KR102466047B1 - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element - Google Patents

Abstract

The present invention relates to a polymer composition containing (A) a copolymer obtained from a monomer mixture comprising the following monomers (A-1) and monomers (A-2). Here, the monomer (A-1) refers to a monomer having one cinnamoyl moiety, 2 to 4 benzene rings not constituting the cinnamoyl moiety, and a polymerizable group, and the monomer (A-2) is a cinnamoyl moiety 1 It means a monomer having a dog, one benzene ring not constituting a cinnamoyl moiety, and a polymerizable group (the cinnamoyl moiety and the benzene ring may have a substituent). Moreover, this invention has the process of apply|coating the said composition on the board|substrate which has a conductive film for lateral electric field drive to form a coating film, the process of irradiating the ultraviolet-ray polarized to the obtained coating film, and the process of heating the obtained coating film, A liquid crystal aligning film It relates to a method for manufacturing a substrate having The liquid crystal aligning agent using the polymer composition by this invention is highly efficient, and orientation control ability is provided, it is excellent in a burn-in characteristic, and can provide a transverse electric field drive type liquid crystal display element.

Description

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

This invention relates to a novel polymer composition, the liquid crystal aligning film using the same, and the manufacturing method of the board|substrate which has the said aligning film. Furthermore, it relates to a novel method for manufacturing a liquid crystal display device having excellent tilt angle characteristics.

BACKGROUND ART A liquid crystal display element is known as a light-weight, thin, and low-power display device, and in recent years it is used for a large-scale television use, and has achieved remarkable development. A liquid crystal display element clamps a liquid crystal layer with a pair of transparent board|substrates provided with an electrode, and is comprised, for example. And in a liquid crystal display element, the organic film which consists of an organic material is used as a liquid crystal aligning film so that a liquid crystal may become a desired orientation state between board|substrates.

That is, a liquid crystal aligning film is formed in the surface in contact with the liquid crystal of the board|substrate which clamps a liquid crystal as a structural member of a liquid crystal display element, and is playing the role of orientating a liquid crystal in a fixed direction between the board|substrates. And in addition to the role of orientating a liquid crystal in fixed directions, such as a direction parallel to a board|substrate, the role of controlling the pretilt angle of a liquid crystal may be calculated|required by a liquid crystal aligning film, for example. The ability to control the orientation of a liquid crystal in such a liquid crystal aligning film (it is hereafter called orientation control ability.) is provided by orientation-processing with respect to the organic film which comprises a liquid crystal aligning film.

Conventionally, the rubbing method is known as an orientation processing method of the liquid crystal aligning film for providing orientation control ability. In the rubbing method, the surface of an organic film such as polyvinyl alcohol, polyamide, or polyimide on a substrate is rubbed with a cloth such as cotton, nylon, or polyester in a certain direction (rubbing), in the rubbing direction (rubbing direction) A method of aligning liquid crystals. Since this rubbing method can implement|achieve the alignment state of a relatively stable liquid crystal easily, it has been used in the manufacturing process of the conventional liquid crystal display element. And as an organic film used for a liquid crystal aligning film, the polyimide-type organic film excellent in reliability, such as heat resistance, and an electrical property, has been mainly selected.

However, as for the rubbing method of rubbing the surface of the liquid crystal aligning film which consists of polyimide etc., generation|occurrence|production of dust generation and static electricity may become a problem. In addition, due to the recent increase in precision of liquid crystal display elements, and irregularities caused by the electrodes on the corresponding substrates or the switching active elements for driving liquid crystals, the surface of the liquid crystal aligning film cannot be uniformly rubbed with a cloth, and uniform liquid crystal alignment can be realized. There were cases where there was no

Then, the photo-alignment method is studied actively as another orientation processing method of the liquid crystal aligning film which does not rub.

Although there are various methods in the photo-alignment method, anisotropy is formed in the organic film which comprises a liquid crystal aligning film by linearly polarized light or collimated light, and a liquid crystal is orientated according to the anisotropy.

As a main photo-alignment method, the decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet light, and anisotropic decomposition is generated using the polarization direction dependence of the ultraviolet absorption of the molecular structure. And it is made to orientate a liquid crystal with the polyimide left without decomposition|disassembly (refer patent document 1).

Moreover, the photo-alignment method by a photocrosslinking type is also known. For example, polyvinyl cinnamate is used and polarized ultraviolet rays are irradiated to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to polarization. Moreover, a pretilt angle is expressed by irradiating a polarization|polarized-light ultraviolet-ray in an oblique direction (refer nonpatent literature 1). In addition, when a side chain polymer having coumarin in the side chain is used, polarized ultraviolet light is irradiated to cause a photocrosslinking reaction in the coumarin portion of the side chain parallel to polarization, and the liquid crystal is oriented in a direction parallel to the polarization direction ( See Non-Patent Document 2).

As in the above example, rubbing is not required in the orientation processing method of the liquid crystal aligning film by a photo-alignment method, and there is no fear of dust generation or static electricity generation. And it can orientation-process also to the board|substrate of the liquid crystal display element with an unevenness|corrugation on the surface, and it becomes the method of the orientation treatment of the liquid crystal aligning film suitable for an industrial production process. Furthermore, since the photo-alignment method can control the orientation direction by ultraviolet rays, it is possible to form a plurality of regions (orientation division) having different orientation directions in a pixel, and to compensate for viewing angle dependence.

On the other hand, the liquid crystal aligning film is also playing the role which provides a certain fixed inclination angle (pretilt angle) with respect to a liquid crystal, and provision of a pretilt angle has become an important subject in development of a liquid crystal aligning film (refer patent documents 1 - 4) ).

Here, it is known that the copolymer obtained from the monomer which has a cinnamic acid ester structure and two benzene rings in a side chain shows photo-alignment property (refer patent document 5). However, this copolymer has low solubility, and when setting it as a varnish, you must use solvents, such as chloroform which cannot be used industrially, and it was difficult to apply as a liquid crystal aligning agent.

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

S. Kobayashi et al., Journal of Photopolymer Science and Technology, Vol.8, No.2, pp25-262 (1995). M. Shadt et al., Nature. Vol 381, 212 (1996).

As mentioned above, the photo-alignment method does not require a rubbing process itself compared with the rubbing method which has been conventionally used industrially as an orientation processing method of a liquid crystal display element, Therefore, it is equipped with a big advantage. And compared with the rubbing method in which orientation controllability becomes substantially constant by rubbing, by the photo-alignment method, the irradiation amount of the polarized light can be changed and orientation controllability can be controlled. However, in the photo-alignment method, when it is intended to realize the same degree of alignment control ability as in the case of the rubbing method, the irradiation amount of a large amount of polarized light may be required, 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 having an output of 500 W for 60 minutes. becomes necessary Moreover, also in the case of the photo-alignment method of a dimerization type|mold or a photoisomerization type|mold, the ultraviolet irradiation of the large quantity of about several J (joule) - several tens of J may be required. In addition, in the case of a photo-alignment method of a photocrosslinking type or a photoisomerization type, since thermal stability and light stability of the alignment of liquid crystals are inferior, when a liquid crystal display element is used, poor alignment or display burn-in occurs. I had a problem doing it.

