JP2001290155A - Method for forming liquid crystal alignment layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve alignment regulating power of a liquid crystal alignment layer alignment treated by an optical aligning method and to provide a method for forming the liquid crystal alignment layer preventing generation of flow alignment or an alignment defect such as disclination when the alignment layer is used for a liquid crystal display element. SOLUTION: The method for forming the liquid crystal alignment layer includes a stage for controlling the alignment direction of the alignment layer by irradiating the alignment layer applied on a substrate with light and containing a polymer having an atomic group capable of cross-linking reaction by light in its side chain with light and a stage for enhancing the liquid crystal alignment regulating power by heating the alignment layer irradiated with light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for forming a liquid crystal alignment film. More specifically, the present invention relates to a method for forming a liquid crystal alignment film having excellent alignment characteristics by irradiating linearly polarized radiation without performing a rubbing treatment.

[0002]

2. Description of the Related Art Conventionally, a nematic liquid crystal having a positive dielectric anisotropy has a sandwich structure with a substrate having a transparent electrode having a liquid crystal alignment film, and a long axis of liquid crystal molecules is continuously twisted by 90 ° or more between the substrates. TN (Twiste
d Nematic) type, STN (Super Twi)
2. Description of the Related Art A liquid crystal display device having a (stable nematic) type liquid crystal cell is known.

As means for aligning liquid crystal in the liquid crystal cell, an organic film is formed on a substrate surface, and then the surface of the organic film is rubbed in one direction with a cloth material such as rayon to impart liquid crystal alignment capability. (A method of performing rubbing treatment), a method of obliquely depositing silicon oxide on a substrate surface, and a method of forming a monomolecular film having a long-chain alkyl group using a Langmuir-Blodgett method (LB method). However, the latter two of these methods are limited in the size of the substrate to be processed or the alignment uniformity of the liquid crystal is insufficient, so that rubbing is advantageous industrially in terms of processing time and processing cost. Orientation of liquid crystal by processing is generally performed.

On the other hand, if the alignment of the liquid crystal is carried out by a rubbing process, there is a problem that dust or static electricity is easily generated during the process. When static electricity is generated,
Dust adheres to the surface of the alignment film, causing display failure. In addition, the TFT (thin film tran)
In the case of a substrate having a (sistor) element, a circuit of the TFT element is destroyed by the generated static electricity, which causes a reduction in yield. Furthermore, in a liquid crystal display device that is increasingly sophisticated in the future, the uniformity of the rubbing treatment poses a problem due to the unevenness of the substrate surface accompanying the increase in the density of pixels.

Another means for aligning the liquid crystal in the liquid crystal cell is to introduce anisotropy into the alignment film by irradiating a linearly polarized ultraviolet ray to a photosensitive organic film such as polyvinyl cinnamate formed on the substrate surface. Liquid crystal alignment ability. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust. As the photosensitive organic film used in the photo-alignment method, those that cause photodecomposition such as polyimide, those that cause photoisomerization such as azobenzene derivatives, polyvinyl cinnamate,
Examples thereof include those that cause a photocrosslinking reaction such as poly (4 ((2-methacryloyloxy) ethoxy) chalcone). Among these, an organic thin film that causes a photocrosslinking reaction is considered to be preferable in terms of thermal stability and electrical characteristics as an alignment film.

[0006]

However, conventionally,
In the alignment film obtained by the photo-alignment method, a sufficient liquid crystal alignment control force cannot be obtained, and therefore, when used in a liquid crystal display device, there is a problem that alignment defects such as flow alignment and disclination are likely to occur. there were. Therefore, an object of the present invention is to improve the alignment regulating force of a liquid crystal alignment film that has been subjected to an alignment treatment by a photo alignment method, and to cause alignment defects such as flow alignment and disclination when used in a liquid crystal display device. It is an object of the present invention to provide a method for forming a liquid crystal alignment film that prevents the occurrence of the problem. Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are achieved by irradiating a film containing a polymer having an atomic group capable of performing a crosslinking reaction with light in a side chain with light. And a step of increasing the liquid crystal alignment regulating force by heating the film irradiated with light to enhance the liquid crystal alignment ability.

The present inventor has found that, when a photocrosslinkable organic thin film is used as a photoalignment film, one of the causes of insufficient liquid crystal alignment control power is the effect of the structure resulting from the photocrosslinking reaction. It was found that the effect of the liquid crystal alignment in the unreacted portions was offset by each other. For example, poly (4 ((2-methacryloyloxy) ethoxy) formed on a substrate
(Chalkon) When a thin film is irradiated with linearly polarized ultraviolet light to form a liquid crystal alignment film, the cross-linked structure of the chalcone dimer is generated by the photoreaction of the linearly polarized ultraviolet light on the alignment film surface. Liquid crystal alignment ability due to anisotropic Van der Waals force. However, at the same time, the unreacted chalcone structure is oriented in the direction perpendicular to that direction, and the above-mentioned liquid crystal alignment ability is offset by the anisotropic Vander Waals force, and as a result, the alignment regulating force as the liquid crystal alignment film is weakened. Became unavoidable.

According to the method of the present invention, however, the liquid crystal alignment film treated by the photo-alignment method is subjected to a heat treatment prior to the liquid crystal injection step, whereby the unreacted chalcone structure is relaxed by heat, and An anisotropic Vander Waals force, which offsets the liquid crystal alignment ability caused by the alignment of the dimer crosslinked structure, is not exerted, and as a result, the alignment regulating force of the alignment film is improved. When the above-mentioned alignment film is used for a liquid crystal display device, occurrence of undesired alignment defects is prevented.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The liquid crystal alignment film formed in the present invention is formed by imparting liquid crystal alignment ability to a film obtained by applying a liquid crystal alignment agent.

Liquid crystal aligning agent The liquid crystal aligning agent used in the present invention is a polymer having a structure capable of undergoing a cross-linking reaction upon irradiation with ultraviolet rays (hereinafter, also referred to as “specific structure”) in a side chain (hereinafter, “specific polymer”). Also called)
Consists of As such a specific structure, a conjugated enone structure represented by the following formula (I), (II), or (III): P ¹ -CR ¹ = CR ² -CO-Q ¹ -... (I ) -P ² -CR ³ = CR ⁴ -CO-Q ² ... (II) -P ³ -CR ⁵ = CR ⁶ -CO-Q ^3- (III) ¹ and Q ² are a monovalent organic group having an aromatic ring, Q ¹ , P ² , P ³ and Q ³ are a divalent organic group having an aromatic ring and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group. A monovalent organic group having an aromatic ring of P ¹ and Q ² , and a monovalent organic group having an aromatic ring of Q ¹ , P ² , P ³ and Q ³
The organic group having a valence preferably includes an organic group having 6 to 20 carbon atoms.

These organic groups may contain a halogen atom. Specifically, 4-pentylphenyl group as P ^1, Q ^2, 4-fluorophenyl group, 3,4-difluorophenyl group, 3,4,5-trifluorophenyl group, 4-octylphenyl group, 4- Pentylbiphenyl group, 4-octylbiphenyl group, 4-fluorobiphenyl group, 3,4-difluorobiphenyl group, 3,4,5-trifluorobiphenyl group, 4-octyl-1-naphthyl group, 5-pentyl-1- Naphthyl group, 6-octyl-2
-Naphthyl group, 9-anthracenyl group, 10-pentyl-9-anthracenyl group and the like.

