KR20150040734A - Manufacturing method for liquid crystal alignment film, photo-alignment agent, and liquid crystal display device - Google Patents

Abstract

The purpose of the present invention is to provide a method for manufacturing a liquid crystal alignment film capable of obtaining a liquid crystal display device having a small amount of remaining electric charge accumulated and exhibiting a high voltage maintenance rate. A liquid crystal alignment film is manufactured by a method comprising the steps of: forming a film by applying, to a substrate, a liquid crystal alignment agent that is a polymer wherein (A) polymer and (B) polymer are included as one or more kinds of polymeric components selected from the group consisting of poly(amic acid), poly(amic acid) ester and polyimide, and (A) polymer has, in a main chain, a structure (Y) represented by formula (1) with the proviso that an amide bond formed by polymerization reaction is excluded if X^1 is -NH-; and making the film into a liquid crystal alignment film by irradiating the film with light. In formula1, X^1 is a sulfur atom, an oxygen atom or -NH-, [*] represents an unpaired electron, and at least one among two [*] is bonded to an aromatic ring.

Description

Technical Field [0001] The present invention relates to a method for manufacturing a liquid crystal alignment film, a liquid crystal alignment film,

TECHNICAL FIELD The present invention relates to a method for manufacturing a liquid crystal alignment film, a photo-dispersing agent, and a liquid crystal display element, and more particularly, to a technique for imparting liquid crystal alignment property to a film by photo-

Conventionally, various driving methods have been developed as liquid crystal display devices, which have different electrode structures and physical properties of liquid crystal molecules to be used. For example, conventional liquid crystal display devices such as TN type, STN type and VA type, IPS type, FFS Liquid crystal display devices such as a liquid crystal display device and a liquid crystal display device such as a liquid crystal display device. Among these, in the liquid crystal display device of the old system type, electrodes are formed on each of a pair of substrates arranged opposite to each other, and an electric field is generated in a direction perpendicular to the substrate, while in a liquid crystal display device of a transverse electric system, An electrode is formed on one of the pair of substrates, and an electric field is generated in a direction parallel to the substrate. Thus, it is known that the liquid crystal display element of the transverse electric field system can improve the contrast and the viewing angle characteristic as compared with the conventional transverse electric field system.

The liquid crystal display element controls the alignment state of the liquid crystal molecules by the liquid crystal alignment film formed on the substrate. As the material of the liquid crystal alignment film, polyamic acid and polyimide are generally used in view of good heat resistance, mechanical strength, and various properties such as affinity with liquid crystals. As a technique for imparting liquid crystal aligning ability to a polymer thin film formed by a liquid crystal aligning agent, a photo alignment method using photoisomerization, photo dimerization, photolysis, or the like has recently been proposed as a technique instead of the rubbing method. This photo alignment method is a method of applying anisotropy to a film of a radiation-sensitive organic thin film formed on a substrate by irradiating polarized or unpolarized radiation, thereby controlling the orientation of the liquid crystal molecules. According to this method, generation of dust and static electricity in the process can be suppressed as compared with the conventional rubbing method, so that it is possible to suppress the occurrence of defective display caused by dust or the like and reduction in the yield. In addition, the organic thin film formed on the substrate has an advantage that the liquid crystal aligning ability can be uniformly given.

As liquid crystal aligning agents to be applied to the photo alignment method, various ones have conventionally been proposed (see, for example, Patent Documents 1 to 4). Patent Document 1 discloses a liquid crystal aligning agent containing a polymer having a group containing a chalcone structure in its side chain, and Patent Document 2 discloses a liquid crystal aligning agent containing a polymer having a flavonoid structure. Patent Document 3 discloses a liquid crystal aligning agent containing a polymer having an azobenzene structure or an anthracene structure, and Patent Document 4 discloses a liquid crystal aligning agent containing an azo compound having a low molecular weight.

Japanese Patent Application Laid-Open No. 2003-307736 Japanese Laid-Open Patent Publication No. 2004-163646 Japanese Patent Application Laid-Open No. 2002-250924 Japanese Patent Application Laid-Open No. 2004-83810

In a liquid crystal display element of a transverse electric field system, a residual image (burn-in of an image) due to the accumulation of residual charges may be a problem, while having a wide viewing angle characteristic and a good contrast characteristic.

Further, by applying the liquid crystal alignment film obtained by the photo alignment method to the liquid crystal display device of the transverse electric field system, it is expected that the above-described characteristics of the photo alignment method can be obtained. However, in the case of the photo-alignment method in which a chemical change is caused by irradiation of ultraviolet rays or the like, the electrical characteristics tend to be generally inferior to the conventional liquid-crystal alignment film by rubbing treatment. Particularly, in the case of involving photolysis of the polymer, there is a problem that impurity ions increase in the liquid crystal cell and the voltage holding ratio tends to decrease. In addition, it is presumed that the liquid crystal alignment film obtained by the photo alignment method has insufficient alignment control force of liquid crystal and becomes a cause of burn-in in the liquid crystal display device of the transverse electric field system. On the other hand, along with the recent high quality of the liquid crystal panel, the liquid crystal display element is required to have excellent electric characteristics and low residual image quality of the liquid crystal display element.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems, and its main object is to provide a method of manufacturing a liquid crystal alignment film capable of obtaining a liquid crystal display element having a small accumulation amount of residual charges and a high voltage holding ratio.

Means for Solving the Problems The present inventors have studied extensively in order to achieve the problems of the prior art as described above and have focused on a light-free potential reaction as a mechanism for generating anisotropy in a film by light irradiation. This light-free-potential reaction generates a skeleton change of the molecular structure by a potential reaction from a phenyl ester to an aromatic hydroxy ketone. Based on this point of view, the inventors of the present invention have found that a polymer of at least one of polyamic acid, polyamic acid ester and polyimide having a structure in which an ester group or a thioester group is bonded to an aromatic ring in the main chain, And a liquid crystal alignment film was formed by the photo alignment method. As a result, it was found that the above problems could be solved, and the present invention was completed. Specifically, according to the present invention, there are provided the following production method of a liquid crystal alignment film, a photo-dispersing agent, and a liquid crystal display element.

(A) a polymer and (B) a polymer as a polymer component selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, wherein the polymer (A) , A liquid crystal aligning agent which is a polymer having in its main chain a structure (Y) represented by the following formula (1) (except that, in the case where X ¹ is -NH-, an amide bond formed by polymerization reaction is excluded) Forming a coating film on the coating film; and irradiating the coating film with light to form a liquid crystal alignment film.

(In the formula (1), X ¹ represents a sulfur atom, an oxygen atom or -NH-; "*" represents a bonding hand, provided that at least one of the two "*" .

In another aspect, the present invention provides a photo-dispersing agent containing the polymer (A) and the polymer (B). According to another aspect of the present invention, there is provided a liquid crystal display element comprising a liquid crystal alignment film formed by using the above-described manufacturing method.

In the transverse electric field type liquid crystal display element, a liquid crystal alignment film is produced by using a polymer having a structure represented by the formula (1) in the main chain and a liquid crystal aligning agent blended with a polymer different from the polymer, It is possible to obtain a liquid crystal display element having a small accumulated charge amount.

(Mode for carrying out the invention)

Hereinafter, a method for producing a liquid crystal alignment film for photo-alignment of the present invention (hereinafter also referred to as " photo-alignment agent ") and a liquid crystal alignment film using the photo-alignment agent will be described. First, each component of the photo-dispersing agent and other components optionally blended as required will be described.

<Polymer Component>

The photo-dispersing agent of the present invention contains, as a polymer component, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide. Further, as the polymer, at least two kinds of polymers of the (A) polymer and the (B) polymer are contained. Hereinafter, the (A) polymer and the (B) polymer will be described in order.

[(A) Polymer]

The polymer (A) is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and has a structure (Y) represented by the following formula (1) (when X ¹ is -NH-, Except for the amide bond formed by &lt; RTI ID = 0.0 &gt;

(In the formula (1), X ¹ represents a sulfur atom, an oxygen atom or -NH-; "*" represents a bonding hand, provided that at least one of the two "*" .

Examples of the aromatic ring bonded with "*" in the above formula (1) include a benzene ring, a naphthalene ring, and an anthracene ring. Of these, benzene rings are preferred from the viewpoints of liquid crystal alignability and transparency. There is no particular limitation on the structure of the two "*" in the formula (1) to be bonded to the other "*", and examples thereof include a chain hydrocarbon structure, an aliphatic ring, an aromatic ring and a heterocyclic ring. Among them, in view of high sensitivity to light, one of two "*" is bonded to an aromatic ring and the other is bonded to at least one selected from the group consisting of aromatic rings, aliphatic rings and heterocyclic rings , And it is particularly preferable that the two &quot; * &quot; are all bonded to the aromatic ring. Further, from the viewpoint of reducing the burn-in of the liquid crystal display element, it is preferable that one of the two "*" is bonded to the aromatic ring and the other is bonded to the aliphatic ring, and the aliphatic ring is more preferably a cyclohexane ring .

X ¹ is preferably a sulfur atom in view of sensitivity to light, and is preferably an oxygen atom in terms of availability and selectivity of available monomers.

The polymer (A) in the present invention is obtained by reacting a tetracarboxylic acid derivative, which is at least one member selected from the group consisting of tetracarboxylic acid dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide, with diamine Can be obtained. Hereinafter, the polyamic acid, the polyamic acid ester and the polyimide as the (A) polymer will be described, respectively.