Therefore, in the photo-alignment method, high efficiency improvement of an orientation process and realization of the stable liquid-crystal orientation are calculated|required, and the liquid crystal aligning film and liquid crystal aligning agent which can provide high orientation control ability with respect to a liquid crystal aligning film with high efficiency are calculated|required.

An object of the present invention is to provide a substrate having a liquid crystal aligning film for liquid crystal display elements, which is highly efficient in alignment control ability and excellent in tilt angle characteristics, and a twisted nematic liquid crystal display element and an OCB liquid crystal display element having the substrate do.

Another object of the present invention is to provide a twisted nematic type liquid crystal display device and an OCB type liquid crystal display device having improved tilt angle characteristics, and a liquid crystal aligning film for the device, in addition to the above object.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining so that the said subject could be achieved.

<1> (A) The polymer composition containing the copolymer obtained from the monomer mixture containing the following monomer (A-1) and a monomer (A-2).

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

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

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

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

<3> In <1>, the component (A) is a monomer 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) and a group represented by the following formula (2). desirable.

[Formula 1]

In the formula, A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO-;

S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with it may each independently be substituted by the halogen group;

T is a single bond or a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the 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, a C1-C5 alkyl group, a (C1-C5 alkyl) carbonyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkyloxy group;

In Y ₁ , P ₁ , Q ₁ and Q ₂ , the hydrogen atoms bonded to the benzene ring are each independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, a (alkyl having 1 to 5 carbon atoms) carbonyl group, or a carbon number You may substituted with the alkyloxy group of 1-5;

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 is 2, X ₁ may be the same or different, and when the number of X ₂ is 2, X ₂ may be the same or different;

When the number of Q ₁ is 2, Q ₁ may be the same or different, and when the number of Q ₂ is 2, Q ₂ may be same or different;

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

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

The broken line indicates a bond with a polymerizable group.

<4> [I] Process of apply|coating the polymer composition in any one of said <1>-<3> on the board|substrate which has an electrode for liquid-crystal drive, and forming a coating film;

[II] The process of irradiating the ultraviolet-ray which polarized from the diagonal direction to the coating film obtained by [I]; 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 twisted nematic-type liquid crystal display elements and OCB type liquid crystal display elements to which orientation control ability was provided by having.

The board|substrate which has the liquid crystal aligning film for twisted nematic-type liquid crystal display elements and/or OCB-type liquid crystal display elements manufactured by the manufacturing method as described in <5> said <4>.

A twisted nematic liquid crystal display element and an OCB liquid crystal display element which have the board|substrate of <6> said <5>.

<7> process of preparing the board|substrate (1st board|substrate) of said <5>;

[I'] Process of apply|coating the polymer composition in any one of said <1>-<4> on a 2nd board|substrate, and forming a coating film;

[II'] The process of irradiating the polarized ultraviolet-ray to the coating film obtained by [I']; and

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

The process of obtaining the 2nd board|substrate which has this liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; and

[IV] Process of opposingly arrange|positioning 1st and 2nd board|substrate so that exposure directions may mutually orthogonally cross so that the liquid crystal aligning film of a 1st and 2nd board|substrate may oppose through a liquid crystal, and obtaining a liquid crystal display element;

The manufacturing method of this liquid crystal display element which obtains a twisted nematic-type liquid crystal display element and an OCB-type liquid crystal display element by having.

<8> Twisted nematic liquid crystal display element and OCB liquid crystal display element manufactured according to <7>.

ADVANTAGE OF THE INVENTION According to this invention, the board|substrate which has a liquid crystal aligning film which is provided with orientation control ability with high efficiency and is excellent in the tilt angle characteristic, and the twisted nematic type liquid crystal display element and OCB type liquid crystal display element which have the board|substrate can be provided.

Since the twist nematic liquid crystal display element and the OCB type liquid crystal display element manufactured by the method of this invention are provided with orientation control ability with high efficiency, even if it drives continuously for a long time, a display characteristic is not impaired in case.

The liquid crystal aligning agent used in the manufacturing method of this invention has the photosensitive side chain type polymer|macromolecule (Hereinafter, it is also simply side chain type polymer|macromolecule) which can express liquid crystal, and is obtained using the said liquid crystal aligning agent A coating film is a film|membrane which has photosensitive side chain type polymer|macromolecule which can express liquid crystallinity. It orientation-processes by polarized light irradiation, without giving a rubbing process to this coating film. And it becomes the coating film (henceforth a liquid crystal aligning film) to which orientation control ability was provided through the process of heating the side chain type polymer film after polarized light irradiation. At this time, the slight anisotropy expressed by polarized light irradiation becomes a driving force, and liquid crystalline side chain type polymer|macromolecule itself is efficiently reorientated by self-organization. As a result, as a liquid crystal aligning film, highly efficient orientation processing is implement|achieved, and the liquid crystal aligning film to which high orientation control ability was provided can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<The manufacturing method of the board|substrate which has a liquid crystal aligning film> and <The manufacturing method of a liquid crystal display element>

<<(A) side chain type polymer>>

(A) A component is a copolymer (henceforth side chain type polymer|macromolecule) obtained from the monomer mixture containing the following monomer (A-1) and a monomer (A-2).

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

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

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

Moreover, as a substituent here, a methyl group, a methoxy group, a tert-butyl group, an acetyl group, a fluorine group, a cyano group, etc. are mentioned, for example.

(A) Side chain polymer|macromolecule has the side chain which has photosensitivity couple|bonded with the principal chain, and it can sensitize light and can raise|generate a crosslinking reaction and an isomerization reaction. Although the structure of the side chain which has photosensitivity is not specifically limited, The structure which responds to light and raise|generates a crosslinking reaction is preferable. In this case, even when exposed to external stress such as heat, the realized orientation controllability can be stably maintained for a long period of time.

(A) More specific examples of the side chain polymer structure of component include hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, α-methylene-γ-butyrolactones, styrenes, vinyls, maleimides It is preferable that it is a structure which has a main chain comprised by at least 1 type selected from the group which consists of radically polymerizable groups, such as norbornene, and siloxane, and a side chain which consists of at least 1 type of following formula (1) and (2) .

[Formula 2]

In the formula, A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO-;

S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with it may each independently be substituted by the halogen group;

T is a single bond or a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the 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, a C1-C5 alkyl group, a (C1-C5 alkyl) carbonyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkyloxy group;

In Y ₁ , P ₁ , Q ₁ and Q ₂ , the hydrogen atoms bonded to the benzene ring are each independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, a (alkyl having 1 to 5 carbon atoms) carbonyl group, or a carbon number You may substituted with the alkyloxy group of 1-5;

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 is 2, X ₁ may be the same or different, and when the number of X ₂ is 2, X ₂ may be the same or different;

When the number of Q ₁ is 2, Q ₁ may be the same or different, and when the number of Q ₂ is 2, Q ₂ may be same or different;

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

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

The broken line indicates a bond with a polymerizable group.