Further, Q ¹ , P ² , P ³ and Q ³ are 1,2-
Examples thereof include a phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and a 4,4′-biphenylene group. P ¹
And Q ² or Q ¹ , P ² , P ³ and Q ³ may be the same or different. In the formula, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ are a hydrogen atom or an alkyl group. Preferably it is a hydrogen atom or a C1-C6 alkyl group. These alkyl groups may be linear or branched, and may be the same or different. Other examples of the specific structure include a cinnamic acid derivative structure, a stilbene derivative structure, and a benzophenone derivative structure. Even though these structures are linear, they have the following formula (IV):

[0013]

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As in the coumarin structure represented by
It may be part of an annular structure. These specific structures are:
They may be used alone or in combination in the specific polymer.
Further, the skeleton of the specific polymer constituting the liquid crystal alignment agent used in the present invention is not particularly limited, but (1) polyimide,
(2) polyamic acid, (3) polyester, (4) polyamide, (5) poly (meth) acrylate, (6) maleimide polymer, styrene polymer or maleimide / styrene copolymer, (7) polysiloxane and the like. Those selected from the group consisting of the copolymers of the above are preferred. In particular, polyimide, because of its excellent heat resistance and electrical properties,
Polyamic acids and maleimide / styrene copolymers are preferred.

The specific polymer contained in the liquid crystal aligning agent used in the present invention has a glass transition temperature of 90 ° C.
Those described above are preferred. When the method of the present invention is used for a specific polymer having a glass transition temperature lower than this, a sufficient effect may not be obtained because the orientation of the structure caused by the photoreaction may be relaxed by heat. The specific polymer contained in the liquid crystal alignment agent used in the present invention,
In order to enhance the thermal stability after the photo-alignment treatment, the main chain may have a group capable of undergoing a cross-linking reaction by irradiation with ultraviolet rays.
Examples of such a photosensitive group include the structures exemplified above as specific structures. The polyimide and the polyamic acid, which are specific examples of the specific polymer contained in the liquid crystal alignment agent used in the present invention, are obtained by reacting (a) a tetracarboxylic dianhydride with a (b) diamine compound to form a polyamic acid. It can be obtained by producing and then subjecting this to dehydration and ring closure to produce a polyimide. At that time, a compound having the above-mentioned specific structure is used for at least one of the components (A) and (B) for the production of polyimide and polyamic acid.

Examples of the tetracarboxylic dianhydride having a specific structure include 2,2'-bis (4-chalconyloxy) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and , 3'-bis (4-chalconyloxy)
-4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -4,
4 ', 5,5'-biphenyltetracarboxylic dianhydride,
4,4'-bis (4-chalconyloxy) -2,2 ', 3,
3'-biphenyltetracarboxylic dianhydride, 6,6 '
-Bis (4-chalconyloxy) -2,2 ', 3,3'-
Biphenyltetracarboxylic dianhydride, 5,5'-bis (4-chalconyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4-
(Conconyloxy) -3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3'-bis (4
-Carbonyloxy) -4,4 ', 5,5'-diphenylethertetracarboxylic dianhydride, 2,2'-bis (4-chalconyloxy) -4,4', 5,5'-diphenylethertetra Carboxylic acid dianhydride, 4,4'-bis (4-chalconyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride, 6,6'-
Bis (4-chalconyloxy) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride 5,5'
-Bis (4-chalconyl) -2,2 ', 3,3'-diphenylethertetracarboxylic dianhydride; and the like.

Examples of the diamine compound having a specific structure include 4- (3,5-diaminophenoxy) chalcone, 4- (2,4-diaminophenoxy) chalcone, and are represented by the following formulas (V) and (VI). And the like. Among these, a compound represented by the following formula (V) is preferable.

[0018]

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(Wherein A ¹ and A ² represent a divalent aromatic group, and n represents an integer of 1 to 10.) In the above formulas (V) and (VI), C _n H _{2n + 1} The alkyl group represented by-may be linear or branched, and a linear one is more preferable. Examples of the divalent aromatic group represented by A ¹ and A ² include a phenylene group, a biphenylene group, a naphthylene group, a binaphthylene group, an anthrene group, a phenanthrylene group; and a polycyclic aromatic compound such as pyrene, chrysene, and naphthacene. Examples include an organic group from which two hydrogen atoms have been removed.

Specific examples of the compound represented by the above formula (V) include 4- (3,5-diaminophenoxy) -4'-
Isopropyl chalcone, 4- (3,5-diaminophenoxy) -4′-pentylchalcone, 4- (3,5-diaminophenoxy) -4′-pentylchalcone, 4-
(3,5-diaminophenoxy) -4′-octylchalcone, 4- (2,4-diaminophenoxy) -4′-pentylchalcone, 4- (2,4-diaminophenoxy)
-4'-octylchalcone, 4- (3,5-diaminobenzoyloxy) -4'-pentylchalcone, 4 '-(4
-Pentylphenyl) -4- (3,5-diaminophenoxy) chalcone is particularly preferred. These can be used alone or in combination of two or more.

Specific examples of the compound represented by the above formula (VI) include 4-isopropyl-4 '(3,5-diaminophenoxy) chalcone and 4-amyl-4' (3,5-diaminophenoxy) chalcone. , 4-pentyl-4 '(3,
5-diaminophenoxy) chalcone, 4-octyl-
4 ′ (3,5-diaminophenoxy) chalcone, 4-pentyl-2-methyl-4 ′ (2,4-diaminophenoxy) chalcone, 4-pentyl-2,5dimethyl-4 ′
(3,5-diaminophenoxy) chalcone, 4-octyl-2-methyl-4 '(3,5-diaminophenoxy)
Chalcone, 4-pentyl-4 ′ (2,4-diaminophenoxy) chalcone, 4-octyl-4 ′ (2,4-diaminophenoxy) chalcone, 4-pentyl-4 ′ (3,
5-diaminobenzoyloxy) chalcone, 4-octyl-4 '(3,5-diaminobenzoyloxy) chalcone,
4-pentyl-3 '(2,4-diaminobenzoyloxy) chalcone, 4-octyl-3' (2,4-diaminobenzoyloxy) chalcone and the like. These can be used alone or in combination of two or more. In the polyimide used in the present invention, other tetracarboxylic dianhydrides and / or diamine compounds can be used in combination without impairing the effects of the present invention.

Other tetracarboxylic dianhydrides include:
For example, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,
3,4-cyclobutanetetracarboxylic dianhydride, 1,3
-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride Anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,
9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural)- 3-methyl-3-cyclohexene-1,2
Aliphatic and alicyclic tetracarboxylic dianhydrides such as dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 2,3,6,
7-naphthalenetetracarboxylic dianhydride, 3,3 ',
4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic acid Dianhydride, 1,2,3,4-
Furantetracarboxylic dianhydride, 4,4'-bis (3,
4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,
4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride , Bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) -4,
An aromatic tetracarboxylic dianhydride such as 4'-diphenylmethane dianhydride can be mentioned.

Of these, 2,3,5-tricarboxycyclopentylacetic dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride are preferred. These can be used alone or in combination of two or more.

As other diamine compounds, for example, p-
Phenylenediamine, m-phenylenediamine, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone,
3'-dimethyl-4,4'-diaminobiphenyl, 4,
4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3
-Dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1, 3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Screw [4-
(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl)
-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-Tetrachloro-4,4'-diaminobiphenyl,2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl,3,3'-dimethoxy-4,4'-diaminobiphenyl, , 4.4'-
(P-phenyleneisopropylidene) bisaniline,
4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2, Aromatic diamines such as 2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl; and heteroatoms such as diaminotetraphenylthiophene Aromatic diamine having 1,1-meta-xylylenediamine, 1,3-
Propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine,
1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine,
Aliphatic and alicyclic diamines such as hexahydro-4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene dimethyl diamine, 4,4'-methylene bis (cyclohexylamine) ;
And diaminoorganosiloxanes such as diaminohexamethyldisiloxane.

Of these, p-phenylenediamine,
4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenylether, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [ 4
-(4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl Hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl preferable. These can be used alone or in combination of two or more.