The "main chain" of the polymer in the present specification refers to a "stem" portion composed of a chain of the longest atoms among the polymers. However, it is permitted that the portion of this "stalk" includes a ring structure. In this case, the atoms constituting the ring structure are bonded to different atoms constituting part of the &quot; stem &quot;, whereby the entire ring structure is present in the main chain. Therefore, "having structure (Y) in the main chain" means that this structure constitutes a part of the main chain. However, the polymer (A) does not exclude that the structure (Y) is also present in a part other than the main chain, for example, a side chain (a part branched from the "stem" of the polymer).

<Polyamic acid>

The polyamic acid (hereinafter also referred to as "(A) polyamic acid") as the polymer (A) in the present invention can be obtained, for example, by [i] a tetracarboxylic acid dianhydride having the above structure (Y) A method in which one or more kinds of tetracarboxylic acid dianhydrides including a carboxylic acid dianhydride are reacted with a diamine having no structure (Y); [Ii] a method of reacting tetracarboxylic acid dianhydride having no structure (Y) with one or more diamines including a diamine having the structure (Y) (hereinafter also referred to as a specific diamine); [Iii] a method of reacting one or two or more tetracarboxylic acid dianhydrides containing a specific tetracarboxylic dianhydride with one or two or more diamines containing a specific diamine; And the like.

[Specific tetracarboxylic acid dianhydride]

The specific tetracarboxylic acid dianhydride is a compound having a group represented by the formula (1) and two acid anhydride groups (-CO-O-CO-), specifically, for example, the following formula (a)

(Wherein (a) one, X ¹ is a sulfur atom, an oxygen atom or -NH-; and R ³ and R ⁴ are, each independently, a monovalent organic group having one acid anhydride, R ³ and R ⁴ At least one of them has an aromatic ring; at least one of the bonding hands of &quot; -CO-X ¹ - &quot; is bonded to the aromatic ring).

As the monovalent organic group of R ³ and R ⁴ in the formula (a), the remaining structure is not particularly limited if it has an acid anhydride group. Examples of the structure of the moiety other than the acid anhydride group include a hydrocarbon group having 1 to 40 carbon atoms, a group in which the hydrogen atom of the hydrocarbon group is substituted with a halogen atom or the like, or a group in which the carbon-carbon bond of the hydrocarbon group is substituted with & -CO-, -CO-O-, -CO-S-, -SO ₂ -, -N═N-, -NH-, Quot; -CO-NH- &quot; and the like.

Herein, the "hydrocarbon group" in the present specification means either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term &quot; chain hydrocarbon group &quot; means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain but consist only of a chain structure. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it is not always necessary to be constituted by only the structure of alicyclic hydrocarbons, and some of them include those having a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it need not be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or a structure of an alicyclic hydrocarbon.

The acid anhydride group of R ³ and R ⁴ is preferably bonded to an aromatic ring, more preferably a benzene ring or naphthalene ring. Specifically, it is preferable that R ³ and R ⁴ are groups represented by each of the following formulas (a1-1) to (a1-3), or a group having any of them:

(Wherein "*" represents a bonding hand bonded to "-O-C (═O) -", "-S-C (═O) -" or "-NH-CO-").

It is more preferable that R ³ and R ⁴ have a group represented by the above formula (a1-1) or (a1-3) from the viewpoint of enhancing liquid crystal alignability, and more preferably a group represented by formula Is more preferable. The bonding hands in each of the above formulas (a1-1) to (a1-3) may be bonded to each other in the form of -OC (= O) -, -SC (= O) - &quot; carbonyl group.

When one of R ³ and R ⁴ is a group represented by any of the formulas (a1-1) to (a1-3), one group may be a group represented by the following formula (a2)

(Wherein (a2) of, Ar ¹ is a benzene ring or a naphthalene ring, X is ^{2, -O-CO- * 3, -S} -CO- * 3, -NH-CO- * 3, -O-, -CO-O- * ³ , -CO-S- * ³ or -CO- (* ³ represents a bonding hand bonded to Ar ¹ ), R ⁵ and R ⁷ are each independently , cyclohexylene group, phenylene group, or a non-phenyl group, which may have a substituent on the ring portion; R ⁶ is, in the case of n1 = n3 = 1, a divalent chain hydrocarbon of 1 to 20 carbon atoms, the hydrocarbon chain art -O-, -O-, -S-, -CO-, -CO-O-, -CO-S-, or -CO- , -SO ₂ -, -N═N-, -NH- or -CO-NH-, and when n 1 = 0 or n 3 = 0, the divalent straight chain hydrocarbon group having 1 to 20 carbon atoms or the carbon of the chain hydrocarbon N1, n2, n3 and m1 are each independently 0 or 1, and &quot; * &quot; denotes a bonding bond.

Ar ¹ in the formula (a2) is preferably a benzene ring in view of good liquid crystal alignability and transparency. X ² is preferably -O-CO- * ³ , -S-CO- * ³ , -CO-O- * ³ or -CO-S- * ^{3 in view} of good sensitivity to light, O-CO- * ³ or -S-CO- * ³ .

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms in R ⁶ include a methylene group, an ethylene group, a propanediyl group, a butane diyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, A nonanediyl group, a decanediyl group, and a dodecanediyl group, and they are preferably linear. By making R ^{6 a} highly flexible structure, it is possible to increase the heat redistribution property of the orientation film during post-baking. The preferred structure of R ⁶ is, for example, a structure represented by the following formula (3):

(In the formula (3), k and i are each independently 0 or 1, 1 is an integer of 2 to 9, j is an integer of 1 to 4, and &quot; * &quot;

In the formula (3), when j is 2 or more, l and i may be the same or different between repeating units. In the formula groups represented by (3), in the case when the formula of n1 is 0, the (a2) is preferably bonded to the alkanediyl group with respect to X ^2, which n3 = 0, the expression (a) - CO-X &lt; ^{1 &gt;} - is preferably bonded to an alkanediyl group.

R ⁵ and R ⁷ are preferably a phenylene group or a biphenylene group in view of high reactivity to light, and are preferably cyclohexylene groups in that the burn-in of a liquid crystal display element can be reduced.

When the ring part of R ⁵ and R ⁷ has a substituent, examples of the substituent include a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, . The position of the substituent may be any of ortho, meta, and para positions relative to X ² for R ^{5 and} to -CO-X ¹ - for R ⁷ . However, when "-CO-O-" or "-CO-S-" is bonded to the benzene ring, it is preferable that the substituent is in ortho position in that sensitivity to light is improved.

It is preferable that at least one of n1 and n3 is 1. n2 is preferably 1 from the viewpoint of improving the liquid crystal alignability, and is preferably 0 from the viewpoint of improving the photoreactivity. m1 is preferably 1 in order to enhance the effect of manifesting anisotropy by light irradiation.

Further, (A) The reason for expressing the liquid crystal aligning capability by the coating film irradiated with light containing polymer is not sure, that mainly due to the optical Friis potential response, group "-CO-X ¹ -" that caused by the photolysis of, Or both. Therefore, in the case where "-CO-O-", "-CO-S-" or "-CO-NH-" is bonded to the benzene ring, the substituent at the ortho position to the group has sensitivity to light Although the reason for the increase is not clear, if photodegradation occurs dominantly for example, it is presumed that the introduction of a substituent to the benzene ring makes it difficult to dislocate and, as a result, photolysis is promoted.

Specific examples of the group represented by the formula (a2) include groups represented by each of the following formulas (a2-1) to (a2-46), and the like:

(Wherein &quot; * &quot; represents a bonding hand bonded to X &^lt; ¹ &gt;).

Specific examples of the specific tetracarboxylic acid dianhydride include compounds represented by the following formulas (a-1) to (a-37), respectively. As specific tetracarboxylic acid dianhydrides, one kind or two or more kinds of them may be used in combination.

(A-1) to (a-14) from the viewpoint of high sensitivity to light among the above-mentioned compounds, More preferably a compound represented by each of formulas (a-13) and (a-14). (A-15) to (a-24) from the viewpoint that it is possible to impart appropriate rigidity and flexibility to the polymer, thereby increasing the orientation of the orientation film by heating during post-baking. From the viewpoint of photoreactivity, it is preferable to use a compound represented by each of the above-mentioned formula (a-5) and (a-25) to (a-29).

[Other tetracarboxylic acid dianhydrides]

In the case of the above methods [i] and [iii], as the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid, specific tetracarboxylic acid dianhydrides may be used, and compounds other than the specific tetracarboxylic acid dianhydrides Other tetracarboxylic acid dianhydride ") may be used in combination. Examples of other tetracarboxylic acid dianhydrides which can be used in the above methods [i] to [iii] include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, etc. .

Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride, compounds represented by the following formulas (ar-6) to (ar-9) , 1,2,5,6-hexanetetracarboxylic acid dianhydride, 1,1,2,2-ethenetetracarboxylic acid dianhydride, a compound represented by the following formula (ar-I), a compound represented by the following formula (ar- Compounds that appear;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetraone, cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutane tetracarboxylic dianhydride, compounds represented by each of the following formulas (ac-1) to (ac-30), and the like;

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride and the following formulas (ar-1) to (ar-5) Compounds that appear;

Tetracarboxylic acid dianhydride described in JP-A-2010-97188, and the like can be used. The other tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

(In the formulas (ar-I) and (ar-II), Z ^{1 to} Z ⁴ each independently represent an alkanediyl group, an aliphatic ring, an aromatic ring or a heterocyclic ring having 1 to 20 carbon atoms, Independently 0 or 1, with the proviso that m3 to m5 are not simultaneously 0;

In the formula (ar-Ⅰ) _{^{"- [Z 1] m3 - [}} Z 2] m4 - [Z 3] m5 - " Z ⁴ of the divalent group and the formula (ar-Ⅱ) represented by Is preferably an alkanediyl group having 1 to 10 carbon atoms, a phenylene group or a cyclohexylene group.

Specific examples of the compound represented by the formula (ar-I) include compounds represented by the formula (ar-6) and the compounds represented by the following formulas (ar-10) to (ar-12) Specific examples of the compound represented by the formula (ar-II) include compounds represented by the following formulas (ar-13) and (ar-14), respectively.

The other tetracarboxylic acid dianhydrides include at least one selected from the group consisting of aromatic tetracarboxylic dianhydrides and tetracarboxylic dianhydrides having nitrogen atoms from the viewpoint of improving the electric characteristics of the liquid crystal display element . When other aromatic tetracarboxylic acid dianhydrides are used as tetracarboxylic dianhydrides, the content thereof is preferably 3 to 90 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydrides used for the synthesis , More preferably 5 to 80 parts by weight.

Specific examples of the tetracarboxylic dianhydride having a nitrogen atom as the other tetracarboxylic dianhydride include compounds represented by the formula (ar-I) and compounds represented by the formula (ar-II) . Of these, compounds represented by each of the above-mentioned formulas (ar-6) and (ar-10) to (ar-14) are more preferable, and the compounds represented by formulas (ar- (ar-14) are more preferable, and compounds represented by the formula (ar-14) are particularly preferable.

When tetracarboxylic acid dianhydride having a nitrogen atom as the other tetracarboxylic dianhydride is used, the content thereof is preferably 3 to 80 parts by mol per 100 parts by mol of the total amount of the tetracarboxylic acid dianhydride used in the synthesis And more preferably 5 to 70 moles.

As other tetracarboxylic acid dianhydrides, tetracarboxylic acid dianhydrides having a cyclobutane skeleton can be preferably used from the viewpoint of enhancing the photosensitivity by the combined use of the photolytic reaction, and 1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride are more preferably used. When tetracarboxylic acid dianhydride having a cyclobutane skeleton is used as the other tetracarboxylic acid dianhydride, the content of the tetracarboxylic acid dianhydride is preferably 5 moles or more per 100 moles of the total tetracarboxylic acid dianhydride used in the synthesis And more preferably 10 moles or more.

In the case of the [i] method, the use ratio of the specific tetracarboxylic acid dianhydride is preferably at least 50 mol%, more preferably at least 50 mol%, based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid, , More preferably at least 60 mol%, and still more preferably at least 70 mol%.

The proportion of the specific tetracarboxylic acid dianhydride in the case of the [iii] method is preferably 30% by mole or more, more preferably 40% by mole or more based on the total amount of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid. Or more, and more preferably 50 mol% or more.

When the tetracarboxylic acid dianhydride having the structure represented by the formula (3) is used, the use ratio thereof is preferably 1 mol% or more with respect to the total amount of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid , More preferably 5 mol% or more, and further preferably 10 mol%. The upper limit of the use ratio is not particularly limited and may be arbitrarily set within a range of 100 mol% or less.

[Specific diamine]

The specific diamine is a compound having a group represented by the formula (1) and two primary amino groups, for example, represented by the following formula (b):

(Formula (b) of, X ¹ is a sulfur atom, an oxygen atom or -NH-; R ⁸ and R ⁹ are each a divalent organic group, each independently, at least one of R ⁸ and R ⁹ is an aromatic ring And at least one of the bonding hands in &quot; -CO-X ¹ - &quot; is bonded to the aromatic ring).

Examples of the divalent organic groups represented by R ⁸ and R ⁹ in the formula (b) include a hydrocarbon group having 1 to 30 carbon atoms, a group in which the hydrogen atom of the hydrocarbon group is substituted with a halogen atom or the like, -Carbon bond includes a group including -O-, -S-, -CO-, -CO-O-, -CO-S-, -N = N- , A group having a heterocyclic ring, and the like. Preferable specific examples of the group -R ⁸ -NH ₂ and the group -R ⁹ -NH ₂ include a group represented by the following formula (b2). The group "-R ⁸ -NH ₂ " and the group "-R ⁹ -NH ₂ " may be the same or different from each other.

(In the formula (b2), A ¹ represents a phenylene group, a biphenylene group, a cyclohexylene group, a bicyclohexylene group, -A ³ -A ⁴ - ** or -A ⁴ -A ³ - ** , A ³ represents a phenylene group, A ⁴ represents a cyclohexylene group, "**" represents a bond to a primary amino group), X ⁴ represents -O-CO-, -S- ^{* 4, -O-, -CO-O-} * 4, -CO-S- * 4, -CO-, -N = N-, -C = C- or -C≡C- (However, the "* ⁴ "it is represents a bond hand coupled to a ¹⁾ and; R ¹⁰ is a phenylene group, a naphthylene group, a cyclohexyl and xylene group or a heterocyclic group containing a nitrogen, which may have a substituent on the ring portion; R ¹¹ is , A divalent straight chain hydrocarbon group having 1 to 20 carbon atoms or a divalent group containing "-O-" at a position adjacent to the carbon-carbon bond of the chain hydrocarbon group or the carbon atom of the chain hydrocarbon group, and R ¹² represents a phenylene group , Naphthylene group or cyclohexylene group, and they may have a substituent at the ring part; n4, n5 and n6 may be the same or different, Is 0 or 1, each independently, m2 is an integer of 0 to 2; when only, R ¹¹ is divalent group containing the "-O-" in a position adjacent to the carbon atoms of chain hydrocarbon group, n4 = n6 = 1; &quot; * &quot; represents a combined hand).

A ¹ in the formula (b2) is preferably a phenylene group or a biphenylene group from the viewpoint of improving the sensitivity to light, and from the viewpoint of the alignment regulating ability, a bicyclohexylene group, -A ³ -A ⁴ - Or -A ⁴ -A ³ - *. X ^{4 is, -O-CO- * 4, -S} -CO- * 4, -CO-O- * 4 or a desirable and ^{-CO-S- * 4, -O-} CO- * 4 , or -S More preferably -CO- * ⁴ .

When the ring part of R ¹⁰ and R ¹² has a substituent, examples of the substituent include a fluorine atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, . When the -CO-O-, -CO-S- or -CO-NH- is bonded to the benzene ring of R ¹⁰ and R ¹² , the position of the substituent is not particularly limited, -O- "," -CO-S- "or" -CO-NH- ".

As to R ¹¹ , the description of R ^{6 in} the above formula (a2) can be applied.

It is preferable that at least one of n4 and n6 is 1. m2 is preferably 1 or 2 from the viewpoint of appropriately performing the anisotropy manifestation by light irradiation, and preferably 0 from the viewpoint of the alignment regulating force.

Specific examples of the groups represented by the above formula (b2) include, for example, groups represented by the following formulas (b2-1) to (b2-26), and the like:

(Where &quot; * &quot; represents a combined hand).

Among the above, it is preferable that the group represented by the formula (b2) is a group represented by each of the formulas (b2-24) to (b2-26) from the viewpoint of the alignment regulating force of the liquid crystal molecules.

Specific examples of the specific diamine include 4-aminophenyl-4'-aminobenzoate (a compound represented by the following formula (b-1)), 3,3'- Aminobenzoate, 3,3 ', 5,5'-tetramethyl-4-aminophenyl-4'-aminobenzoate, 3-methyl- 2) to (b-42), and the like. As the specific diamine, one kind or two or more kinds of them may be used in combination.

Of these, diamines having a structure of "-oriented ring -CO-X ¹ -aromatic ring-" are preferable from the viewpoint of high sensitivity to light. Specifically, the diamines represented by formulas (b-1), (B-3) to (b-13), (b-15) to (b-20) and (b-25) to (b-27). Compounds represented by each of the above formulas (b-28) to (b-38) are preferable from the viewpoint of high alignment control force of liquid crystal molecules.

[Other diamines]

In the case of the methods [ii] and [iii] above, as the diamine to be used for the synthesis of the polyamic acid, only the above-mentioned specific diamine may be used, and diamines other than the above specific diamines (hereinafter also referred to as "other diamines" May be used in combination. Examples of other diamines that can be used in the above methods [i] to [iii] include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Specific examples thereof include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As the aromatic diamine, for example, p-phenylenediamine, 4,4'-ethylenedianiline, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diamino Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - (m- phenylenediisopropylidene) bisaniline, (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6- diaminopyridine, 3,4-diaminopyridine, 2,4- N, N'-bis (4-aminophenyl) -benzidine, 3,6-diamino acridine, 3,6-diaminocarbazole, - bis (4-aminophenyl) -N, N'-dimethylbenzene (4-aminophenyl) -piperazine, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, octadecanoxy- Diaminobenzene,

Diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy- Benzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanthanil 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4,4'-diaminobenzophenone, Diaminobenzophenone, {4- [2- (3,5-diaminophenoxy) -ethoxy] -phenyl} -ethanone, 3,4-diaminobenzophenone, Phenyl} -phenylmethanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -phenylmethanone (4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -p-tolyl-methanone, {4- [2- -Ethoxy] -phenyl} -o-tolyl-methanone, 2,7-diaminofluorenone, 2,7-di Aminofluorene, 9,9-bis (4-aminophenyl) fluorene,

Diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'- Phenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl- - diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane- -Diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid and , The following formulas (b3-1) to (b3-14)

And the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 3,3 '- [1,4-phenylenebis (dimethylsilanediyl)] bis 1-propanamine) and the like; The diamine described in JP-A-2010-97188 can be used. As other diamines, these may be used singly or in combination of two or more kinds.