Content of the side chain derived from (A-1) which occupies for the sum total of content of the side chain derived from (A-1) in side chain type polymer|macromolecule of this invention, and content of the side chain derived from (A-2), From the same point as the solubility of liquid-crystal orientation and side chain type polymer|macromolecule, 10 mol% - 90 mol% are preferable, 20 mol% - 80 mol% are more preferable, 30 mol% - 70 mol% are still more preferable.

Even if the side chain type polymer|macromolecule of this invention contains other side chains other than the side chain derived from said (A-1) and the side chain derived from (A-2) in the range which does not impair the effect of this invention, do. The content is the remaining part, when the sum total of content of the said photoreactive side chain and a liquid crystalline side chain does not reach 100 %.

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

The photosensitive side chain type polymer|macromolecule which can express said liquid crystal property can be obtained by superposing|polymerizing the monomer mixture containing said monomer (A-1) and a monomer (A-2) at least.

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

A photoreactive side chain monomer means the monomer which can form the polymer|macromolecule which has a photosensitive side chain in the side chain site|part of a polymer|macromolecule, when polymer|macromolecule is formed.

As a photoreactive group which a side chain has, the following structure and its derivative(s) are preferable.

More specific examples of the monomer (A-1) and the monomer (A-2) include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl , a polymerizable group composed of at least one selected from the group consisting of radically polymerizable groups and trialkoxysilyl groups such as maleimide and norbornene, and a photosensitive side chain selected from the structures represented by the formulas (1) and (2) above It is preferable that it has a structure.

The polymerizable group is preferably selected from groups represented by the following formulas PG1 to PG8. Among them, the acryl group or methacryl group represented by PG1 is preferable from the viewpoint of easy control of the polymerization reaction and the stability of the polymer. In addition, in formula, a broken line shows the bond with the photosensitive side chain represented by said Formula (1) or (2).

[Formula 3]

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

As a monomer (A-1), the monomer chosen from following formula A-1-1 - A-1-7 is mentioned, for example.

[Formula 4]

[Formula 5]

(In formulas A-1-1 to A-1-7, PG represents a polymerizable group selected from the groups represented by formulas PG1 to PG8, s1 and s2 each independently represent the number of methylene groups, 2 to 9 is a natural number of

As a monomer (A-2), the monomer chosen from following formula A-2-1 - A-2-14 is mentioned, for example.

[Formula 6]

[Formula 7]

[Formula 8]

(In formulas A-2-1 to A-2-14, PG represents a polymerizable group selected from the groups represented by formulas PG1 to PG8, s1 and s2 each independently represent the number of methylene groups, 2 to 9 is a natural number of

Any of the said monomer (A-1) and the monomer (A-2) are commercially available, and any can be manufactured, for example by the method described in International Patent Application Laid-Open WO2014/074785 etc.

(A) Side chain type polymer|macromolecule can be obtained by the copolymerization reaction of the above-mentioned monomer (A-1) and a monomer (A-2). Moreover, it can copolymerize with another monomer in the range which does not impair liquid crystalline expression ability.

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

As a specific example of another monomer, an unsaturated carboxylic acid, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned.

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, palmityl 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, 8-ethyl-8-tricyclodecyl acrylate, etc. are mentioned.

As a methacrylic acid ester compound, For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate Rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, palmityl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate acrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl -2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. can be heard

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.

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene etc. are mentioned, for example.

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

As for content of the photoreactive side chain shown by (A-1) and (A-2) in side chain type polymer|macromolecule of this invention, 10 mol% - 100 mol% are preferable from the point similar to liquid-crystal orientation, 20 mol% - 100 mol% are more preferable, and 30 mol% - 100 mol% are still more preferable.

It does not specifically limit about the manufacturing method of side chain type polymer|macromolecule of this embodiment, The general-purpose method handled industrially can be used. Specifically, it can manufacture by cationic polymerization using the vinyl group of (A-1) or (A-2) monomer, radical polymerization, or anionic polymerization. Among these, radical polymerization is especially preferable from a viewpoint of the easiness of reaction control, etc.

As the conditions such as a polymerization initiator for radical polymerization, reaction temperature, and solvent, known conditions described in International Patent Application Publication No. WO2014/074785 and the like can be used.

[Method for producing polysiloxane]

When the polymer which is (A) component used for this invention is polysiloxane, the method of obtaining the said polysiloxane is not specifically limited. In this invention, it is obtained by condensing the alkoxysilane mixture which has as an essential component the monomer whose polymeric group is a trialkoxysilyl group in said monomer (A-1) and a monomer (A-2) in an organic solvent. Usually, polysiloxane polycondenses such an alkoxysilane, and is obtained as a solution which melt|dissolved uniformly in the organic solvent.

In this invention, the alkoxysilane represented by following formula (3) other than said monomer (A-1) and monomer (A-2) can also be used. Since it is possible to provide various characteristics to polysiloxane, the alkoxysilane represented by Formula (3) can select and use 1 type or multiple types according to a required characteristic.

(R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureide group, R ⁶ is It is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3, 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 hetero rings; unsaturated bonds; and a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and may have a branched structure, and is an organic group having 1 to 6 carbon atoms. Furthermore, this 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.

Although the specific example of the alkoxysilane represented by such Formula (3) is given, it is not limited to this.

The alkoxysilane of Formula (3) WHEREIN: Trimethoxysilane, a triethoxysilane, a tripropoxysilane, tributoxysilane etc. are mentioned as a specific example of the alkoxysilane in case R< ⁵ > is a hydrogen atom. .

Moreover, in the alkoxysilane of Formula (3), as a specific example of the alkoxysilane in case R< ⁵ > is a 3rd organic group, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrie Toxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropyl Triethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, 3-(2-aminoethylaminopropyl)trimethoxysilane, 3-(2-aminoethylaminopropyl)triethoxysilane , 2-aminoethylaminomethyltrimethoxysilane, 2-(2-aminoethylthioethyl)triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane , 3-isocyanate propyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyl Dimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane , trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, and γ-ureidopropyltripropoxysilane.

The polysiloxane used for this invention is for the purpose of adhesiveness with a board|substrate, affinity improvement with a liquid crystal molecule, etc., unless the effect of this invention is impaired, 1 type of alkoxysilane represented by said Formula (3) Or you may have multiple types.

The alkoxysilane represented by Formula (3) WHEREIN: The alkoxysilane whose n is 0 is tetraalkoxysilane. Since tetraalkoxysilane is easy to condense with the alkoxysilane represented by Formula (1) and Formula (2), in order to obtain the polysiloxane of this invention, it is preferable.