The polyimide used in the present invention is:
The (a) tetracarboxylic dianhydride component and the (b) diamine component are polycondensed to obtain a polyamic acid, and then imidized by heating, if necessary, in the presence of a dehydrating agent and an imidization catalyst. It can be obtained by: The reaction temperature in the case of imidization by heating is usually 60 to 300 ° C, preferably 100 to 170 ° C. When the reaction temperature is lower than 60 ° C., the progress of the reaction is delayed, and when it exceeds 300 ° C., the molecular weight of the polyamic acid may be greatly reduced. Further, the reaction for imidization in the presence of a dehydrating agent and an imidization catalyst can be performed in an organic solvent. The reaction temperature is usually 0 to 180 ° C, preferably 60 to 150 ° C. Acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. As the imidization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but are not limited thereto. The amount of the dehydrating agent used is preferably 1.6 to 20 mol per 1 mol of the repeating unit of the polyamic acid. The amount of the imidization catalyst used is preferably 0.5 to 10 mol per 1 mol of the dehydrating agent used.
The content of the amic acid residue in the polyimide can be adjusted by the amount of the imidization catalyst and the dehydrating agent used.

The polyester is obtained by reacting (c) a dicarboxylic acid (dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid halide) with (d) a diol compound. At that time, in the production of polyester,
A compound having the above specific structure is used for at least one component of (c) the dicarboxylic acid component and (d) the diol compound.

The dicarboxylic acids having a specific structure include, for example, 2,3-chalcone dicarboxylic acid, 2,4-chalcone dicarboxylic acid, 3,4-chalcone dicarboxylic acid,
3,4-chalcone dicarboxylic acid, 3,5-chalcone dicarboxylic acid, 1- (4-chalconyloxy) -2,4-benzenedicarboxylic acid, 1- (4-chalconyloxy)-
2,5-benzenedicarboxylic acid, 1- (4-chalconyloxy) -2,6-benzenedicarboxylic acid and 1-
Examples thereof include (4-chalconyloxy) -3,5-benzenedicarboxylic acid, ester compounds such as alkyl esters thereof, and carboxylic acid halides such as carboxylic acid chloride.

Examples of the diol compound having a specific structure include 2,3-dihydroxychalcone, 2,4-dihydroxychalcone, 3,4-dihydroxychalcone,
4-dihydroxychalcone, 3,5-dihydroxychalcone, 1- (4-chalconyloxy) -2,4-benzenediol, 1- (4-chalconyloxy) -2,5-
Benzenediol, 1- (4-chalconyloxy)-
Examples include 2,6-benzenediol and 1- (4-chalconyloxy) -3,5-benzenediol.

Of these, 1- (4-chalconyloxy) -3,5-benzenedicarboxylic acid and 1- (4-
(Conconyloxy) -3,5-benzenediol is preferred. These can be used alone or in combination of two or more. Other dicarboxylic acids and / or diol compounds can be used in combination with the polyester used in the present invention to the extent that the effects of the present invention are not impaired.

Other dicarboxylic acid compounds include, for example, oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±) -malic acid, meso-tartaric acid, itacone Acid, maleic acid, methyl maleic acid, fumaric acid,
Methyl fumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyladipic acid, tetramethyladipic acid, methyleneadipic acid, muconic acid, galactal Acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,
Aliphatic carboxylic acids such as 3,6,6-tetramethylsuberic acid, azelaic acid, sebacic acid, perfluorosebacic acid, brassic acid, dodecyldicarboxylic acid, tridecyldicarboxylic acid and tetradecyldicarboxylic acid; cycloalkyldicarboxylic acids; Alicyclic carboxylic acids such as adipic acid, hexahydrophthalic acid, 1,4- (norbornene) dicarboxylic acid, bicycloalkyldicarboxylic acid, adamantanedicarboxylic acid, spiroheptanedicarboxylic acid; phthalic acid, isophthalic acid, dithioisophthalic acid, methyl Isophthalic acid, dimethyl isophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methyl terephthalic acid, dimethyl terephthalic acid, chloroterephthalic acid, bromoterephthalic acid, naphthalenedicarboxylic acid, oxofluorene orange Acid, anthracene dicarboxylic acids, biphenyl dicarboxylic acids, biphenylene dicarboxylic acid, dimethyl biphenylenedicarboxylic acid, 4,4 '' -
p-Telephenylenedicarboxylic acid, 4,4 '''-p-
Quarrelphenyl dicarboxylic acid, bibenzyl dicarboxylic acid, azobenzene dicarboxylic acid, homophthalic acid, phenylene diacetic acid, phenylenedipropionic acid, naphthalenedicarboxylic acid, naphthalenedipropionic acid, biphenyl diacetic acid, biphenyl dipropionic acid, 3,3'- [4,4 '
-(Methylenedi-p-biphenylene) dipropionic acid,
Aromatic dicarboxylic acids such as 4,4'-bibenzyldiacetic acid, 3,3 '-(4,4'-bibenzyl) dipropionic acid, oxydi-p-phenylenediacetic acid, and ester compounds such as respective alkyl esters; And carboxylic acid halides such as acid chloride. These can be used alone or in combination of two or more.

Other diol compounds include, for example, polyphenols such as catechol, alkyl catechol and hydroquinone; methylene bisphenol, isopropylidene bisphenol, butylidene bisphenol, thiobisphenol, sulfinyl bisphenol, sulfonylun bisphenol, oxybisphenol and the like. Bisphenols. These can be used alone or in combination of two or more.

The polyester used in the present invention can be obtained by heating and polycondensing the above-mentioned (c) dicarboxylic acid component and (d) diol compound component in the presence of a catalyst, if necessary. In the case of polycondensation of a dicarboxylic acid and a diol compound, as a catalyst, a protic acid such as sulfuric acid or p-toluenesulfonic acid, an oxide or salt of a heavy metal, or an organic metal compound such as titanium, tin, or lead is used. In the case of a reaction between a dicarboxylic acid ester and a diol compound, as a catalyst, an acetate or a carbonate compound such as lead, zinc, manganese, calcium, cobalt, or cadmium; or an oxide such as metallic magnesium, zinc, lead, antimony, or germanium. Is used. In the case of a reaction between a dicarboxylic acid halide and a diol compound, a basic catalyst such as pyridine or trierylamine is used as a catalyst.

The polyamide is obtained by reacting (e) dicarboxylic acids (dicarboxylic acid, dicarboxylic acid ester, dicarboxylic acid halide) with (f) a diamine compound. At that time, in the production of the polyamide, a compound having a specific structure is used for at least one of the (e) dicarboxylic acid component and the (f) diamine compound component.

As the dicarboxylic acids having a specific structure, the above-mentioned dicarboxylic acids (c) are used. Further, as the diamine compound having a specific structure, the diamine compound (b) described above is used. These can be used alone or in combination of two or more. Other dicarboxylic acid compounds and diamine compounds can be used in combination with the polyamide used in the present invention to the extent that the effects of the present invention are not impaired. As the other dicarboxylic acid compounds and diamine compounds, the above-mentioned other dicarboxylic acid compounds and diamine compounds are used. These can be used alone or in combination of two or more.

The polyamide used in the present invention is:
It is obtained by polycondensing the above-mentioned (e) dicarboxylic acid component and (f) diamine component in the presence of an acidic catalyst such as paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, etc., if necessary. The poly (meth) acrylate is obtained by polymerizing a (g) (meth) acrylate compound. At that time, in the production of poly (meth) acrylate, a compound having a specific structure is used as the (g) (meth) acrylate compound.