In the case of the method [ii], from the viewpoint of obtaining a liquid crystal display element having a good sensitivity to light, the use ratio of the specific diamine is preferably 30 mol% or more based on the total amount of the diamine used for the synthesis of the polyamic acid , More preferably 40 mol% or more, and still more preferably 50 mol% or more. In the case of the above method (iii), the use ratio of the specific diamine is preferably 20 mol% or more, more preferably 30 mol% or more, relative to the total amount of the diamine used in the synthesis of the polyamic acid , And still more preferably 40 mol% or more.

(A) The content of the structure (Y) in the polymer ^{is, 1 × 10 -5 ~1 × 10} - and preferably set to ² mol ^{/ g, 5 × 10 -5 ~5} × 10 - 3 mole / g Is more preferable. Therefore, it is preferable to set the kind and amount of the specific tetracarboxylic acid dianhydride and the specific diamine to be used so that the content of the structure (Y) in the polymer (A) is in the above range.

As the tetracarboxylic acid dianhydrides and diamines to be used in the reaction, from the viewpoint of improving the sensitivity of the polymer to light (A), the diamine to be used in the reaction is preferably a tetracarboxylic acid dianhydride having a structure of "-oriented ring -CO-X ¹ -aromatic ring" (A-5) as the tetracarboxylic acid dianhydride to be used in the reaction, from the viewpoint of increasing the photoreactivity (light absorbing property) , A compound represented by the formula (a-28), and a compound represented by the formula (a-29). Examples of the compound having the structure represented by the formula (3) include compounds represented by the formulas (a-15) to (a-27) Or the like is preferably used.

Specific tetracarboxylic acid dianhydrides and specific diamines all have the same function in that a polyamic acid having a common structure (Y) in its main chain can be obtained. Therefore, even those not described in the following examples can be used in the present invention. Also, with respect to other tetracarboxylic acid dianhydrides and other diamines to be used together with a specific tetracarboxylic acid dianhydride or a specific diamine, those not described in the following examples can also be used in the present invention.

[Molecular Weight Regulator]

In the synthesis of the polyamic acid (A), a terminal modifier type polymer may be synthesized by using a suitable molecular weight modifier (terminal endblock) together with the above-mentioned tetracarboxylic dianhydride and diamine.

Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. Specific examples thereof include acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride , 3- (3-trimethoxysilyl) propyl) -3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran- ; Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 3- (trifluoromethoxy) - (trifluoromethoxy) aniline, triethoxysilylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethoxydiethoxysilane and the like; As the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate and the like; Respectively.

The use ratio of the molecular weight regulator is preferably 20 moles or less, more preferably 10 moles or less, per 100 moles of the total amount of the tetracarboxylic acid dianhydride and diamine to be used.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid in the present invention is such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of one equivalent of the amino group of the diamine is 0.2 to 2 equivalents , More preferably from 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 캜 to 150 캜, more preferably 0 to 100 캜. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Such as lactone, tetramethylurea, hexamethylphosphoric triamide and the like; As the phenolic solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

As the alcohol, for example, methanol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether and the like; As the ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like; As the ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate and the like; Examples of the ether include diethyl ether, diisopentyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether Acetate, diethylene glycol dimethyl ether, tetrahydrofuran and the like; As halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and the like; Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene and the like; Respectively.

Among these organic solvents, at least one selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (first group of organic solvents), or at least one selected from organic solvents of the first group, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the proportion of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably not more than 30% by weight. The amount (?) Of the organic solvent used is preferably such that the total amount (?) Of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by weight based on the total amount (? +?) Of the reaction solution .

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be supplied as it is to the preparation of the photo-dispersing agent as it is, or may be provided to the preparation of the photo-dispersing agent after isolation of the polyamic acid contained in the reaction solution, or may be provided to the preparation of the photo- good. When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- May be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid can be isolated and purified by a known method.

<Polyamic acid ester>

The polyamic acid ester (hereinafter also referred to as (A) a polyamic acid ester) as the polymer (A) of the present invention can be obtained, for example, by reacting a polyamic acid (A) A method of reacting a tetracarboxylic acid diester with a diamine, [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, And the like.

Examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; Phenols such as phenol and cresol, and the like. Examples of the acetal-based esterifying agent include N, N-dimethylformamide diethyl acetal and N, N-diethylformamide diethylacetal. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and the epoxy group-containing compound For example, propylene oxide.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the polyamic acid (A) using the above-mentioned alcohols. The reaction of the tetracarboxylic acid diester and the diamine is preferably carried out in the presence of a suitable dehydration catalyst. As the dehydration catalyst, for example, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, .

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride.

In the above methods [II] and [III], a polyamic acid ester having the structure (Y) can be obtained by using a compound having the structure (Y) in at least one of tetracarboxylic acid dianhydride and diamine . In addition, the polyamic acid ester may have only an acid ester structure, or may be a partial ester ester in which an acid structure and an acid ester structure coexist.

In this way, a reaction solution obtained by dissolving a polyamic acid ester is obtained. The reaction solution may be supplied as it is to the preparation of the photo-dispersing agent. Alternatively, the polyamic ester contained in the reaction solution may be isolated and then added to the preparation of the photo-dispersing agent. Alternatively, after the isolated polyamic acid ester is purified, May be provided. The polyamic acid ester can be isolated and purified by a known method.

<Polyimide>

The polyimide (hereinafter also referred to as &quot; polyimide (A) &quot;) as the polymer (A) contained in the photo-dispersing agent of the present invention can be obtained by, for example, dehydrating and ring closure of the polyamic acid (A) .

The polyimide (A) may be a completely imidized product obtained by dehydrating and ring-closure of the entire acid structure of the polyamic acid (A), which is the precursor thereof, and dehydrating and cyclizing a part of the acid structure to form an acid structure and an imidazole ring structure The imide cargo may be partially imbedded. The polyimide (A) preferably has an imidization rate of 5% or more, more preferably 10 to 60%, and further preferably 15 to 50%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating a polyamic acid, or a method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating . Of these, the latter method is preferable.

In the method of imidizing a polyamic acid solution by adding a dehydrating agent and a dehydrating ring-opening catalyst, an acid anhydride such as acetic anhydride, anhydrous propionic acid or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

Thus, a reaction solution containing (A) polyimide is obtained. The reaction solution may be supplied as it is to the preparation of the photo-dispersing agent as it is or may be added to the preparation of the photo-dispersing agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, Alternatively, after the isolated polyimide is purified, it may be added to the preparation of the light distribution agent. These purification operations can be carried out according to a known method. The polymer (A) contained in the photo-dispersing agent of the present invention may be used singly or in combination of two or more.

[(B) Polymer]

The polymer (B) contained in the photo-dispersing agent of the present invention is at least one member selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and is a polymer different from the above-mentioned (A) polymer. In the case where the polymer component of the photopolymerization initiator is used only as the polymer (A), even when the voltage storage ratio of the liquid crystal display element is lowered or the accumulation of the residual charges occurs, it is possible to improve this by using a blend of different resins.

When the (B) polymer is a polyamic acid (hereinafter also referred to as "(B) polyamic acid"), the (B) polyamic acid can be obtained by reacting, for example, tetracarboxylic acid dianhydride with a diamine. Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polymer (B) include the compounds exemplified as tetracarboxylic dianhydrides which can be used for the synthesis of the (A) polymer. Among them, from the viewpoint of suppressing the charge transfer within the molecule and the molecule, it is preferable to contain an alicyclic tetracarboxylic acid dianhydride, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, bicyclo [3.3.0 ] Octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydrous, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- 1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- -2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetra More preferably at least one specific alicyclic tetracarboxylic acid dianhydride selected from the group consisting of carboxylic acid dianhydride and cyclohexanetetracarboxylic acid dianhydride.

The blending ratio (or the total amount when two or more species are included) of these specific alicyclic tetracarboxylic acid dianhydrides is preferably 30 mol% or more based on the total amount of the tetracarboxylic acid dianhydrides used in the synthesis , And more preferably 40 mol% or more.

The tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (B) may contain a tetracarboxylic acid dianhydride (specific tetracarboxylic dianhydride) having the above structure (Y). The ratio of the specific tetracarboxylic acid dianhydride to the tetracarboxylic acid dianhydride used in the synthesis is such that the amount of the tetracarboxylic acid dianhydride to be used in the synthesis can be appropriately selected so that the component exhibiting properties (for example, electrical characteristics or transparency) It is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total amount of the anhydride.

Examples of the diamine used for the synthesis of the polyamic acid (B) include (A) a compound exemplified as a diamine (specific diamine and other diamines) which can be used for synthesizing a polymer. At this time, the use ratio of the specific diamine is preferably 30 mol% or less, more preferably 20 mol% or less, based on the total amount of the diamine used in the synthesis.