As the alkoxysilane in which n is 0 in the formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and particularly, tetramethoxysilane or tetraethoxysilane Preference is given to oxysilane.

As a method of polycondensing polysiloxane, the method described in International Patent Application Laid-Open WO2010/126108 etc. can be used.

[Recovery of polymer]

What is necessary is just to pour in the reaction solution to a poor solvent, and to precipitate these polymers, when collect|recovering the produced|generated polymer|macromolecule from the reaction solution of the photosensitive side chain type polymer|macromolecule which was obtained by the reaction mentioned above and can express liquid crystallinity. . Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can be heard After the polymer which was charged into the poor solvent and precipitated was recovered by filtration, the polymer can be dried at room temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to dissolve again in an organic solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons, and the use of three or more types of poor solvents selected from these is preferable because the efficiency of purification further increases.

The molecular weight of the (A) side chain polymer of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method when the strength of the obtained coating film, workability at the time of coating film formation, and the uniformity of the coating film are taken into consideration, 2000-1000000 are preferable, More preferably, it is 5000-100000.

<Organic solvent>

The organic solvent used for the polymer composition used for this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. The specific example is given below.

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

<Liquid crystal aligning agent>

A liquid crystal aligning agent is apply|coated to the side in which the electrode of the said board|substrate was formed.

The liquid crystal aligning agent of this invention uses the polymer composition by this invention, (A) The copolymer obtained from the monomer mixture containing the said monomer (A-1) and a monomer (A-2) is contained.

[Preparation of liquid crystal aligning agent]

It is preferable that the liquid crystal aligning agent used for this invention is prepared as a coating liquid so that it may become suitable for formation of a liquid crystal aligning film. That is, it is preferable that the liquid crystal aligning agent used for this invention is prepared as a solution in which the resin component for forming a resin film melt|dissolved in the organic solvent. Here, the resin component is a resin component containing the side chain type polymer|macromolecule which is the (A) component already demonstrated. In that case, as for content of a resin component, 1 mass % - 20 mass % are preferable, More preferably, they are 3 mass % - 15 mass %, Especially preferably, they are 3 mass % - 10 mass %.

Liquid crystal aligning agent of this invention WHEREIN: As for the resin component mentioned above, although the side chain type polymer|macromolecule whose whole is (A) component may be sufficient, other polymers other than those may be mixed in the range which does not impair liquid-crystal aligning ability. In that case, content of the other polymer in a resin component is 0.5 mass % - 80 mass %, Preferably they are 1 mass % - 50 mass %.

Such another polymer consists of poly(meth)acrylate, a polyamic acid, a polyimide, etc., for example, and polymers other than the side chain type polymer|macromolecule etc. which are (A) component are mentioned.

The polymer composition used for this invention may contain components other than the side chain type polymer|macromolecule which are said (A) component, and an organic solvent. Although the solvent and compound which improve film thickness uniformity and surface smoothness at the time of apply|coating a liquid crystal aligning agent as the example, and the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate are mentioned, It is not limited to this.

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

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-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, 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, 3-methoxymethyl propionate, 3-ethoxy methyl propionate Ethyl, 3-methoxyethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxybutyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2 -Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Ethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. Solvents with low surface tension and the like.

The number of these poor solvents may be one, and they may mix and use multiple types. When using the solvent as mentioned above, it is preferable that it is 5 mass % - 80 mass % of the whole solvent so that the solubility of the whole solvent contained in a polymer composition may not be reduced remarkably, More preferably, 20 They are mass % - 60 mass %.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florad FC430, FC431 (manufactured by Sumitomo 3M), AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Corporation), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Semichemical) ) and the like. To [ the usage ratio of these surfactant / 100 mass parts of the resin component contained in a polymer composition ], Preferably they are 0.01 mass part - 2 mass parts, More preferably, they are 0.01 mass part - 1 mass part.

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

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

Moreover, in addition to the improvement of the adhesiveness of a board|substrate and a liquid crystal aligning film, for the purpose of preventing the fall of the electrical property by the backlight when a liquid crystal display element is comprised, etc., the additive of the following phenoplast type and an epoxy group containing compound, liquid crystal You may make it contain in an aligning agent. Although a specific phenoplast type additive is shown below, it is not limited to this structure.

[Formula 9]

Specific examples of the epoxy group-containing compound 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-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 liquid crystal aligning agent, More preferably, 1 mass part - 20 parts by mass. When the usage-amount is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

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

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, and amino substituted, aromatic 2-hydroxyketones (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-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoyl Methylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naph Tooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3- Methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- nitroacenaphthene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone) ), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocumarin, and the like.

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

The manufacturing method of the board|substrate which has a liquid crystal aligning film of this invention,

[I] (A) Process of apply|coating the liquid crystal aligning agent containing side chain type polymer|macromolecule and an organic solvent on the board|substrate which has a transparent electrode, and forming a coating film;

[II] The process of irradiating the ultraviolet-ray which polarized to the coating film obtained by [I]; and

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

has

According to the said process, the liquid crystal aligning film for liquid crystal display elements to which orientation control ability was provided can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

Moreover, a liquid crystal display element can be obtained by preparing a 2nd board|substrate other than the board|substrate (1st board|substrate) obtained above.

A 2nd board|substrate can obtain the 2nd board|substrate which has a liquid crystal aligning film to which orientation control ability was provided by using the said process [I] - [III] for the 2nd board|substrate which has a transparent electrode.

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

[IV] Process of opposingly arrange|positioning the 1st and 2nd board|substrate obtained above so that the liquid crystal aligning film of a 1st and 2nd board|substrate may oppose through a liquid crystal, and obtaining a liquid crystal display element;

has Thereby, a twisted nematic type liquid crystal display element can be obtained.

Hereinafter, each process of [I] - [III], and [IV] which the manufacturing method of this invention has is demonstrated.

<Process [Ⅰ]>

At process [I], on the board|substrate which has an electrode for liquid crystal drives, the liquid crystal aligning agent containing (A) side chain type polymer|macromolecule and an organic solvent is apply|coated, and a coating film is formed.

<substrate>

Although limitation in particular is not carried out about a board|substrate, When the liquid crystal display element manufactured is a transmissive type, it is preferable that a board|substrate with high transparency is used. In that case, limitation in particular is not carried out, Plastic substrates, such as a glass substrate or an acryl substrate and a polycarbonate board|substrate, etc. can be used.

As an electrode for driving the liquid crystal, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. are preferable. In the reflective liquid crystal display element, an opaque material such as a silicon wafer may be used as long as it is only a one-side substrate, and a light-reflecting material such as aluminum may be used for the electrode in this case.

A conventionally well-known method can be used for the method of forming an electrode in a board|substrate.