Examples of the (meth) acrylate compound having a specific structure include 4- (meth) acryloyloxychalcone, 4- (meth) acryloyloxy-4'-phenylchalcone, and 4- (meth) acryloyloxy-4'-pentylchalcone. , 4- (meth) acryloyloxy-4'-
(4-pentylphenyl) chalcone and the like.
These can be used alone or in combination of two or more. The poly (meth) acrylate used in the present invention includes other (meth) acrylates to the extent that the effects of the present invention are not impaired.
An acrylate compound can be used in combination.

Other (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Aliphatic (meth) acrylate compounds such as 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane tri (meth) acrylate; tetrahydrofurfuryl (meth) acrylate , Cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Alicyclic (meth) acrylate compounds such as sobornyl (meth) acrylate; benzyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Such as aromatic (meth) acrylate compounds. These can be used alone or in combination of two or more. Also, a maleimide polymer,
The styrene polymer and the maleimide / styrene copolymer include the following formula (II) -2 having the specific structure (II).

[0039]

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Here, the definitions of P ² , Q ² , R ³ and R ⁴ are the same as in the above formula (II), S ¹ is a hydrogen atom or a monovalent organic group, and X ¹ is a divalent A bonding group or a single bond, and / or the following formula (II) -3:

[0041]

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Here, the definitions of P ² , Q ² , R ³ and R ⁴ are the same as in the above formula (II), and X ² represents a divalent linking group or a single bond. Is used. That is, a styrene polymer having a chalcone structure represented by the above formula (II) -2, a maleimide polymer having a chalcone structure represented by the above formula (II) -3, and the above-mentioned formulas (II) -2 and (II) ) -3 is a copolymer containing both chalcone structures.

The above formulas (II) -2 and (II) -3
X ¹ and X ^{2 in} are a divalent linking group or a single bond. The divalent linking group is preferably an organic group containing an ether bond and / or an ester bond, more preferably an organic group having 6 to 24 carbon atoms containing an ether bond and / or an ester bond. Preferably an ether linkage and / or an ester linkage,
An organic group containing a straight-chain alkylene structure having 6 or more carbon atoms. S ¹ is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a methyl group.

The polymer is selected from the group consisting of a styrene derivative having a conjugated enone structure represented by the following formula (II) -2M and a maleimide derivative having a conjugated enone structure represented by the following formula (II) -3M. It can be obtained by radical polymerization of a monomer component containing at least one monomer in the presence of an initiator.

[0045]

