A22) having a solid concentration of 4.0 wt%. This polymer solution is directly used as a liquid crystal aligning agent for forming a liquid crystal alignment film.

Using this aligning agent A22, the degree of orientation and the pretilt angle were measured in the same manner. As shown in Table 5, the result showed a pretilt angle of 9.9 ° which was optimum for the OCB mode.

Claims (8)

(A) A polymer composition comprising a copolymer obtained from a monomer mixture comprising the following monomer (A-1) and monomer (A-2).
Monomer (A-1): a monomer having a cinnamoyl moiety, 2 to 4 benzene rings which do not constitute a cinnamoyl moiety, and a polymerizable group.
Monomer (A-2): A monomer having a cinnamoyl moiety, a benzene ring not constituting a cinnamoyl moiety, and a polymerizable group.
(The cinnamoyl moiety and the benzene ring may have substituents). The method according to claim 1,
Wherein the polymerizable group of the monomer (A-1) and the monomer (A-2) is an acrylic group or a methacryl group. The method according to claim 1,
Wherein the monomer (A-1) and the monomer (A-2) are monomers in which a polymerizable group is bonded to any one group selected from the group consisting of a group represented by the following formula (1) Polymer composition.

Wherein, A, B, D are, each independently, a single _{bond, -O-, -CH 2 -, -COO-} , represents an -OCO-, -CONH- or -NH-CO-;
S is an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded thereto may be independently substituted with a halogen group;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to them may be substituted with a halogen group;
When T is a single bond, B also represents a single bond;
Y ₁ is a divalent benzene ring;
P ₁ , Q ₁ and Q ₂ are each independently a group selected from the group consisting of a benzene ring and an alicyclic hydrocarbon ring having 5 to 8 carbon atoms;
R ₁ is a hydrogen atom, -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
The hydrogen atoms bonded to the benzene ring in each of Y ₁ , P ₁ , Q ₁ and Q ₂ are independently selected from the group consisting of -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, an (alkyl having 1 to 5 carbon atoms) carbonyl group, Or an alkyloxy group having 1 to 5 carbon atoms;
X ₁ and X ₂ each independently represent a single bond, -O-, -COO- or -OCO-;
n1 and n2 are each independently 0, 1 or 2;
When the number of X ₁ to be 2, and X may be the same or different each other and _1, when the number of X ₂ is 2, X ₂ may be the same with each other and may be different;
When the number of Q ₁ is 2, may be the same or different with each other even if Q _1, when the number of Q ₂ be the two, and may be the same or different each other and Q _2;
In the monomer (A-1), the sum of the number of benzene rings other than Y ₁ is 2 to 4;
In the monomer (A-2), the total number of benzene rings other than Y ₁ is 1;
The dashed line represents the bond with the polymerizable group. [I] A process for forming a coating film by applying the polymer composition according to any one of claims 1 to 3 onto a substrate having an electrode for driving a liquid crystal;
[II] a step of irradiating polarized ultraviolet rays from the oblique direction onto the coating film obtained in [I]; And
A step of heating the coating film obtained in [III] [II];
To thereby obtain a liquid crystal alignment film having the alignment control ability imparted to the liquid crystal alignment film. A substrate having a liquid crystal alignment film produced by the method according to claim 4. A twisted nematic liquid crystal display device having the substrate according to claim 5. Preparing a substrate (first substrate) according to claim 5;
[I '] a step of applying a polymer composition according to any one of claims 1 to 4 on a second substrate to form a coating film;
A step of irradiating the coating film obtained in [II '] [I'] with polarized ultraviolet rays; And
A step of heating the coating film obtained in [III '] [II'];
To obtain a liquid crystal alignment film having the alignment control ability, thereby obtaining a second substrate having the liquid crystal alignment film; And
[IV] a step of opposing the first and second substrates so that the ultraviolet ray exposing directions are orthogonal to each other so that the liquid crystal alignment layers of the first and second substrates are opposed to each other with the liquid crystal interposed therebetween to obtain a liquid crystal display element;
To obtain a twisted nematic liquid crystal display element. A twisted nematic liquid crystal display element produced by the method according to claim 7.