The method of apply|coating the liquid crystal aligning agent mentioned above on the board|substrate which has the electrode for liquid crystal drives is not specifically limited.

As for the coating method, industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method (rotary coating method), the spray method, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on the board|substrate which has an electrode for liquid crystal drive, 50-230 degreeC by heating means, such as a hotplate, heat circulation type oven, or IR (infrared) type|mold oven, Preferably it is 50-200 A coating film can be obtained by evaporating a solvent at 0 degreeC for 0.4 minutes - 60 minutes, Preferably it is 0.5 minutes - 10 minutes. It is preferable that the drying temperature at this time is lower than the inside of the temperature range of the temperature (henceforth liquid-crystal expression temperature) at which side chain type polymer|macromolecule of side chain type polymer|macromolecule which is (A) component expresses liquid crystallinity.

When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm.

Moreover, it is also possible to provide the process of cooling the board|substrate on which the coating film was formed to room temperature after the [I] process before the subsequent [II] process.

<Process [II]>

In process [II], the ultraviolet-ray which polarized from the diagonal direction is irradiated to the coating film obtained by process [I]. When irradiating the polarized ultraviolet-ray to the film surface of a coating film, the polarized ultraviolet-ray is irradiated through a polarizing plate from a fixed direction with respect to a board|substrate. As the ultraviolet ray to be used, an ultraviolet ray having a wavelength of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter etc. according to the kind of coating film to be used. And, for example, in order to selectively cause a photocrosslinking reaction, an ultraviolet ray having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

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

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

As a method of adjusting the irradiation direction to the above angle, there are a method of tilting the substrate itself and a method of tilting the light source. However, tilting the light source itself is more preferable from the viewpoint of throughput.

As a pretilt angle obtained, 1 degree - 20 degrees are preferable as a pretilt angle suitable for a twist nematic mode, and 2 degrees - 15 degrees are more preferable.

Moreover, in this invention, it is also possible to control a tilt angle by adjusting the irradiation amount, irradiation time, or both of the said process [II].

<Process [III]>

In process [III], the coating film irradiated with the ultraviolet-ray which polarized in process [II] is heated. By heating, orientation control ability can be provided to a coating film.

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

It is preferable that heating temperature exists in the temperature range of the temperature (henceforth liquid-crystal expression temperature) at which side chain type polymer|macromolecule expresses liquid crystallinity. In the case of the surface of a thin film like a coating film, it is expected that the liquid crystal expression temperature of the surface of a coating film is lower than the liquid crystal expression temperature at the time of observing the side chain type polymer|macromolecule which is (A) component in bulk. For this reason, as for heating temperature, it is more preferable that it exists in the temperature range of the liquid-crystal expression temperature of the coating-film surface. That is, the temperature range of the heating temperature after polarization ultraviolet irradiation is a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer to be used as the lower limit, and the temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is a temperature in the range made into an upper limit. When the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy by heat in the coating film tends to be insufficient, and when the heating temperature is too high than the above temperature range, the state of the coating film is in an isotropic liquid state (isotropic phase) , and in this case, it may be difficult to reorient in one direction due to self-organization.

In addition, the liquid crystal expression temperature is above the glass transition temperature (Tg) at which the side chain polymer or the surface of the coating film undergoes phase transition from the solid phase to the liquid crystal phase, and the isotropic phase transition temperature causing the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase). (Tiso) or lower temperature.

Moreover, in this invention, it is also possible to control a tilt angle by adjusting the heating temperature, heating time, or both of the said process [III].

The thickness of the coating film formed after heating is from the same reason described in process [I], Preferably it is 5 nm - 300 nm, It is preferable that it is 50 nm - 150 nm more preferably.

By having the above process, in the manufacturing method of this invention, highly efficient and anisotropic introduction|transduction with respect to a coating film can be implement|achieved. And the board|substrate with a liquid crystal aligning film can be manufactured with high efficiency.

<Process [IV]>

[IV] Process is formed between the board|substrate obtained by [III] of 2 sheets arrange|positioned so that the side in which the liquid crystal aligning film of the board|substrate was formed opposes, the liquid crystal layer formed between the board|substrates, a board|substrate, and a liquid crystal layer, and the liquid crystal aligning agent of this invention It is a liquid crystal display element provided with the liquid crystal cell which has the said liquid crystal aligning film formed by. As such a liquid crystal display element of the present invention, a twisted nematic (TN: Twisted Nematic) method, a vertical alignment (VA: Vertical Alignment) method, a horizontal alignment (IPS: In-Plane Switching) method, OCB alignment (OCB: Optically Compensated Bend), etc. are mentioned.

If an example of preparation of a liquid crystal cell or a liquid crystal display element is given, the above-mentioned 1st and 2nd board|substrates are prepared, a spacer is disperse|distributed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made to be inside, and an ultraviolet-ray The other side board|substrate is bonded so that an exposure direction may mutually be orthogonal, After the method of injecting and sealing a liquid crystal under reduced pressure, or dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, the board|substrate is bonded and sealed How to do it can be exemplified. The diameter of the spacer at this time is preferably 1 µm to 30 µm, and more preferably 2 µm to 10 µm. The 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.

It is preferable that the obtained liquid crystal display element further anneals for orientation stability. The heating temperature is the phase transition temperature of the liquid crystal, preferably 10 to 160°C, more preferably 50 to 140°C.

After the manufacturing method of the board|substrate with a coating film of this invention apply|coats a liquid crystal aligning agent on a board|substrate and forms a coating film, it irradiates the ultraviolet-ray which polarized. Next, by heating, highly efficient anisotropic introduction|transduction with respect to a side chain type polymer film is implement|achieved, and the board|substrate with a liquid crystal aligning film provided with the orientation control ability of a liquid crystal is manufactured.

In the coating film used for this invention, highly efficient anisotropic introduction to a coating film is implement|achieved using the principle of molecular reorientation caused by the self-organization based on the photoreaction of a side chain 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, a coating film is formed on the substrate using the side chain polymer, then irradiated with polarized ultraviolet rays, and then, After heating, a liquid crystal display element is manufactured.

Therefore, the coating film used for the method of this invention can be set as the liquid-crystal aligning film excellent in the orientation control ability by introducing anisotropy with high efficiency by performing irradiation of the ultraviolet-ray which polarized with respect to the coating film, and heat processing sequentially.

And in the coating film used for the method of this invention, the irradiation amount of the ultraviolet-ray which polarized to a coating film, and the heating temperature in heat processing are optimized. Thereby, highly efficient and anisotropic introduction|transduction with respect to a coating film can be implement|achieved.