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Examples of the styrene derivative having a conjugated enone structure include 4- (4-chalconyloxy) styrene, 4- (4-chalconyloxy) α-methylstyrene, and 4- (2- (4-chalconyloxy) ) Ethoxy) styrene, 4- (2- (4-chalconyloxy) ethoxy) α-methylstyrene, 4- (4- (4-chalconyloxy) butoxy) styrene, 4- (4- (4-chalconyl) Oxy) butoxy) α-methylstyrene, 4- (6
-(4-chalconyloxy) hexanoxy) styrene,
4- (6- (4-chalconyloxy) hexanoxy) α
-Methylstyrene, 4- (8- (4-carconyloxy) octanoxy) styrene, 4- (8- (4-chalconyloxy) octanoxy) α-methylstyrene, 4-
(4-chalconylcarboxy) styrene, 4- (4-chalconylcarboxy) α-methylstyrene, 4- (2-
(4-chalconylcarboxy) ethoxy) styrene, 4
-(2- (4-chalconylcarboxy) ethoxy) α-
Methylstyrene, 4- (4- (4-carconylcarboxy) butoxy) styrene, 4- (4- (4-carconylcarboxy) butoxy) α-methylstyrene, 4- (6
-(4-chaconylcarboxy) hexanoxy) styrene, 4- (6- (4-carconylcarboxy) hexanoxy) α-methylstyrene, 4- (8- (4-carconylcarboxy) octanoxy) styrene, 4- ( 8-
(4-chalconylcarboxy) octanoxy) α-methylstyrene, 4- (2- (4-chalconyl) ethoxy)
Styrene, 4- (2- (4-chalconyl) ethoxy) α
-Methylstyrene, 4- (4- (4-carconyl) butoxy) styrene, 4- (4- (4-carconyl) butoxy) α-methylstyrene, 4- (6- (4-carconyl) hexanoxy) styrene, -(6- (4-chalconyl) hexanoxy) α-methylstyrene, 4- (8-
(4-chalconyl) octanoxy) styrene, 4- (8
-(4-Carconyl) octanoxy) α-methylstyrene, 4- (2- (4-carconyloxy) ethyl) styrene, 4- (2- (4-carconyloxy) ethyl) α
-Methylstyrene, 4- (4- (4-chalconyloxy) butyl) styrene, 4- (4- (4-carconyloxy) butyl) α-methylstyrene, 4- (6- (4-
(Conconyloxy) hexyl) styrene, 4- (6-
(4-chalconyloxy) hexyl) α-methylstyrene, 4- (8- (4-carconyloxy) octyl) styrene, 4- (8- (4-carconyloxy) octyl) α-methylstyrene, -(2- (4-carbonylcarboxy) ethyl) styrene, 4- (2- (4-carbonylcarboxy) ethyl) α-methylstyrene, 4-
(4- (4-Carconylcarboxy) butyl) styrene, 4- (4- (4-carconylcarboxy) butyl)
α-methylstyrene, 4- (6- (4-carconylcarboxy) hexyl) styrene, 4- (6- (4-carconylcarboxy) hexyl) α-methylstyrene, 4-
(8- (4-chaconylcarboxy) octyl) styrene, 4- (8- (4-carconylcarboxy) octyl) α-methylstyrene, 4- (2- (4-carconyl) ethyl) styrene, 4- ( 2- (4-chalconyl)
Ethyl) α-methylstyrene, 4- (4- (4-chalconyl) butyl) styrene, 4- (4- (4-chalconyl) butyl) styrene, 4- (4- (4-chalconyl)
Butyl) α-methylstyrene, 4- (6- (4-chalconyl) hexyl) styrene, 4- (6- (4-chalconyl) hexyl) α-methylstyrene, 4- (8- (4-
(Conconyl) octyl) styrene, 4- (8- (4-chalconyl) octyl) α-methylstyrene, 4- (4-
(Conconyloxymethyl) styrene, 4- (4-carconyloxymethyl) α-methylstyrene, 4- (2-
(4-chalconyloxy) ethoxymethyl) styrene,
4- (2- (4-chalconyloxy) ethoxymethyl)
α-methylstyrene, 4- (4- (4-carconyloxy) butoxymethyl) styrene, 4- (4- (4-carconyloxy) butoxymethyl) α-methylstyrene,
4- (6- (4-carconyloxy) hexanoxymethyl) styrene, 4- (6- (4-carconyloxy) hexanoxymethyl) α-methylstyrene, 4- (8-
(4-chaconyloxy) octanoxymethyl) styrene, 4- (8- (4-chaconyloxy) octanoxymethyl) α-methylstyrene, 4- (4-chaconylcarboxymethyl) styrene, 4- (4-chalconylcarboxymethyl) α-methylstyrene, 4- (2- (4-
Chalconylcarboxy) ethoxymethyl) styrene, 4
-(2- (4-carconylcarboxy) ethoxymethyl) α-methylstyrene, 4- (4- (4-carconylcarboxy) butoxymethyl) styrene, 4- (4-
(4-Carconylcarboxy) butoxymethyl) α-methylstyrene, 4- (6- (4-carconylcarboxy) hexanoxymethyl) styrene, 4- (6- (4-
Carconylcarboxy) hexanoxymethyl) α-methylstyrene, 4- (8- (4-carconylcarboxy))
Octanoxymethyl) styrene, 4- (8- (4-chalconylcarboxy) octanoxymethyl) α-methylstyrene, 4- (2- (4-chalconyl) ethoxymethyl) styrene, 4- (2- ( 4- (carconyl) ethoxymethyl) α-methylstyrene, 4- (4- (4-carconyl) butoxymethyl) styrene, 4- (4- (4-carconyl) butoxymethyl) α-methylstyrene, 4-
(6- (4-Carconyl) hexanoxymethyl) styrene, 4- (6- (4-Carconyl) hexanoxymethyl) α-methylstyrene, 4- (8- (4-Carconyl) octanoxymethyl) Styrene, 4- (8- (4-
(Conconyl) octanoxymethyl) α-methylstyrene, 4- (4′-fluoro-4-chaconyloxy) styrene, 4- (4′-fluoro-4-chaconyloxy) α-methylstyrene, 4- ( 2- (4'-fluoro-4-chaconyloxy) ethoxy) styrene, 4-
(2- (4′-fluoro-4-chalconyloxy) ethoxy) α-methylstyrene, 4- (4- (4′-fluoro-4-chalconyloxy) butoxy) styrene, 4-
(4- (4′-fluoro-4-chalconyloxy) butoxy) α-methylstyrene, 4- (6- (4′-fluoro-4-chalconyloxy) hexanoxy) styrene,
4- (6- (4'-fluoro-4-chalconyloxy)
Hexanoxy) α-methylstyrene, 4- (8- (4 ′
-Fluoro-4-chaconyloxy) octanoxy) styrene, 4- (8- (4'-fluoro-4-chaconyloxy) octanoxy) α-methylstyrene, 4-
(4'-fluoro-4-camonylcarboxy) styrene, 4- (4'-fluoro-4-camonylcarboxy) α-methylstyrene, 4- (2- (4'-fluoro-4-camonylcarboxy) carboxy) Ethoxy) styrene, 4
-(2- (4'-fluoro-4-chaconylcarboxy) ethoxy) α-methylstyrene, 4- (4- (4 ′
-Fluoro-4-chaconylcarboxy) butoxy) styrene, 4- (4- (4'-fluoro-4-chaconylcarboxy) butoxy) α-methylstyrene, 4- (6
-(4'-fluoro-4-chaconylcarboxy) hexanoxy) styrene, 4- (6- (4'-fluoro-4)
-Camonylcarboxy) hexanoxy) α-methylstyrene, 4- (8- (4′-fluoro-4-chaconylcarboxy) octanoxy) styrene, 4- (8-
(4′-fluoro-4-chalconylcarboxy) octanoxy) α-methylstyrene, 4- (2- (4′-fluoro-4-chalconyl) ethoxy) styrene, 4- (2
-(4'-fluoro-4-chalconyl) ethoxy) α-
Methylstyrene, 4- (4- (4′-fluoro-4-chalconyl) butoxy) styrene, 4- (4- (4′-fluoro-4-chalconyl) butoxy) α-methylstyrene, 4- (6- ( 4'-fluoro-4-chaconyl) hexanoxy) styrene, 4- (6- (4'-fluoro-
4-chalconyl) hexanoxy) α-methylstyrene,
4- (8- (4′-fluoro-4-chalconyl) octanoxy) styrene, 4- (8- (4′-fluoro-4-)
Carconyl) octanoxy) α-methylstyrene, 4-
(2- (4′-fluoro-4-chalconyloxy) ethyl) styrene, 4- (2- (4′-fluoro-4-chalconyloxy) ethyl) α-methylstyrene, 4- (4
-(4'-fluoro-4-camonyloxy) butyl)
Styrene, 4- (4- (4′-fluoro-4-chaconyloxy) butyl) α-methylstyrene, 4- (6-
(4'-fluoro-4-chalconyloxy) hexyl)
Styrene, 4- (6- (4′-fluoro-4-chalconyloxy) hexyl) α-methylstyrene, 4- (8-
(4'-fluoro-4-chalconyloxy) octyl)
Styrene, 4- (8- (4′-fluoro-4-chaconyloxy) octyl) α-methylstyrene, 4- (2-
(4′-fluoro-4-chaconylcarboxy) ethyl) styrene, 4- (2- (4′-fluoro-4-camonylcarboxy) ethyl) α-methylstyrene, 4-
(4- (4′-fluoro-4-chalconylcarboxy))
Butyl) styrene, 4- (4- (4′-fluoro-4-)
Chalconylcarboxy) butyl) α-methylstyrene,
4- (6- (4'-fluoro-4-chaconylcarboxy) hexyl) styrene, 4- (6- (4'-fluoro-4-chaconylcarboxy) hexyl) α-methylstyrene, 4- (8- (4′-fluoro-4-chaconylcarboxy) octyl) styrene, 4- (8- (4′-
Fluoro-4-chaconylcarboxy) octyl) α-
Methylstyrene, 4- (2- (4′-fluoro-4-chalconyl) ethyl) styrene, 4- (2- (4′-fluoro-4-chalconyl) ethyl) α-methylstyrene,
4- (4- (4′-fluoro-4-chalconyl) butyl) styrene, 4- (4- (4′-fluoro-4-chalconyl) butyl) α-methylstyrene, 4- (6-
(4′-fluoro-4-chaconyl) hexyl) styrene, 4- (6- (4′-fluoro-4-chalconyl) hexyl) α-methylstyrene, 4- (8- (4′-fluoro-4-chalconyl) ) Octyl) styrene, 4- (8
-(4'-fluoro-4-chalconyl) octyl) α-
Methylstyrene, 4- (4'-fluoro-4-chalconyloxymethyl) styrene,-(4'-fluoro-4-
Chalconyloxymethyl) α-methylstyrene, 4-
(2- (4′-fluoro-4-chaconyloxy) ethoxymethyl) styrene, 4- (2- (4′-fluoro-
4-chalconyloxy) ethoxymethyl) α-methylstyrene, 4- (4- (4′-fluoro-4-chalconyloxy) butoxymethyl) styrene, 4- (4- (4 ′)
-Fluoro-4-chaconyloxy) butoxymethyl)
α-methylstyrene, 4- (6- (4′-fluoro-4
-Chalconyloxy) hexanoxymethyl) styrene,
4- (6- (4'-fluoro-4-chalconyloxy)
Hexanoxymethyl) α-methylstyrene, 4- (8-
(4′-fluoro-4-chaconyloxy) octanoxymethyl) styrene, 4- (8- (4′-fluoro-4)
-Chaconyloxy) octanoxymethyl) α-methylstyrene, 4- (2- (4′-fluoro-4-chalconyl) ethoxymethyl) styrene, 4- (2- (4′-fluoro-4-chalconyl) Ethoxymethyl) α-methylstyrene, 4- (4′-fluoro-4-chaconylcarboxymethyl) styrene, 4- (4′-fluoro-4-)
Chalconylcarboxymethyl) α-methylstyrene, 4
-(2- (4'-fluoro-4-chaconylcarboxy) ethoxymethyl) styrene, 4- (2- (4'-fluoro-4-chaconylcarboxy) ethoxymethyl)
α-methylstyrene, 4- (4- (4′-fluoro-4
-Chalconylcarboxy) butoxymethyl) styrene,
4- (4- (4′-fluoro-4-chaconylcarboxy) butoxymethyl) α-methylstyrene, 4- (6-
(4'-fluoro-4-chalconylcarboxy) hexanoxymethyl) styrene, 4- (6- (4'-fluoro-4-chalconylcarboxy) hexanoxymethyl) α
-Methylstyrene, 4- (8- (4'-fluoro-4-
Chalconylcarboxy) octanoxymethyl) styrene, 4- (8- (4′-fluoro-4-carconylcarboxy) octanoxymethyl) α-methylstyrene,
-(2- (4'-fluoro-4-chaconyl) ethoxymethyl) styrene, 4- (2- (4'-fluoro-4-
Chalconyl) ethoxymethyl) α-methylstyrene, 4
-(4- (4'-fluoro-4-chaconyl) butoxymethyl) styrene, 4- (4- (4'-fluoro-4-
Chalconyl) butoxymethyl) α-methylstyrene, 4
-(6- (4'-fluoro-4-chalconyl) hexanoxymethyl) styrene, 4- (6- (4'-fluoro-
4-chalconyl) hexanoxymethyl) α-methylstyrene, 4- (8- (4′-fluoro-4-chalconyl)
Octanoxymethyl) styrene, 4- (8- (4′-fluoro-4-chalconyl) octanoxymethyl) α-methylstyrene, 4-((3- (4-vinylphenyl))
Propionyloxy) -4′-fluorochalcone, 4-
((3- (4-vinylphenyl)) propionyloxy) chalcone, and compounds represented by the following formulas (1) to (8).