Further, regarding the various reaction conditions in the synthesis of the polyamic acid (B), the description of the polymer (A) can be applied. The polyamic acid ester and the polyimide as the (B) polymer can also be obtained by the method described in the polymer (A). As the polymer (B) contained in the photo-dispersing agent of the present invention, one species may be used alone, or two or more species may be used in combination.

The polymer (B) is preferably a polymer in which the content of at least one of a fluorine atom and a silicon atom (hereinafter also referred to as &quot; specific atom &quot;) is different from that of the polymer (A). Generally, when two kinds of polymers having different specific atom content are blended, a polymer having a higher specific atom content is localized in the upper layer and a polymer having a lower specific atom content It tends to be localized in the lower layer. By using such a phenomenon, it is possible to make the content of specific atom in the polymer (A) and the polymer (B) be different from each other, .

When at least one of the polymer (A) and the polymer (B) has specific atoms (F, Si), for example, the following [1] to [4] .

[1] A solar cell wherein the polymer (A) and the polymer (B) have specific atoms, and the polymer (A) has a higher specific atom content than the polymer (B).

[2] A method wherein (A) the polymer has specific atoms and (B) the polymer has substantially no specific atoms.

[3] A solar cell wherein the polymer (A) and the polymer (B) have specific atoms and the polymer (B) has a higher specific atom content than the polymer (A).

[4] A method wherein (B) the polymer has specific atoms and (A) the polymer has substantially no specific atoms.

Among these, it is preferable that the polymer (A) has a higher content of specific atoms than the polymer (B), from the viewpoint of appropriately controlling the orientation of the liquid crystal molecules. Specifically, it is preferable to use the mode of [1] or [2], and the mode of [2] is more preferable. The term &quot; substantially no specific atom &quot; means that the specific atom is not contained or the content ratio of the repeating unit having a specific atom to all repeating units of the polymer is 1 mol% or less, preferably 0.5 Mol% or less.

In order to obtain a polymer having a specific atom, for example, in the synthesis of a polymer, there may be mentioned a method of [i] polymerization using a monomer including a tetracarboxylic acid derivative having a specific atom; [Ii] a method of polymerizing with a monomer containing a diamine having a specific atom; [Iii] a method of polymerization using a monoamine having a specific atom as a terminal endblock; [Iv] a method of polymerization using an acid anhydride having a specific atom as a terminal endblocker, and the like.

Examples of the tetracarboxylic acid derivative having a specific atom include 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, an acid anhydride group-containing silicone oil (for example, trade name "X-22- 2290AS &quot; (manufactured by Shin-Etsu Silicone Co., Ltd.); Examples of the diamine having a specific atom include 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-bis Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4- Bis (3-aminopropyl) -tetramethyldisiloxane, 3,3 '- [1,4-phenylenebis (triphenylphosphine) Dimethylsilanediyl)] bis (1-propanamine) and the like; Examples of the monoamine having a specific atom include 3- (trifluoromethoxy) aniline, 4- (trifluoromethoxy) aniline, triethoxysilylamine, 3-aminopropyltrimethoxysilane, Triethoxysilane, 3-aminopropylmethoxydiethoxysilane and the like; Examples of the acid anhydride having a specific atom include 3- (3-trimethoxysilyl) propyl) -3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoro Isobenzofuran-1,3-dione, and the like. In order to obtain a polymer having a specific atom, one of these methods [i] to [iv] may be used, or two or more of them may be used in combination.

The content of the repeating unit having a specific atom in the polymer having a specific atom is preferably 70 mol% or less, more preferably 60 mol% or less, and 50 mol% or less, based on the total repeating units of the polymer More preferable. The lower limit value is not particularly limited and may be, for example, 1 mol% or more, and preferably 5 mol% or more.

ㆍ Structure (Z)

At least one of the polymer (A) and the polymer (B) is a polymer having a structure represented by the following formula (2-1) and a structure represented by the following formula (2-2) And a nitrogen-containing heterocyclic ring), and at least one structure (Z) selected from the group consisting of nitrogen-containing heterocyclic rings. By introducing such a structure Z into the polymer, it becomes possible to improve the electric characteristics such as the voltage holding ratio and the afterimage characteristic of the liquid crystal display element:

(In the formula (2-1), R ¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, r ¹ is an integer of 0 to 2, r 2 is an integer of 0 to 3; (2-2), R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; "* 2" indicates a bonding hand; ).

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, It may be in phase or in phase. Examples of the alkoxy group having 1 to 10 carbon atoms include groups in which an alkyl group having 1 to 10 carbon atoms is bonded to an oxygen atom, and specific examples thereof include a methoxy group, ethoxy group and propoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

r1 and r2 are preferably 0 or 1, respectively.

The R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Examples of the nitrogen-containing heterocycle include piperidine, pyrrolidine, pyridine, pyrazine, piperazine, pyrimidine and homopiperazine. Among them, a piperidine ring or a piperazine ring is preferable, and a piperidine ring is more preferable in view of the effect of relaxing the accumulated residual charge.

The structure (Z) is preferably a structure represented by the formula (2-2) or a nitrogen-containing heterocyclic ring, and more preferably a nitrogen-containing heterocyclic ring because of its high effect of improving electrical characteristics.

The structure (Z) may be introduced into either the main chain or the side chain of the polymer. The polymer having the structure (Z) can be obtained by using, for example, a diamine having a carboxyl group in the synthesis of the polymer, the polymer having the structure represented by the formula (2-1). Further, by using the diamine represented by each of the formulas (b3-4) and (b3-10) or the tetracarboxylic acid dianhydride represented by the formula (ar-1) Structure can be obtained. The diamine represented by each of the above formulas (b-21), (b3-1) to (b3-3), (b3-8), (b3-9), (b3-11) , A polymer having a nitrogen-containing heterocycle can be obtained.

The structure (Z) may have the polymer (A) and the polymer (B), or may have only the polymer (A) and only the polymer (B). (A) a polymer and (B) a polymer in the coating film, from the viewpoint of suitably performing the copolymerization of the polymer (A) and the polymer (B) , It is more preferable that the content ratio of the structure (Z) is higher than that of the other structure, and it is more preferable that the other polymer does not substantially contain the structure (Z). Preferably, (B) the polymer has the structure (Z). The term "substantially free of the structure (Z)" means that the structure (Z) is not contained or the content ratio of the repeating unit having the structure (Z) to all the repeating units of the polymer is 1 mol% Or less, preferably 0.5 mol% or less.

In the polymer having the structure (Z), the content of the repeating unit having the structure (Z) is preferably from 2 to 50 mol%, more preferably from 5 to 40 mol%, based on the total repeating units of the polymer desirable.

Preferable combinations of the polymer components of the photo-dispersing agent of the present invention include, for example, the following [1] to [5].

[1] The sun is a polymer wherein the polymer (A) is a polymer having a structure (Y) and a specific atom, and the polymer (B) has a structure (Z) and has a specific atom content lower than that of the polymer (A).

[2] The polymer according to [1], wherein the polymer (A) is a polymer having a structure (Y), a structure (Z) and a specific atom, and the polymer (B) has a structure (Z) The sun, which is a low polymer.

(3) A polymer composition according to the above (1), wherein the polymer (A) is a polymer having a structure (Y) and a specific atom and a mixture of a polymer having a structure (Y) (A) a polymer having a lower specific atom content than the polymer.

[4] The polymer according to [1], wherein the polymer (A) is a polymer having a structure (Y) and a structure (Z), and the polymer (B) is a polymer having a structure (Y) Sun.

[5] The polymer composition according to any one of [1] to [5], wherein the polymer (A) is a polymer having a structure (Y) and a structure (Z), wherein the polymer (B) has substantially no structure (Y) This high polymer, the sun.

The combination of the polymer (A) and the polymer (B) is preferably an embodiment of [1], [2] or [3]. Although not necessarily clear, when a coating film is formed on a substrate using the photopolymerization initiator of [1], the polymer (A) having high photoreactivity is uniformized in the upper layer in the coating film, It is presumed that the high (B) polymer is localized in the lower layer. Accordingly, it is presumed that it exhibits excellent liquid crystal alignability and electric characteristics.

&Lt; Solution viscosity of polymer &gt;

The polymer (A) and the polymer (B) preferably have a solution viscosity of 10 to 800 mPa · s and a solution viscosity of 15 to 500 mPa · s, respectively, when the solution is a 10 wt% More preferable. The solution viscosity (mPa.s) of the polymer is preferably 10 weight% or less by weight, which is prepared by using a good solvent (for example,? -Butyrolactone, N-methyl- % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer.

The weight average molecular weight of the (A) polymer and the (B) polymer in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 500,000, more preferably 1,000 to 300,000.

The content ratio of the polymer (A) and the polymer (B) in the photopolymerization initiator is preferably 2/8 to 8/2 in terms of weight ratio (A / B) from the viewpoint of sufficiently obtaining the effect of the present invention, Preferably, it is 3/7 to 7/3.

<Other components>

The photo-dispersing agent of the present invention may contain other components as required. Examples of such other components include a polymer other than the polymer (A) and the polymer (B), a compound having at least one epoxy group in the molecule (hereinafter referred to as an &quot; epoxy group-containing compound &quot;), Compounds, bismaleimide compounds, allyl group-containing compounds, and the like.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Examples of such other polymers include polyesters, polyamides, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylates .

When the other polymer is added to the photo-dispersing agent, the blending ratio thereof is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total polymer in the composition.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used for improving the adhesion to the substrate surface and electric characteristics in the liquid crystal alignment film. 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 Diallyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromonopentyl glycol di N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidylbenzylamine, N, N-diglycidylaminomethylcyclohexane, N, N- Diglycidylcyclohexylamine, the following formulas (e-1) to (e-9):

, Sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, diglycidyl terephthalate and the like can be preferably used. In addition, as the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used. When these epoxy compounds are added to the photopolymerization initiator, the compounding ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the total amount of the polymers contained in the photopolymerization initiator.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printing property of the photo-dispersing agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyl tri Methoxysilane and the like. When these functional silane compounds are added to the photo-dispersing agent, the blending ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight per 100 parts by weight of the total amount of the polymers.

[Bismaleimide compound]

The bismaleimide compound can be used to improve the heat resistance and electric characteristics of the liquid crystal alignment film and the abrasion resistance of the coating film. Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, 2,2'- (4-maleimidophenoxy) phenyl] propane, 4-methyl-1,3-phenylene bismaleimide and the like. When these bismaleimide compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the total amount of the polymers.

[Allyl group-containing compound]

The allyl group-containing compound can be used to suppress the improvement of the electric characteristics of the liquid crystal alignment layer and the decrease of the voltage holding ratio. Examples of the allyl group-containing compound include compounds represented by each of the following formulas (al-1) to (al-3). When these allyl group-containing compounds are added, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymers.

In addition to the above, additives other than the above described additives commonly added to the photo-dispersing agent, for example, a compound having at least one oxetanyl group in the molecule, an antioxidant, a photosensitizer and the like may be used. Further, in order to improve the strength of the coating film, lactams, glutaric acid imide compounds, hydroxypiperidone compounds and piperidine compounds as described in Japanese Patent Publication No. 3245849; A heterocyclic compound having at least one heterocyclic structure selected from the group consisting of oxetane, thiirane and oxazoline as described in Japanese Patent Publication No. 5045241; And inorganic particles having a particle size of 1,000 ANGSTROM or less (for example, silica particles and the like).

<Solvent>

The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the above polymer component and other components added as required are dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent to be used include organic solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamylphosphate Propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration (the ratio of the total weight of components other than the solvent of the photo-dispersing agent to the total weight of the photo-dispersing agent) in the photo-dispersing agent of the present invention is appropriately selected in consideration of viscosity, volatility, etc., 10% by weight. That is, the coating composition to be the liquid crystal alignment film is formed by coating the surface of the substrate, preferably by heating, as will be described later. When the concentration of the solid content is less than 1% by weight, And it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the photo-dispersing agent is increased and the coating property is poor.

Particularly preferable range of the solid content concentration differs depending on the method used when applying the light distribution agent to the substrate. For example, in the case of the spinner method, it is particularly preferable that the solid concentration is in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 wt%, and the solution viscosity is in the range of 12 to 50 mPa · s accordingly. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and accordingly the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the photo-dispersing agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film in the present invention is formed using the photo-dispersing agent prepared as described above. The liquid crystal alignment film is preferably applied to a TN type, STN type, or transverse electric field type liquid crystal display device. In particular, it is preferable to apply the present invention to a liquid crystal display element of a transverse electric field system such as an IPS or FFS type, because the effect of reducing the burn-in of the liquid crystal display element can be maximized.

The liquid crystal alignment film in the present invention can be produced by a method including a film forming step of applying a photo-dispersing agent of the present invention on a substrate to form a coating film and a light irradiation step of forming a liquid crystal alignment film by irradiating the formed coating film with light . &Lt; / RTI &gt;

[Film forming process]

In this step, the photo-dispersing agent of the present invention is applied onto the substrate, and then the coated surface is heated to form a coating film on the substrate.

In the case of applying to a TN type or STN type liquid crystal display device, two pairs of substrates on which a patterned transparent conductive film is formed are paired, and the photo-dispersing agent of the present invention is coated on the respective transparent conductive film- Thereby forming a coating film. On the other hand, when applied to a liquid crystal display device of a transverse electric field system, a pair of a substrate having an electrode composed of a patterned transparent conductive film or a metal film on one side and an opposing substrate on which electrodes are not formed, And the opposite surface of the counter substrate, respectively, to form a coating film.

In either case, as the substrate, for example, a transparent substrate made of plastic such as glass such as float glass, soda glass, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film can be performed by, for example, a method of forming a pattern by a photo-etching method, a sputtering method, or the like after forming a transparent conductive film without a pattern; A method using a mask having a desired pattern when forming a transparent conductive film; And so on. Further, at the time of applying the photo-dispersing agent, a functional silane compound, a functional titanium compound or the like is added to the surface of the substrate surface on which the coating film is formed in order to improve the adhesion between the substrate, the conductive film or the electrode and the coating film It is also possible to carry out a pre-treatment for pre-coating.

The application of the photo-dispersing agent to the substrate can be preferably performed by a coating method such as an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. After the application of the photo-brightening agent, preheating (pre-baking) is preferably performed for the purpose of preventing the flow of the applied photo-brightening agent or the like (pre-baking step). The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a post-baking step is carried out in which the solvent is completely removed and the post-baked coating film is baked for the purpose of thermally modifying the arid acid structure present in the polymer as required. The post-baking temperature at this time is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the coated film after post baking is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

[Light irradiation step]

In this step, a coating film formed on a substrate is irradiated with a polarized light or a non-polarized radiation to impart liquid crystal aligning ability. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation to be used is linearly polarized light or partial polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction, or in combination thereof. In the case of irradiating non-polarized radiation, the irradiation direction is set to the oblique direction.

As the light source to be used, for example, 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 can be used. The ultraviolet ray in the preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter, a diffraction grating, or the like.

The light irradiation is carried out in the following manner: [1] a method of irradiating a coating film after the post-baking step, [2] a method of irradiating the coating film before the post-baking step after the pre-baking step, [3] And a method in which the coating film is irradiated to the coating film while heating the coating film. Is preferably the method of [2] in that the effect of reducing the burn-in in the liquid crystal display element is high. The dose of light is preferably 100 to 50,000 J / m 2, and more preferably 300 to 20,000 J / m 2. The light irradiation to the coating film may be performed while heating the coating film to enhance the reactivity. The temperature at the time of heating is usually 30 to 250 占 폚, preferably 40 to 200 占 폚, and more preferably 50 to 150 占 폚. Thus, a liquid crystal alignment film is formed on the substrate.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises the liquid crystal alignment film obtained as described above. The liquid crystal display element of the present invention can be produced, for example, as follows. First, a pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which liquid crystal is sandwiched between the pair of substrates is manufactured. To produce a liquid crystal cell, for example, the following two methods can be mentioned. The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. The peripheral portions of the two substrates are bonded together using a sealant, A liquid crystal is injected and filled in the cell gap, and then the injection port is sealed to manufacture a liquid crystal cell.

The second method is a method called ODF (One Drop Fill) method. First, for example, an ultraviolet curable sealing agent is applied to a predetermined position on one substrate, liquid crystal is dropped on the liquid crystal alignment film surface, the other substrate is bonded so that the liquid crystal alignment film is opposed, The liquid crystal cell is manufactured by irradiating ultraviolet light to the entire surface of the substrate to cure the sealant. In either case, it is preferable to heat the liquid crystal cell to a temperature at which the liquid crystal using the liquid crystal has an isotropic phase, and then gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal. The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. When the radiation is linearly polarized, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the irradiated radiation and the angle between each substrate and the polarizing plate with respect to the two substrates on which the liquid crystal alignment film is formed have.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide spheres as a spacer and a curing agent can be used.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. Among them, those having a positive dielectric anisotropy for forming a nematic liquid crystal are preferable. For example, Based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quaternary liquid crystal and the like are used. In addition, a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate in a liquid crystal; Chiral agent sold under the trade names "C-15" and "CB-15" (manufactured by Merck Ltd.); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, and the like may further be added and used.

Examples of the polarizing plate include a polarizing plate sandwiching a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state with a cellulose acetate protective film, and a polarizing plate made of H film itself.

Since the liquid crystal display element of the present invention has a liquid crystal alignment layer formed by the photo alignment method using the photo-dispersing agent of the present invention, particularly when applied to a transverse electric field type liquid crystal display element, . Therefore, the liquid crystal display device of the present invention can be effectively applied to various devices, and can be applied to various devices such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a PDA, It can be suitably applied as a liquid crystal display element used in a display device such as a telephone, a smart phone, various monitors, a liquid crystal television, and an information display.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

The weight average molecular weight of each polymer, the solution viscosity of each polymer solution and the imidation rate in the synthesis examples were measured by the following methods.

[Weight average molecular weight of polymer]

The weight average molecular weight Mw of the polymer is a polystyrene reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Solution viscosity of polymer solution]

The solution viscosity [mPa.s] of the polymer solution was measured at 25.degree. C. using an E-type rotational viscometer with respect to a solution prepared by using N-methyl-2-pyrrolidone (NMP) did.

[Measurement of imidization rate]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the equation shown in the following equation (1).

Imidization rate [%] = {(1-A ¹ ) / (A ² x?)} 100 ... (One)

(In the formula (1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and α is the peak area derived from the proton The ratio of the number of other protons to one proton in the NH group).