The optimal dose of polarized UV light for introducing highly efficient anisotropy to the coating film used in the present invention corresponds to the dose of polarized UV light that optimizes the amount of photosensitive group photocrosslinking reaction or photoisomerization reaction in the coating layer. As a result of irradiating the ultraviolet-ray which polarized with respect to the coating film used for this invention, when there are few photosensitive groups of the side chain which photocrosslinking reaction or a photoisomerization reaction, it will not become sufficient photoreaction amount. In that case, even if it heats after that, sufficient self-organization does not advance. On the other hand, in the coating film used for this invention, as a result of irradiating the ultraviolet-ray which polarized with respect to the structure which has a photocrosslinkable group, when the photosensitive group of the side chain which crosslinks reacts excessively, the crosslinking reaction between side chains will advance too much. In that case, the obtained film|membrane becomes rigid, and it may interfere with advancing of the self-organization by subsequent heating.

Therefore, the coating film used for this invention WHEREIN: 0.1 mol% - 60 mol of the photosensitive group which the photosensitive group of a side chain has the optimal quantity which the photosensitive group of a side chain has a photocrosslinking reaction or a photoisomerization reaction by irradiation of a polarization|polarized-light ultraviolet-ray is the side chain type polymer film. % is preferable, and it is more preferable to set it as 0.1 mol% - 40 mol%. By making the quantity of the photosensitive group of the side chain which photoreacts into such a range, self-organization in subsequent heat processing advances efficiently, and highly efficient anisotropic formation in a film|membrane is attained.

In the coating film used for the method of this invention, the quantity of the photocrosslinking reaction of a photosensitive group in the side chain of a side chain type polymer film, a photoisomerization reaction, or an optical Fris rearrangement reaction by optimization of the irradiation amount of the polarized ultraviolet-ray Optimize. And the anisotropic introduction|transduction with respect to the coating film used for this invention which is highly efficient and is combined with subsequent heat processing is implement|achieved. In that case, about the quantity of a preferable polarization|polarized-light ultraviolet-ray, it can implement based on evaluation of the ultraviolet absorption of the coating film used for this invention.

That is, with respect to the coating film used for this invention, the ultraviolet absorption of the direction parallel to the polarization direction of the polarized ultraviolet-ray after polarized-ultraviolet irradiation, and the ultraviolet absorption of the perpendicular|vertical direction are measured, respectively. From the measurement result of ultraviolet absorption, (DELTA)A which is the difference of the ultraviolet absorbance of the direction parallel to the polarization direction of the ultraviolet-ray which polarized in the coating film, and the ultraviolet absorbance of the perpendicular|vertical direction is evaluated. And the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays that realize it are calculated. In the manufacturing method of this invention, on the basis of the polarization|polarized-light ultraviolet irradiation amount which implement|achieves this (DELTA)Amax, the amount of the ultraviolet-ray which polarized in the preferable quantity irradiated in manufacture of a liquid crystal aligning film can be determined.

In the manufacturing method of this invention, it is preferable to make the irradiation amount of the polarized ultraviolet-ray with respect to the coating film used for this invention into 1% - 70% of the range of the amount of polarized ultraviolet-ray which implement|achieves ΔAmax, and 1% to 50% It is more preferable to set it as within the range. The coating film used for this invention WHEREIN: The irradiation amount of the polarization|polarized-light ultraviolet-ray within the range of 1% - 50% of the quantity of the polarization|polarized-light ultraviolet-ray which implement|achieves (DELTA)Amax is 0.1 mol% - 20 mol% of the whole photosensitive group which the side chain type polymer film has. It corresponds to the amount of polarized ultraviolet light that causes a photocrosslinking reaction.

From the above, in the manufacturing method of this invention, in order to implement|achieve highly efficient anisotropic introduction with respect to a coating film, it is preferable to determine the preferable heating temperature as mentioned above on the basis of the liquid crystal temperature range of the side chain type polymer|macromolecule as a reference. . Therefore, for example, when the liquid crystal temperature range of side chain type polymer|macromolecule used for this invention is 100 degreeC - 200 degreeC, it is preferable to make the temperature of the heating after polarization|polarized-light ultraviolet irradiation into 90 degreeC - 190 degreeC. By doing in this way, larger anisotropy is provided in the coating film used for this invention.

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

As described above, the substrate for twisted nematic type 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 is excellent in reliability. It can be used suitably for a large-screen, high-definition liquid crystal television. Moreover, it is useful also for a liquid crystal antenna, a dimming element, etc.

Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to the Example.

Example

The abbreviation used in the Example is as follows.

<Methacryl Monomer>

[Formula 10]

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

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

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

MA-4 was synthesized by the synthesis method described in the pamphlet of International Patent Application Publication No. WO2014/054785.

MA-5 was synthesized by the synthesis method described in the patent document (Unexamined-Japanese-Patent No. 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 and used.

<Organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS : Butyl Cellosolve

BCA: Butyl Cellosolve Acetate

CHN: cyclohexanone

GBL: γ-butyllactone

PGME: propylene glycol monomethyl ether

PGMEA: Propylene glycol monomethyl ether acetate

<Polymerization Initiator>

AIBN: 2,2'-azobisisobutyronitrile

<Synthesis Example 1: Methacryl Polymer>

MA-1 (21 g: 40 mmol) and MA-2 (26 g: 60 mmol) were dissolved in THF (270 g), and after degassing with a diaphragm pump, AIBN (0.5 g: 3 mmol) was added. and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P1.

Also about Synthesis Examples 2 and 3 under the conditions shown in Table 1, methacrylate polymer powders P2 and P3 were produced using the same method as in Synthesis Example 1.

<Synthesis Example 4: Methacryl Polymer>

MA-3 (23 g: 40 mmol) and MA-2 (26 g: 60 mmol) were dissolved in THF (282 g), and after degassing with a diaphragm pump, AIBN (0.5 g: 3 mmol) was added. and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P4.

Also about the synthesis example 5 on the conditions shown in Table 1, using the method similar to the synthesis example 4, the methacrylate polymer powder P5 was produced.

<Synthesis Example 6: Methacryl Polymer>

MA-3 (23 g: 40 mmol) and MA-4 (31 g: 60 mmol) were dissolved in THF (310 g), and after degassing with a diaphragm pump, AIBN (0.5 g: 3 mmol) was added. and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P6.

Also about the synthesis example 7 on the conditions shown in Table 1, using the method similar to the synthesis example 6, the methacrylate polymer powder P7 was produced.

<Synthesis Example 8: Methacryl Polymer>

After dissolving MA-1 (21 g: 40 mmol), MA-2 (13 g: 30 mmol), and MA-4 (9 g: 30 mmol) in THF (246 g), degassing with a diaphragm pump , AIBN (0.5 g: 3 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P8.

Also about the synthesis example 9 on the conditions shown in Table 1, using the method similar to the synthesis example 8, the methacrylate polymer powder P9 was produced.

<Synthesis Example 10: Methacryl 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), degassing with a diaphragm pump , AIBN (0.5 g: 3 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P10.

Also about the synthesis example 11 on the conditions shown in Table 1, using the method similar to the synthesis example 10, the methacrylate polymer powder P11 was produced.