[0047]

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Of these, 4- (6- (4-chalconyloxy) hexanoxy) styrene and the above formula (1)
Compounds represented by-(8) are preferred. These can be used alone or in combination of two or more.

Examples of the maleimide derivative having a conjugated enone structure include 4- (4-chalconyloxy) phenylmaleimide, 4- (2- (4-chalconyloxy) ethoxy) phenylmaleimide, and 4- (4- (4 -Chalconyloxy) butoxy) phenylmaleimide, 4- (6
-(4-chalconyloxy) hexanoxy) phenylmaleimide, 4- (8- (4-carconyloxy) octanoxy) phenylmaleimide, 4- (4-chalconylcarboxy) phenylmaleimide, 4- (2- (4- Chalconylcarboxy) ethoxy) phenylmaleimide, 4
-(4- (4-carconylcarboxy) butoxy) phenylmaleimide, 4- (6- (4-carconylcarboxy) hexanoxy) phenylmaleimide, 4- (8-
(4-chalconylcarboxy) octanoxy) phenylmaleimide, 4- (2- (4-chalconyl) ethoxy)
Phenylmaleimide, 4- (4- (4-chalconyl) butoxy) phenylmaleimide, 4- (6- (4-chalconyl) hexanoxy) phenylmaleimide, 4- (8-
(4-chalconyl) octanoxy) phenylmaleimide, 4- (2- (4-chalconyloxy) ethyl) phenylmaleimide, 4- (4- (4-chalconyloxy)
Butyl) phenylmaleimide, 4- (6- (4-chalconyloxy) hexyl) phenylmaleimide, 4- (8
-(4-chaconyloxy) octyl) phenylmaleimide, 4- (2- (4-carconylcarboxy) ethyl) phenylmaleimide, 4- (4- (4-carconylcarboxy) butyl) phenylmaleimide, 4- ( 6-
(4-carbonylcarboxy) hexyl) phenylmaleimide, 4- (8- (4-carbonylcarboxy) octyl) phenylmaleimide, 4- (2- (4-carbonyl) ethyl) phenylmaleimide, 4- (4- ( 4-chalconyl) butyl) phenylmaleimide, 4- (6-
(4-chalconyl) hexyl) phenylmaleimide, 4
-(8- (4-chalconyl) octyl) phenylmaleimide, 4- (4'-fluoro-4-chalconyloxy)
Phenylmaleimide, 4- (2- (4′-fluoro-4
-Chalconyloxy) ethoxy) phenylmaleimide,
4- (4- (4'-fluoro-4-chalconyloxy)
Butoxy) phenylmaleimide, 4- (6- (4′-fluoro-4-chalconyloxy) hexanoxy) phenylmaleimide, 4- (8- (4′-fluoro-4-chalconyloxy) octanoxy) phenylmaleimide,
-(4'-fluoro-4-camonylcarboxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chaconylcarboxy) ethoxy) phenylmaleimide,
4- (4- (4'-fluoro-4-chaconylcarboxy) butoxy) phenylmaleimide, 4- (6- (4 '
-Fluoro-4-chaconylcarboxy) hexanoxy) phenylmaleimide, 4- (8- (4'-fluoro-4-carbonylcarboxy) octanoxy) phenylmaleimide, 4- (2- (4'-fluoro-4-chalconyl) ) Ethoxy) phenylmaleimide, 4- (4-
(4′-fluoro-4-chalconyl) butoxy) phenylmaleimide, 4- (6- (4′-fluoro-4-chalconyl) hexanoxy) phenylmaleimide, 4- (8
-(4'-fluoro-4-chalconyl) octanoxy)
Phenylmaleimide, 4- (2- (4′-fluoro-4
-Chalconyloxy) ethyl) phenylmaleimide, 4
-(4- (4'-fluoro-4-chalconyloxy) butyl) phenylmaleimide, 4- (6- (4'-fluoro-4-chalconyloxy) hexyl) phenylmaleimide, 4- (8- (4 '-Fluoro-4-chaconyloxy) octyl) phenylmaleimide, 4- (2-
(4′-fluoro-4-chalconylcarboxy) ethyl) phenylmaleimide, 4- (4- (4′-fluoro-4-chalconylcarboxy) butyl) phenylmaleimide, 4- (6- (4′-fluoro- 4-chalconylcarboxy) hexyl) phenylmaleimide, 4- (8-
(4′-fluoro-4-chalconylcarboxy) octyl) phenylmaleimide, 4- (2- (4′-fluoro-4-chalconyl) ethyl) phenylmaleimide, 4-
(4- (4'-fluoro-4-chalconyl) butyl) phenylmaleimide, 4- (6- (4'-fluoro-4-
(Conconyl) hexyl) phenylmaleimide, 4- (8
-(4'-fluoro-4-chalconyl) octyl) phenylmaleimide, 4- (8- (4'-fluoro-4-chalconyloxy) octanoxymethyl) phenylmaleimide, 4- (8- (4'- Fluoro-4-chaconylcarboxy) octanoxymethyl) phenylmaleimide,
4- (2- (4'-fluoro-4-chalconyl) ethoxymethyl) phenylmaleimide, 4- (4- (4'-fluoro-4-chalconyl) butoxymethyl) phenylmaleimide, 4- (6- (4 ' -Fluoro-4-chaconyl) hexanoxymethyl) phenylmaleimide, 4-
(8- (4′-fluoro-4-chalconyl) octanoxymethyl) phenylmaleimide, the following formulas (9) to (1)
And the like. Of these,
4- (6- (4-chalconyloxy) hexanoxy) phenylmaleimide, 4- (8- (4-chalconyloxy) octanoxy) phenylmaleimide, 4- (6-
(4'-fluoro-4-chalconyloxy) hexyl)
Phenylmaleimide, 4- (8- (4′-fluoro-4
-Conconyloxy) octyl) phenylmaleimide,
Compounds represented by the following formulas (9) to (12) are preferred.
These can be used alone or in combination of two or more. Further, it can be used in combination with the styrene derivative.

[0050]

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The polysiloxane has the specific structure (II)
Formula (III) -1 having the following I) Here, P ³ , Q ³ , R ⁵ and R ⁶ are defined by the above formula (II)
The same as in I), and Z ¹ is a hydroxyl group or a methyl group, and / or the following formula (IV) -1 having the above specific structure (IV) Here, P ⁴ , Q ⁴ , R ⁷ and R ⁸ are defined by the above formula (IV)
And Z ² is a hydroxyl group or a methyl group.

The polysiloxane can be obtained by subjecting a cyclic oligosiloxane derivative to ring-opening polymerization in the presence of an acid or base catalyst, or hydrolyzing a dichlorosilane derivative. The polysiloxane used in the present invention can be obtained by using a compound having the above specific structure as at least a part of the cyclic oligosiloxane derivative or the dichlorosilane derivative. Another method for obtaining the polysiloxane used in the present invention is a method of reacting a polysiloxane derivative having a Si-H bond with a compound having the above specific structure and allyl group in the presence of a catalyst such as platinum chloride. is there.