&Quot; Synthesis of polymer &quot;

The polymers (A-1) to (A-14) and the polymers (B-1) to (B-7) were synthesized using the following compounds in each synthesis example.

<Tetracarboxylic acid derivatives>

Specific tetracarboxylic acid dianhydride

Other tetracarboxylic acid dianhydrides and tetracarboxylic acid diesters

(In the formula (t-6), R is an ethyl group; and in the formula (t-12), m is an integer of 1 to 15).

<Diamine>

ㆍ Specific diamine

ㆍ Other diamines

<Monoamine>

&Lt; Synthesis of (A) Polymer &

ㆍ Synthesis of polyimide

[Synthesis Example a1: Synthesis of Polymer (A-1)] [

100 molar parts of the compound (a-2) as the tetracarboxylic acid dianhydride, 70 mol parts of the compound (b-1) as diamine and 30 mol of the compound (d-7) ) And reacted at room temperature for 6 hours. Thus, a polyamic acid solution having a solid concentration of 15% by weight was obtained. Next, N-methylpiperidine and acetic anhydride were added to the resulting polyamic acid solution in an amount of 0.5 times the amount of the tetracarboxylic acid dianhydride, respectively, and the dehydration ring-closure reaction was carried out at 75 占 폚 for 3 hours. After dehydration ring closure, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing 15% by weight of polyimide having an imidization rate of 30%. This polyimide was used as the polymer (A-1). The polymer (A-1) had a weight average molecular weight Mw of 50,000.

 [Synthesis Example a7: Synthesis of Polymer (A-7)] [

A polyimide having an imidization rate of 35% was synthesized by carrying out the same operation as in Synthesis Example a1 except that the kind and amount of the tetracarboxylic acid dianhydride and the diamine used were changed as shown in Table 1 below. The obtained polyimide was designated as polymer (A-7). The polymer (A-7) had a weight average molecular weight Mw of 80,000.

[Synthesis Example a10: synthesis of polymer (A-10)] [

The same operations as those of Synthetic Example a1 were performed except that the kind and amount of the tetracarboxylic acid dianhydride and the diamine used were changed as shown in Table 1 and 20 moles of the compound (m-1) was added as the monoamine, , And a polyimide having an imidization rate of 20% were synthesized. The obtained polyimide was used as the polymer (A-10). The polymer (A-10) had a weight average molecular weight Mw of 95,000.

ㆍ Synthesis of polyamic acid

[Synthesis Example a2: Synthesis of Polymer (A-2)] [

(A-2) as a diamine, 80 parts by mole of the compound (a-2) as a tetracarboxylic acid dianhydride, 40 moles of the compound (a-15), 10 moles of the compound 20 mols of the compound (d-8) was dissolved in NMP and reacted at room temperature for 8 hours. Thus, a polyamic acid solution having a solid concentration of 15% by weight was obtained. The obtained polyamic acid was used as the polymer (A-2). The polymer (A-2) had a weight average molecular weight Mw of 40,000.

Synthesis Examples a4 to a6, a8 and a14: synthesis of polymers (A-4) to (A-6), (A-8) and (A-

A polyamic acid solution having a solid content concentration of 10% by weight was obtained by carrying out the same operation as in Synthesis Example a2 except that the kind and amount of tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 1 below. The weight average molecular weight Mw of each polymer is shown in Table 1 below.

Synthesis Examples a9 and a11: Synthesis of Polymers (A-9) and (A-11)

Except that the kind and amount of the tetracarboxylic acid dianhydride and the diamine to be used were changed as shown in Table 1 and that the compound (m-1) or the compound (m-2) was added as the monoamine, Was carried out to obtain a polyamic acid solution having a solid concentration of 10% by weight. The weight average molecular weight Mw of each polymer is shown in Table 1 below.

ㆍ Synthesis of polyamic acid ester

[Synthesis Example a3: Synthesis of Polymer (A-3)] [

(B-10) as a diamine and 10 mols of the compound (d-8) as a diamine were dissolved in a mixed solvent of 70 molar parts of tetracarboxylic acid dianhydride, 30 molar parts of the compound (t-8) And reacted at room temperature for 6 hours. Further, 80 molar portions of N, N-dimethylformamide diethyl acetal were added dropwise to this reaction solution, and the mixture was reacted at 50 DEG C for 2 hours to obtain a polyamic acid ester solution. The polymer (A-3) had a weight average molecular weight of 120,000.

[Synthesis Example a12: synthesis of polymer (A-12)] [

30 g of the compound (t-5) as a tetracarboxylic acid dianhydride was added to 500 mL of ethanol to obtain a tetracarboxylic acid diester. The obtained precipitate was separated by filtration, washed with ethanol, and then dried under reduced pressure to obtain a tetracarboxylic acid diester powder. 15 mol parts of the obtained tetracarboxylic acid diester (compound (t-6)), 70 mol of compound (a-2) and 15 mol of compound (t-11) were dissolved in NMP, (b-10) were dissolved in 100 parts by mol of water. 300 moles of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, 15 +/- 2 wt% hydrate) And the reaction was carried out at room temperature for 4 hours to obtain a polyamic acid ester solution. The polymer (A-12) had a weight average molecular weight Mw of 40,000.

[Synthesis Example a13: synthesis of polymer (A-13)] [

The procedure of Synthesis Example 12 was repeated except that the kind and amount of the tetracarboxylic acid diester, tetracarboxylic acid dianhydride and diamine to be used were changed as shown in Table 1 below to obtain a polyamic acid ester solution having a solid concentration of 10% by weight &Lt; / RTI &gt; The polymer (A-13) had a weight average molecular weight Mw of 65,000.

<Synthesis of (B) Polymer>

Synthesis Examples b1 to b7: Synthesis of Polymers (B-1) to (B-7)

A polyamic acid solution having a solid content concentration of 10% by weight was obtained by carrying out the same operation as in Synthesis Example a2 except that the type and amount of tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 2 below. The weight average molecular weight Mw of each polymer is shown in Table 2 below.

In Table 1 and Table 2, the numerical values in parentheses of each column of the compound show the compounding ratio (molar ratio) relative to the total 100 moles of tetracarboxylic acid derivatives used.

[Example 1]

<Preparation of light aroma>

50 parts by weight of the polymer (A-1) obtained in the above Synthesis Example a1 and 50 parts by weight of the polymer (B-1) obtained in the above Synthesis Example b1 were added to NMP and butyl cellosolve BC) were added and sufficiently stirred to obtain a solution having a solvent composition of NMP: BC = 70: 30 (weight ratio) and a solid content concentration of 3.0% by weight. This solution was filtered using a filter having a pore diameter of 0.45 mu m to prepare a photo-dispersing agent.

&Lt; Production of liquid crystal display element &

A glass substrate having two metal electrodes (electrode A and electrode B) made of chrome patterned in a comb shape and capable of independently applying voltage to the electrodes A and B was prepared. The glass substrate and the opposing glass substrate on which the electrodes were not formed were paired with each other using a spinner to coat the surface of the glass substrate with the electrode and the surface of the opposing glass substrate with the prepared photo-dispersing agent. Subsequently, pre-baking was performed for 1 minute on a hot plate at 80 DEG C, and then 10,000J / m &lt; 2 &gt; of polarized ultraviolet rays was irradiated onto the surface of the substrate on the side coated with the photo-diffusing agent by using an Hg-Xe lamp and a gantry prism, In the vertical direction. After irradiation with light, the tube was heated (post-baking) in an oven in which the inside of the tube was replaced with nitrogen at 200 DEG C for one hour. Thus, a pair of substrates having a liquid crystal alignment film with a thickness of 0.1 mu m was obtained.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film among the pair of substrates by screen printing, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The polarizing ultraviolet rays were irradiated to each other in such a manner that the directions of the substrates were opposite to each other, and they were pressed and bonded together, and the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, a liquid crystal "MLC-7028" manufactured by Merck Ltd. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 캜 and then gradually cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other and perpendicular to the projection direction of the optical axis of the polarized ultraviolet ray of the liquid crystal alignment film to the substrate surface, thereby producing a liquid crystal display element . Further, by carrying out the series of operations described above by changing the amount of ultraviolet radiation before prebaking, three or more liquid crystal display elements having different ultraviolet radiation doses were produced.

&Lt; Evaluation of liquid crystal display element &

Evaluation of the following items (1) to (5) was carried out using the liquid crystal display device manufactured as described above. With respect to the following (2) to (4), based on the result of the sensitivity evaluation in the same manner as in (1), an optimum sensitivity is selected from three or more liquid crystal display elements having different ultraviolet radiation dose amounts, The evaluation results of the liquid crystal display element with the optimum sensitivity are shown.

 (1) Evaluation of sensitivity to ultraviolet rays

Using the liquid crystal display device manufactured as described above, the presence or absence of an abnormal (abnormal) domain in the change of light and dark when a voltage of 5 V was applied / released was observed by an optical microscope. The lower the dose of ultraviolet radiation when the liquid crystal alignability was observed (when no abnormal domains were observed), the better the sensitivity of the coating film to ultraviolet rays. In the evaluation, an abnormal domain was observed at an ultraviolet irradiation dose of 5,000 J / m &lt; 2 &gt; while an abnormal domain was observed at an ultraviolet irradiation dose of 7,000 J / m2 and 10,000 J / The sensitivity was "impossible" when no observations were made, and when the abnormal domains were observed at 5,000 J / m2 and 7,000 J / m2 ultraviolet irradiation amount, the sensitivity was "impossible".