<Synthesis Example 12: methacrylic polymer>

After dissolving MA-1 (21 g: 40 mmol), MA-2 (26 g: 60 mmol), and MA-7 (3 g: 10 mmol) in THF (283 g), degassing with a diaphragm pump , AIBN (0.5 g: 3 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P12.

Also about Synthesis Examples 13 and 14 under the conditions shown in Table 1, methacrylate polymer powders P13 and 14 were produced in the same manner except that MA-7 of Synthesis Example 12 was replaced with MA-8 and MA-9. .

<Synthesis Example 15: Methacryl Polymer>

After dissolving MA-3 (34 g: 60 mmol), MA-2 (9 g: 20 mmol), MA-5 (6 g: 20 mmol) in THF (282 g), degassing with a diaphragm pump , AIBN (0.5 g: 3 mmol) was added and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This deposit was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P15.

<Synthesis Example 16: Methacryl Polymer>

MA-1 (21 g: 40 mmol) and MA-5 (6 g: 60 mmol) were dissolved in THF (154 g), and after degassing with a diaphragm pump, AIBN (0.5 g: 3 mmol) was added. and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P16.

Also about the synthesis example 17 under the conditions shown in Table 1, the method similar to the synthesis example 16 was used, and the methacrylate polymer powder P17 was produced.

<Synthesis Example 18: Methacryl Polymer>

MA-3 (46 g: 80 mmol) and MA-5 (6 g: 20 mmol) were dissolved in THF (297 g), and after degassing with a diaphragm pump, AIBN (0.5 g: 3 mmol) was added. and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P18.

<Synthesis Example 19: methacrylic polymer>

MA-2 (44 g: 100 mmol) was dissolved in THF (251 g) and degassed with a diaphragm pump, followed by addition of AIBN (0.5 g: 3 mmol) and degassed again. Then, it was made to react at 60 degreeC for 6 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dripped at methanol (2000 mL), and the obtained deposit was filtered. This precipitate was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P19.

Also about Synthesis Example 20 under the conditions shown in Table 1, methacrylate polymer powder P20 was produced in the same manner except that MA-2 of Synthesis Example 19 was replaced with MA-3.

<Production of liquid crystal aligning agent: A1>

NMP (11.4 g) was added to the methacrylate polymer powder P1 (0.6 g) obtained in Synthesis Example 1, and stirred at room temperature for 1 hour to dissolve. BCS (3.0 g) was added to this solution, and the polymer solution (A1) whose solid content concentration is 4.0 wt% was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent A2, A3, A5, A11, A12, A16-A20 on the conditions shown in Table 1, the liquid crystal aligning agent was produced using the method similar to liquid crystal aligning agent A1.

<Production of liquid crystal aligning agent: B1>

NMP (11.4 g) was added to the methacrylate polymer powder P16 (0.6 g) obtained in Synthesis Example 16, and the mixture was dissolved by stirring at room temperature for 1 hour. BCS (3.0g) was added to this solution, and the polymer solution (B1) whose solid content concentration is 4.0 wt% was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent B2, B4, B5 on the conditions shown in Table 1, the liquid crystal aligning agent was produced using the method similar to liquid crystal aligning agent B1.

<Production of liquid crystal aligning agent: A4>

To the methacrylate polymer powder P3 (0.6 g) obtained in Synthesis Example 3, NMP (9.9 g) was added, and the mixture was dissolved by stirring at room temperature for 1 hour. BCA (4.5 g) was added to this solution, and the polymer solution (A4) whose solid content concentration is 4.0 wt% was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent A6, A7, A13 on the conditions shown in Table 1, the liquid crystal aligning agent was produced using the method similar to liquid crystal aligning agent A4.

<Production of liquid crystal aligning agent: A8>

CHN (11.4 g) was added to the methacrylate polymer powder P5 (0.6 g) obtained in Synthesis Example 5, and the mixture was dissolved by stirring for 1 hour while heating at a temperature of 50°C. PGME (3.0 g) was added to this solution, and the polymer solution (A8) whose solid content concentration is 4.0 wt% was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent A9 on the conditions shown in Table 1, except having replaced PGME of liquid crystal aligning agent A8 with PGMEA, the liquid crystal aligning agent was produced using the same method.

<Production of liquid crystal aligning agent: A10>

CHN (15.0 g) was added to the methacrylate polymer powder P5 (0.6 g) obtained in Synthesis Example 5 above, and stirred for 1 hour while heating at a temperature of 50° C. to dissolve, and a polymer solution having a solid content concentration of 4.0 wt% (A10) ) was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent A15 and A21 on the conditions shown in Table 1, the liquid crystal aligning agent was produced using the method similar to liquid crystal aligning agent A10.

<Production of liquid crystal aligning agent: A14>

NMP (5.4 g) was added to the methacrylate polymer powder P9 (0.6 g) obtained in Synthesis Example 9, and the mixture was dissolved by stirring at room temperature for 1 hour. GBL (4.5g) and BCA (4.5g) were added to this solution, and the polymer solution (A14) whose solid content concentration is 4.0 wt% was obtained. This polymer solution becomes a liquid crystal aligning agent for forming a liquid crystal aligning film as it is.

Also about liquid crystal aligning agent B3 on the conditions shown in Table 1, except having replaced BCA of liquid crystal aligning agent A14 with BCS, the liquid crystal aligning agent was produced using the same method.

<Manufacture of substrate for measuring in-plane order parameter>

The board|substrate for a photoreaction rate measurement was produced in the procedure shown below using the liquid crystal aligning agent obtained above. As the substrate, a quartz substrate having a size of 40 mm x 40 mm and a thickness of 1.0 mm was used. After filtering liquid crystal aligning agent A1 with the filter with a filter hole diameter of 1.0 micrometer, it spin-coated on a quartz substrate, and after drying for 90 second on a 70 degreeC hotplate, the liquid crystal aligning film with a film thickness of 100 nm was formed.

(Example 1)

After irradiating 80 mJ/cm<2> of 313 nm ultraviolet-ray to a coating-film surface through a polarizing plate, it heated for 20 minutes with a 120 degreeC hotplate, and obtained the board|substrate with a liquid crystal aligning film in which photoreaction was completed.

Also about Examples 2-21 and Comparative Examples 1-5 on the conditions shown in Table 2, the board|substrate for in-plane orientation degree measurement was manufactured using the method similar to Example 1.

<Measurement of in-plane orientation>

In order to measure the optical anisotropy of a liquid crystal aligning film using the board|substrate with a liquid crystal aligning film produced above, S which is an in-plane orientation degree was computed from the following formula from the absorbance of polarized light. For the calculated value, the highest value within the range of irradiation dose was used.

In addition, the ultraviolet-visible near-infrared spectrophotometer U-3100PC by Shimadzu Corporation was used for the measurement of the absorbance.