Examples of the cyclic oligosiloxane derivative having a specific structure include 1,3,5,7-tetra (4-chalconyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5, 7-tetra (4'-chalconyl)-
1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra (3- (4-chalconyloxy)
Propyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3- (4′-chaconyloxy) propyl) -1,3,5,7-tetramethyl Cyclotetrasiloxane 1,3,5,7-tetra (3-
(4-chalconyl) propyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3- (4′-chalconyl) propyl) -1,3,5,7
-Tetramethylcyclotetrasiloxane, 1,3,5,7-
Tetra (6- (4-chalconyloxy) hexyl)-
1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7-tetra (6- (4′-chaconyloxy) hexyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (6- ( 4-chalconyl) hexyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (6- (4 ′
-Chaconyl) hexyl) -1,3,5,7-tetramethylcyclotetrasiloxane. These can be used alone or in combination of two or more.

These cyclic oligosiloxane derivatives having a specific structure include a cyclic oligosiloxane such as 1,3,5,7-tetramethylcyclotetrasiloxane and a compound having a specific structure such as 4-allyloxychalcone. It is obtained by reacting in the presence of a platinum catalyst or the like. Examples of the dichlorosilane derivative having a specific structure include, for example, monomethylmono (4-chalconyl) dichlorosilane, monomethylmono (4'-carconyl) dichlorosilane, monomethylmono (3- (4-chalconyloxy) propyl) dichlorosilane, monomethyl Things (3-
(4′-chaconyloxy) propyl) dichlorosilane, monomethylmono (3- (4-carconyl) propyl) dichlorosilane, monomethylmono (3- (4′-carconyl) propyl) dichlorosilane, and the like. These can be used alone or in combination of two or more.

The dichlorosilane derivatives having these specific structures are prepared by reacting a dichlorosilane such as dichloromethylsilane with a compound having a specific structure such as 4-allyloxychalcone in the presence of a platinum catalyst or the like. can get. Of these, 1,3,5,7-tetra (3- (4-chalconyloxy) propyl) -1,3,
Polymers derived from 5,7-tetramethylcyclotetrasiloxane are preferred. Other cyclic oligosiloxane derivatives or other dichlorosilane derivatives can be used in combination with the polysiloxane used in the present invention to the extent that the effects of the present invention are not impaired.

Examples of other cyclic oligosiloxane derivatives include, for example, 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane, 1,3,5,7-tetrahydroxy-1,3, 5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5,7,7-octahydroxycyclotetrasiloxane, 1,1,3,3,5,5,7,7-octaphenyl Examples thereof include cyclotetrasiloxane, 1,3,5,7-tetrahydroxy-1,3,5,7-tetraphenylcyclotetrasiloxane.

Of these, 1,1,3,3,5,5,7,7
-Octamethylcyclotetrasiloxane is preferred. These can be used alone or in combination of two or more. Examples of other dichlorosilane derivatives include dichlorodimethylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, and dichlorodiethylsilane. Of these, dichlorodimethylsilane is preferred. These can be used alone or in combination of two or more. The polysiloxane polymer used in the present invention generally has a weight average molecular weight in terms of polystyrene (hereinafter, also referred to as “Mw”) of 5,000 to 100,000.
The liquid crystal aligning agent used in the present invention comprises a solution of a specific polymer and another polymer. The solvent used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the polymer, and can be used alone or in combination of two or more solvents.

The liquid crystal aligning agent used in the present invention comprises:
In order to stabilize the pretilt angle and increase the film strength,
Various thermosetting crosslinking agents may be included. As the thermosetting crosslinking agent, a polyfunctional epoxy-containing compound is effective, and bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl diamine type Epoxy resins, heterocyclic epoxy resins, epoxy group-containing acrylic resins and the like can be used. In a commercial product, for example, Epolite 4
00E, 3002 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.),
Epicoat 828, 152, Epoxy Novolak 18
OS (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like. Furthermore, when using the above-mentioned polyfunctional epoxy-containing compound, a base catalyst such as 1-benzyl-2-methylimidazole can be added for the purpose of efficiently causing a crosslinking reaction.

Further, the liquid crystal aligning agent used in the present invention may contain a functional silane-containing compound for the purpose of improving the adhesion to the substrate. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)
-3-aminopropyltrimethoxysilane, N- (2-
Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3
-Ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane,
N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxyisylyl-
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-aminopropyltriethoxysilane and the like. Further, tetracarboxylic acid described in JP-A-63-291922 can be used. A reaction product of an acid dianhydride and an amino group-containing silane compound may, for example, be mentioned.

[0060] As a method for forming a liquid crystal alignment film using the liquid crystal aligning agent of the liquid crystal alignment film present invention include, for example, the following method. First, the liquid crystal aligning agent of the present invention is applied to the transparent conductive film side of the substrate provided with the transparent conductive film by a roll coater method, a spinner method, a printing method or the like, and heated at a temperature of 40 to 200 ° C. to form a coating film. Is formed. The thickness of the coating film is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm.

As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, or a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate can be used. As the transparent conductive film, a NESA film made of SnO ² , In ² O ³ —S
An ITO film made of nO ² or the like can be used. For the patterning of these transparent conductive films, a photo-etching method, a method using a mask in advance, or the like is used.

In applying the liquid crystal aligning agent, a functional silane-containing compound, titanate, or the like is previously applied onto the substrate and the transparent conductive film in order to further improve the adhesion between the substrate and the transparent conductive film. You can also. The coating is then irradiated with light, preferably linearly polarized radiation. The radiation used is preferably between 150 nm and 8
Ultraviolet and visible light having a wavelength of 00 nm,
Among them, ultraviolet light having a wavelength of 240 nm to 450 nm is particularly preferable. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser.

Further, the coating film is subjected to a heat treatment at a temperature not lower than room temperature (25 ° C.). The heat treatment temperature is 100
-250 ° C is preferred, and 100-200 ° C is particularly preferred. If the heat treatment temperature is too low, a sufficient effect of improving the liquid crystal alignment regulating force cannot be obtained. If the heat treatment temperature is too high, thermal decomposition of the alignment film may occur. The heat treatment time is preferably from 15 minutes to 4 hours, particularly preferably from 1 hour to 2 hours. In addition, this heat treatment step can be performed simultaneously with the thermosetting step of the sealant when the periphery of the liquid crystal cell is sealed with the sealant in the manufacturing process of the liquid crystal display element.

Liquid crystal display device A liquid crystal display device formed using the liquid crystal alignment film formed according to the present invention is obtained as follows. The two substrates on which the liquid crystal alignment film is formed are opposed to each other so that the polarization direction of the linearly polarized radiation irradiating the liquid crystal alignment film is at a predetermined angle, the peripheral portion between the substrates is sealed with a sealant, and the liquid crystal is removed. The liquid crystal cell is constructed by filling and sealing the filling hole. Then, a polarizing plate is adhered to both sides of the polarizing plate such that the polarizing direction of the polarizing plate forms a predetermined angle with the polarizing direction of the linearly polarized radiation irradiating the liquid crystal alignment film of the substrate, thereby forming a liquid crystal display device. By adjusting the angle between the polarization directions of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment films are formed, a TN type or STN type liquid crystal cell is provided. A liquid crystal display element can be obtained arbitrarily.

As the sealing agent, for example, a curing agent and an epoxy resin containing aluminum oxide spheres as a spacer can be used. As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a TN type liquid crystal cell, a liquid crystal cell which forms a nematic type liquid crystal is preferable. For example, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, and a pyrimidine. Liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, and the like are used. In the case of the STN type liquid crystal cell, the liquid crystal may be a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate or the like, or trade names C-15 and CB-1.
5 (manufactured by Merck & Co.) and the like can be further used. further,
Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

The polarizing plate used outside the liquid crystal cell may be a polarizing plate in which a polarizing film called an H film in which polyvinyl alcohol is stretched and oriented and iodine is absorbed is sandwiched between cellulose acetate protective films, or the H film itself. And the like.