(2) Evaluation of Voltage Conservation Rate

Using the liquid crystal display device manufactured as described above, a voltage of 5 V was applied at 60 캜 for an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio after 167 milliseconds after the application was released was measured. VHR-1 &quot; manufactured by Toyo Technica Co., Ltd. was used as the measuring device. The voltage holding ratio of this liquid crystal display element was 99%.

(3) Measurement of charge accumulation amount (RDC)

Using a liquid crystal display device manufactured as described above, a direct current voltage of 2 V was applied at 71 캜 for 10 minutes, followed by a short circuit for 0.2 seconds, and then a voltage accumulated in the liquid crystal display element Was measured by a dielectric absorption method. The evaluation was performed when the charge accumulation amount was 0.1 V or less and the case where the charge accumulation amount was larger than 0.1 V and 0.2 V or less was allowed (?) And the case where the charge accumulation amount was larger than 0.2 V was evaluated as &quot; △) ". As a result, it was possible to evaluate the charge accumulation amount of the liquid crystal display element.

(4) Evaluation of AC afterimage characteristic

The AC afterimage characteristic (burn-in characteristic) was evaluated using the liquid crystal display device manufactured as described above. First, the liquid crystal display element was placed under an environment of 25 占 폚 and 1 atm, no voltage was applied to the electrode B, and an AC voltage of 4 V was applied to the electrode A for 2 hours. Immediately thereafter, a voltage of 4 V of AC was applied to both the electrode A and the electrode B. The time from when the application of the voltage of 4 V of alternating current to both the electrodes until the difference in the light transmittance between the electrodes A and B became visually confirmed was measured. The burn-in characteristic is "possible (O)" when the burn-in characteristic is "good" (⊚) when the burn-in characteristic is less than 60 seconds, 60 seconds or more and less than 100 seconds when burn- He said. As a result, the liquid crystal display element exhibited a burn-in property of &quot; possible &quot;.

(5) Evaluation of contrast after driving stress

The minimum relative transmittance (%) shown by the following formula (2) was calculated using the apparatus in which the polarizer and the analyzer were arranged between the light source and the light amount detector after driving the liquid crystal display device manufactured as described above for 30 hours under an alternating voltage of 10 V Respectively.

Minimum relative transmittance (%) = {(? - B ⁰ ) / (B ^{100 -} B ⁰ )} × 100 (2)

B ⁰ is a transmittance of light under cross nicol in a blank, B ¹⁰⁰ is a transmittance of light under para-nicol in a blank, B is a transmittance of light under a cross nicolol between a polarizer and an analyzer, Which is the minimum amount of light passing through the optical fiber.

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the lower the black level in the dark state, the better the contrast. Good "means that the minimum relative transmittance is less than 0.5%," Possible "means that it is 0.5% or more and less than 1.0%, and" Bad "means that it is 1.0% or more. As a result, the contrast evaluation of this liquid crystal display element was judged to be &quot; good &quot;.

[Examples 2, 6 to 10, 12, 13 and 14, Comparative Examples 1 to 3]

A liquid crystal display device was prepared by preparing a photo-dispersing agent in the same manner as in Example 1 except that the types of polymers used were changed as shown in Tables 3 and 4, respectively. Various evaluations of the manufactured liquid crystal display device were also performed. The evaluation results are shown in Tables 3 and 4, respectively.

[Examples 3 to 5, 11, 15]

A liquid crystal display device was prepared by preparing a photo-dispersing agent in the same manner as in Example 1 except that the types of polymers used were changed as shown in Tables 3 and 4, respectively, and additives were mixed. Various evaluations of the manufactured liquid crystal display device were also performed. The evaluation results are shown in Tables 3 and 4, respectively.

In Table 3 and Table 4, the numerical value of the blending amount of the polymer indicates the compounding ratio (parts by weight) of each polymer to the total 100 parts by weight of the polymer used for preparing the photo-dispersing agent. The name of the additive is as follows.

[additive]

Q-1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (Compound (Q-1)

Q-2: The following compound (Q-2)

As shown in Tables 3 and 4, in Examples 1 to 13, the voltage holding ratio was all 99% or more and the charge accumulation amount was small. In addition, the AC afterimage characteristic, the contrast characteristic, and the sensitivity to ultraviolet ray were &quot; good &quot; or &quot; possible &quot; In Examples 14 and 15, the same results are obtained. On the other hand, in Comparative Examples 1 to 3, the voltage holding ratio was as low as less than 99% and the charge accumulation amount was large.

&Lt; Synthesis of polymer (A) [2] &gt;

The procedure of Synthesis Example a2 was repeated except that the kind and amount of the tetracarboxylic acid dianhydride and the diamine used were changed as shown in Table 5 to obtain a polyamic acid solution having a solid concentration of 10% by weight. The weight average molecular weight Mw of each polymer is shown in Table 5 below.

In Table 5, the numerical values in parentheses of each column of the compound show the compounding ratio (molar ratio) relative to the total 100 moles of tetracarboxylic acid derivatives used.

&Lt; Preparation of optically brightener, preparation and evaluation of liquid crystal display element [2] &gt;

[Examples 16 to 21]

A liquid crystal display device was prepared in the same manner as in Example 1 except that the types of polymers used were changed as shown in Table 6 below. Various evaluations of the manufactured liquid crystal display device were also performed. The evaluation results are shown in Table 6 below.

In Table 6, the numerical value of the blending amount of the polymer indicates the mixing ratio (parts by weight) of each polymer to the total 100 parts by weight of the polymer used for preparing the photo-dispersing agent.

As shown in Table 6, in Examples 16 to 21, various characteristics were balanced by evaluating the voltage holding ratio, the charge accumulation amount, the AC afterimage characteristic, the contrast characteristic, and the sensitivity to ultraviolet rays as "good" or "possible" .

Claims (14)

(A) a polymer and (B) a polymer, wherein the polymer (A) is at least one polymer component selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, A step of applying a liquid crystal aligning agent, which is a polymer having a main chain of the structure (Y) (except for the amide bond formed by polymerization reaction when X ¹ is -NH-), onto a substrate to form a coating film; ,
A step of irradiating the coating film with light to form a liquid crystal alignment film
A method for producing a liquid crystal alignment film comprising:

(In the formula (1), X ¹ represents a sulfur atom, an oxygen atom or -NH-; "*" represents a bonding hand, provided that at least one of the two "*" . The method according to claim 1,
Wherein the content of at least one specific atom of the fluorine atom and the silicon atom is different in the polymer (A) and the polymer (B). 3. The method of claim 2,
Wherein the polymer (A) is higher in content of the specific atom than the polymer (B). 3. The method of claim 2,
Wherein the proportion of the repeating unit having the specific atom to the total repeating units of the polymer in the polymer having the specific atom is 1 to 70 mol%. The method according to claim 1,
Wherein the content ratio of the polymer (A) to the polymer (B) is 2/8 to 8/2 in weight ratio (A / B). The method according to claim 1,
At least one of the polymer (A) and the polymer (B) is a polymer having a structure represented by the following formula (2-1) and a structure represented by the following formula (2-2) And a nitrogen-containing heterocycle. The method for producing a liquid crystal alignment film according to claim 1,

(In the formula (2-1), R ¹ is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, r ¹ is an integer of 0 to 2, r 2 is an integer of 0 to 3; (2-2), R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; "* 2" indicates a bonding hand; ). The method according to claim 6,
Wherein the content of the repeating unit having the structure (Z) in the polymer having the structure (Z) is 2 to 40 mol% with respect to the total repeating units of the polymer. The method according to claim 6,
Wherein at least one of the polymer (A) and the polymer (B) has at least one specific atom selected from the group consisting of a fluorine atom and a silicon atom,
Wherein the polymer having a lower content of the specific atom in the polymer (A) and the polymer (B) has the structure (Z). The method according to claim 6,
Wherein the polymer (B) has the structure (Z). The method according to claim 6,
The polymer (A) has the structure (Y) and at least one specific atom of a fluorine atom and a silicon atom,
Wherein the polymer (B) has the structure (Z) and the content of the specific atom is lower than that of the polymer (A). The method according to claim 1,
The polymer (B) is preferably selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4, Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan Dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ At least one member selected from the group consisting of furan-1,3-dione, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic acid dianhydride, Wherein the tetracarboxylic acid dianhydride is a polymer obtained by reacting a tetracarboxylic acid dianhydride and a diamine. The method according to claim 1,
The polymer (A) is a process for producing a liquid crystal alignment film having a structure represented by the following formula (3) in the main chain:

(In the formula (3), k and i are each independently 0 or 1, 1 is an integer of 2 to 9, j is an integer of 1 to 4, and &quot; * &quot; (A) a polymer and (B) a polymer, wherein the polymer (A) is at least one polymer component selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, A photopolymerization initiator which is a polymer having, in a main chain thereof, a structure (Y) (excluding an amide bond formed by a polymerization reaction when X ¹ is -NH-)

(In the formula (1), X ¹ represents a sulfur atom, an oxygen atom or -NH-; "*" represents a bonding hand, provided that at least one of the two "*" . A liquid crystal display element comprising a liquid crystal alignment film produced by the method according to any one of claims 1 to 12.