Here, A _para represents the absorbance in the parallel direction to the irradiated polarized UV direction, and A _per represents the absorbance in the perpendicular direction to the irradiated polarized UV direction. A _large indicates the absorbance of the side with a larger value by comparing the absorbances in the parallel and vertical directions, and A _small indicates the absorbance of the side with a smaller value by comparing the absorbances in the parallel and vertical directions. It has shown that it has become a more uniform orientation state, so that the absolute value of the in-plane orientation degree is close|similar to 1.

As shown in Table 2, when the liquid crystal aligning agent of Examples 1-21 is used, it turns out that the orientation degree of a parallel direction is all high with respect to polarization UV direction. In Comparative Examples 1 and 2, the reason for not orientating in the parallel direction is that the amount of photosensitive group introduced is small, and the orientation by isomerization is superior to dimerization.

<Production of liquid crystal cell>

After filtering a liquid crystal aligning agent (A1) with a 0.45 micrometer filter, it spin-coated on the glass substrate with a transparent electrode, and after drying for 90 second on a 70 degreeC hotplate, the liquid crystal aligning film with a film thickness of 100 nm was formed.

(Example 15)

After inclining a coating film surface 40 degrees and irradiating 80 mJ/cm<2> of 313 nm ultraviolet-rays to a board|substrate through a polarizing plate, it heated with a 140 degreeC hotplate for 20 minutes, and obtained the board|substrate with a liquid crystal aligning film. After preparing two such substrates with a liquid crystal aligning film, and providing a 4 µm spacer on the liquid crystal aligning film surface of one substrate, the two substrates are combined so that the rubbing directions are parallel, leaving the liquid crystal injection port and sealing the periphery Thus, an empty cell having a cell gap of 4 µm was produced. Liquid crystal MLC-2003 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the antiparallel liquid crystal cell was obtained. After heating at the temperature of 120 degreeC for 30 minutes, the pretilt angle was measured with respect to this liquid crystal cell.

Also about Examples 22-42 and Comparative Examples 6-10 on the conditions shown in Table 3, the liquid crystal cell was manufactured using the method similar to Example 1, and the pretilt angle was measured.

As shown in Table 3, when the liquid crystal aligning agents of Examples 22-42 were used, it was possible for all to obtain the liquid crystal pretilt angle suitable for a twist nematic mode. In Comparative Examples 6 and 7, the reason that the pretilt angle is not expressed is considered to be because the tilt is not expressed in the uniaxial direction. In Comparative Example 9, although a favorable tilt angle was expressed, the obtained liquid crystal aligning film was cloudy. In Comparative Example 10, a tilt angle preferable for the twisted nematic mode was not expressed.

The board|substrate for an in-plane orientation degree measurement was manufactured using the method similar to Example 1 on the conditions of Table 4 using liquid crystal aligning agent A10. And as a result of measuring an orientation degree and a pretilt angle according to the said Example, as shown in Table 4, it became clear that a pretilt angle can be adjusted by the polarization|polarized-light ultraviolet irradiation amount and main baking conditions.

<Production of liquid crystal aligning agent: A22>

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

The orientation degree and pretilt angle were measured similarly using this orientation agent A22. As shown in Table 5, the result showed the pretilt angle of 9.9 degrees optimal for OCB mode.

Claims (8)

A polymer composition comprising (A) a copolymer obtained from a monomer mixture comprising the following monomers (A-1) and monomers (A-2),
Monomer (A-1): A monomer having one cinnamoyl moiety, 2 to 4 benzene rings not constituting a cinnamoyl moiety, and a polymerizable group;
Monomer (A-2): a monomer having one cinnamoyl moiety, one benzene ring not constituting the cinnamoyl moiety, and a polymerizable group;
(The cinnamoyl moiety and the benzene ring may have a substituent.)
The monomer (A-1) and the monomer (A-2) are a monomer 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) and a group represented by the following formula (2), polymer composition.

In the formula, A, B, and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, or -NH-CO-;
S is a C1-C12 alkylene group, and the hydrogen atom couple|bonded with it may each independently be substituted by the halogen group;
T is a single bond or a C1-C12 alkylene group, and the hydrogen atom couple|bonded with them may be substituted by the 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, a C1-C5 alkyl group, a (C1-C5 alkyl) carbonyl group, a C3-C7 cycloalkyl group, or a C1-C5 alkyloxy group;
In Y ₁ , P ₁ , Q ₁ and Q ₂ , the hydrogen atoms bonded to the benzene ring are each independently —CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, a (alkyl having 1 to 5 carbon atoms) carbonyl group, or a carbon number You may substituted with the alkyloxy group of 1-5;
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 is 2, X ₁ may be the same or different, and when the number of X ₂ is 2, X ₂ may be the same or different;
When the number of Q ₁ is 2, Q ₁ may be the same or different, and when the number of Q ₂ is 2, Q ₂ may be same or different;
In a monomer (A-1), the sum total of the number of benzene rings other than Y< ₁ > is 2-4;
In a monomer (A-2), the sum total of the number of benzene rings other than Y< ₁ > is 1;
The broken line indicates a bond with a polymerizable group. The method of claim 1,
The polymer composition in which the polymerizable group of the said monomer (A-1) and a monomer (A-2) is an acryl group or a methacryl group. [I] The process of apply|coating the polymer composition of Claim 1 or 2 on the board|substrate which has an electrode for liquid-crystal drive, and forming a coating film;
[II] The process of irradiating the ultraviolet-ray which polarized from the diagonal direction to the coating film obtained by [I]; 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 to which orientation control ability was provided by having. The board|substrate which has a liquid crystal aligning film manufactured by the method of Claim 3. A twisted nematic liquid crystal display device comprising the substrate according to claim 4 . [I] The process of apply|coating the polymer composition of Claim 1 or 2 on the board|substrate which has an electrode for liquid-crystal drive, and forming a coating film;
[II] The process of irradiating the ultraviolet-ray which polarized from the diagonal direction to the coating film obtained by [I]; and
[III] A step of heating the coating film obtained in [II];
The process of preparing the board|substrate (1st board|substrate) which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having;
[I'] The process of apply|coating the polymer composition of Claim 1 or 2 on a 2nd board|substrate, and forming a coating film;
[II'] The process of irradiating the polarized ultraviolet-ray to the coating film obtained by [I'];
[III'] A step of heating the coating film obtained in [II'];
The process of obtaining the 2nd board|substrate which has the said liquid crystal aligning film which obtains the liquid crystal aligning film to which orientation control ability was provided by having; and
[IV] a step of arranging the first and second substrates to face each other so that the liquid crystal aligning films of the first and second substrates face each other through a liquid crystal so that the ultraviolet exposure directions are orthogonal to each other to obtain a liquid crystal display element;
The manufacturing method of the said liquid crystal display element which obtains a twisted nematic type liquid crystal display element by having. A twisted nematic liquid crystal display device manufactured by the method according to claim 6 . delete