[0067]

The liquid crystal alignment film formed by the method of the present invention has a higher liquid crystal alignment control force than the conventional optical alignment film, and therefore, when a liquid crystal display device is formed using the same, undesirable alignment defects are unlikely to occur. Therefore, a liquid crystal display element having high contrast without display unevenness can be configured.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Reference Example Liquid Crystal Alignment Agent (Optomer AL-125 manufactured by JSR Corporation)
4) was applied to a transparent electrode surface using a spinner on a glass substrate with a transparent electrode made of an ITO film so as to have a thickness of 0.05 μm, and dried at 180 ° C. for 1 hour to form a thin film. The thin film was subjected to a rubbing treatment by a rubbing machine having a roll around which a nylon cloth was wound at a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. Next, the outer edge of each of the pair of rubbed substrates having the liquid crystal alignment film has a diameter of 17 μm.
After the epoxy resin adhesive containing aluminum oxide spheres was screen-printed and applied, a pair of substrates were overlapped so that the liquid crystal alignment film surfaces faced each other, and the rubbing directions were orthogonal, and pressure-bonded to cure the adhesive. .

Next, between the pair of substrates from the liquid crystal injection port,
Nematic liquid crystal (ZLI-1565, manufactured by Merck)
After filling, the liquid crystal injection port was sealed with an epoxy adhesive. After the cell was heat-treated at 120 ° C. for 10 minutes and returned to room temperature, a polarizing plate was attached to both outer surfaces of the substrate such that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film of each substrate. Thus, a liquid crystal display device was manufactured.

The orientation of the liquid crystal in this liquid crystal display element was good, and there was no visible flow orientation and disclination. When a voltage of 5 V was applied, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage, and the contrast was good.

Example 1 (1) 0.05 mol (24.8 g) of 4- (6- (4-chalconyloxy) hexanoxy) phenylmaleimide
0.005 mol of p-trifluoromethylstyrene (0.005 mol)
86 g), 0.045 mol (4.7 g) of styrene and 3.0 g of azobisisobutyronitrile were dissolved in 500 ml of dimethylacetamide and reacted at 80 ° C. for 10 hours under a nitrogen atmosphere. The viscous reaction mixture was poured into methanol to precipitate and dry the polymer, and the following formula (1)

[0072]

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24.3 g of a copolymer (polymer 1) consisting of the above repeating units was obtained. (2) Using Polymer 1, a thin film was formed on a substrate in the same manner as in Reference Example. The surface of the thin film was irradiated with a linearly polarized ultraviolet ray having a wavelength of 365 nm of 1.0 J / cm ² by an ultraviolet polarization exposure apparatus (manufactured by Run Technical Service).

Next, the substrates were overlapped and crimped in the same manner as in the reference example, except that the direction in which the liquid crystal alignment films were overlapped was not in the rubbing direction but in the polarization direction of the ultraviolet light.
The adhesive was cured at 150 ° C. for 1 hour and the substrate was heat-treated. Further, a liquid crystal display device was manufactured in the same manner as in the reference example. The orientation of the liquid crystal was as good as the reference example, and there was no visible flow orientation and no disclination. When a voltage was applied under the same conditions as in Comparative Example 1, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage, and the contrast was good.

Example 2 (1) 0.045 mol (19.3 g) of 4- (6- (4-chalconyloxy) hexanoxy) styrene, 0.005 mol (0.86 g) of p-trifluorostyrene, 0.05 mol (8.7 g) of phenylmaleimide and 3.0 g of azobisisobutyronitrile were added to 50 parts of dimethylacetamide.
It was dissolved in 0 ml and reacted at 80 ° C. for 10 hours under a nitrogen atmosphere. The viscous reaction mixture is poured into methanol to precipitate and dry the polymer, and the following formula (2)

[0076]

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A polymer comprising a repeating unit (Polymer 2)
25.5 g were obtained. (2). A liquid crystal display device was produced in the same manner as in Example 1 except that Polymer 2 was used instead of Polymer 1. All of the liquid crystal display devices had good liquid crystal orientation, and had visible flow alignment and There was no disclination. When a voltage was applied under the same conditions as in the reference example, the ON-OF of the applied voltage
In response to F, a change in brightness of the liquid crystal display element is observed,
The contrast was good.

Example 3 (1) 0.05 mol (21.4 g) of 4- (6- (4-chalconyloxy) hexanoxy) styrene, 4- (6-
(4-chalconyloxy) hexanoxystyrene 0.0
45 mol (22.3 g), p-trifluorostyrene 0.5%
005 mol (0.86 g) and 3.0 g of azobisisobutyronitrile were dissolved in 500 ml of dimethylacetamide and reacted at 80 ° C. for 10 hours under a nitrogen atmosphere. The viscous reaction mixture is poured into methanol to precipitate and dry the polymer.

[0079]

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A polymer comprising a repeating unit (Polymer 3)
34.8 g were obtained. (2) A liquid crystal display device was prepared in the same manner as in Example 1 except that polymer 3 was used instead of polymer 1. There was no disclination. When a voltage was applied under the same conditions as in the reference example, the ON-OF of the applied voltage
In response to F, a change in brightness of the liquid crystal display element is observed,
The contrast was good.

Comparative Example 1 A liquid crystal display device was produced in the same manner as in Example 1 except that the adhesive was cured at room temperature using the above-mentioned polymer 1, and a flow orientation and an orientation such as disclination were obtained. Defects were seen. When a voltage was applied under the same conditions as in the reference example, a change in the brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage, but the contrast was low due to light leakage from the alignment defect site. Was.

[0082]

According to the method for forming a liquid crystal alignment film using the liquid crystal alignment agent of the present invention, dust adhesion due to static electricity generated during the conventional rubbing treatment and circuit destruction of the TFT element do not occur. A liquid crystal alignment film can be formed with a high yield. Further, the liquid crystal aligning agent formed by the method of the present invention,
Because it has a higher liquid crystal alignment control force than the conventional photo alignment film,
When used for display of TN type, STN type, etc., undesired poor alignment is unlikely to occur, and a liquid crystal display element with high display quality can be obtained, which can be effectively used for various devices. For example,
It is suitably used for desktop computers, watches, clocks, coefficient display boards, word processors, personal computers, and display devices such as liquid crystal televisions.

Continued on the front page (72) Inventor Shoichi Nakata 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Atsushi Kumano 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Inc. (72) Inventor Yasumasa Takeuchi 2--11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation F-term (reference) 2H090 HB09Y HB10Y HC05 KA05 KA08 MB12 MB13 4F073 AA14 AA32 BA18 BA19 BA23 BA29 BA31 BA33 BB01 CA45 CA53 EA01 EA52 GA01 HA05

Claims (3)

[Claims] 1. A step of irradiating a film containing a polymer having an atomic group capable of undergoing a cross-linking reaction with light in a side chain to impart liquid crystal alignment ability, and heating the film irradiated with the light. A method of forming a liquid crystal alignment film, the method comprising: 2. The method according to claim 1, wherein the glass transition temperature of the polymer is 90 ° C. or higher. 3. The method according to claim 1, wherein the atomic group is represented by the following formula (I), (II) or (III): P ¹ -CR ¹ = CR ² -CO-Q ^1- (I) -P ² -CR ³ = CR ⁴ -CO-Q ² ... (II) -P ³ -CR ⁵ = CR ⁶ -CO-Q ³ -... (III) wherein P ¹ and Q ² are aromatic. Q ¹ , P ² , P ³ and Q ³ are divalent organic groups having an aromatic ring, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and 3. The method according to claim 1, wherein R ⁶ is a hydrogen atom or an alkyl group.