KR20220166817A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent that forms a liquid crystal aligning film having a high light transmittance because it has a high refractive index and does not have colorability, and a liquid crystal aligning agent that forms a liquid crystal aligning film that has high homeotropic alignment in addition to the above characteristics.
It is a liquid crystal aligning agent containing the following (A) component and (B) component.
Component (A): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide product of the polyimide precursor (A)
Component (B): It has a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and is characterized in that at least a part of the triazine ring terminal is capped with an arylamino group having a crosslinking group. Polymer (B)

Description

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

This invention relates to the liquid crystal display element which has a liquid crystal aligning agent, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

Conventionally, as a liquid crystal display element, various drive methods having different electrode structures and physical properties of liquid crystal molecules used have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment ) type, IPS (In-Plane Switching) type, FFS (fringe field switching) type, etc. various display elements are known.

A liquid crystal display element is generally constructed by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several micrometers) and encapsulating a liquid crystal between the electrode substrates. And display in a liquid crystal display element is performed by applying a voltage between the transparent conductive films which comprise each electrode of an electrode substrate. Moreover, these liquid crystal display elements have a liquid crystal aligning film for orienting liquid crystal molecules. As a material of a liquid crystal aligning film, polyamic acid (polyamic acid), polyamic acid ester, a polyimide, etc. are known, for example (refer patent document 1 etc.).

International Publication No. 2016-080458

The above-mentioned transparent conductive film in the liquid crystal display element is usually formed of a composition (ITO) in which indium oxide is the main component and tin oxide is doped therein by several percent (ITO), but its refractive index is high, unlike the refractive index of the liquid crystal aligning film. has a value For this reason, when trying to transmit the light from a display light source to an electrode substrate, light will be reflected by the boundary surface of the transparent conductive film and the liquid crystal aligning film in each electrode substrate. As a result, the light transmittance of the electrode substrate cannot be obtained sufficiently, resulting in a problem that the display luminance is lowered.

In particular, ultra-high-definition panels such as 4K and 8K have been developed in recent years, but in these panels, the share of black matrix (BM), TFT, etc. increases and the aperture ratio of the panel decreases, so improving the transmittance of the display section is important. It is becoming.

Then, the present inventors studied variously about the formation material in order to raise the refractive index of a liquid crystal aligning film from a viewpoint that the said problem can be solved if the difference of the refractive index of a transparent conductive film and the refractive index of a liquid crystal aligning film is made small. In order to raise the refractive index of a liquid crystal aligning film specifically, the kind of polymer contained in the liquid crystal aligning agent which forms a liquid crystal aligning film was searched for variously.

As a result, by selecting a specific polymer, it was possible to obtain a liquid crystal aligning film having a high refractive index close to the refractive index of the transparent conductive film, but on the other hand, it became clear that the polymer forming the liquid crystal aligning film having a high refractive index has colorability in most cases. . A liquid crystal aligning film formed from a liquid crystal aligning agent containing a polymer having colorability decreases the transmittance of light thereby causing a decrease in display luminance, and as a result, the above object is not achieved. Moreover, it became clear that the liquid crystal aligning film with high vertical alignment was hard to obtain a high refractive index under the influence of a side chain structure, and the liquid crystal aligning film which had a high refractive index and vertical alignment was calculated|required.

In view of the above circumstances, since the object of the present invention has a high refractive index and does not have colorability, the liquid crystal aligning agent which forms a liquid crystal aligning film having a high light transmittance, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film It is to provide the liquid crystal display element which has. Furthermore, in addition to the said characteristic, it is providing the liquid crystal display element which has the liquid crystal aligning agent which forms the liquid crystal aligning film which has high homeotropic alignment, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

As a result of earnestly researching in order to achieve the said subject, this inventor discovered that the liquid crystal aligning agent containing a specific polymer was effective in order to achieve the said objective, and came to complete this invention.

The present invention includes the following aspects.

[1] A liquid crystal aligning agent characterized by containing the following (A) component and (B) component.

Component (A): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide product of the polyimide precursor (A)

Component (B): It has a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and is characterized in that at least a part of the triazine ring terminal is capped with an arylamino group having a crosslinking group. Polymer (B)

[Formula 1]

(R and R' represent, independently of each other, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group,

Ar represents at least one selected from the group represented by formulas (2) to (12).)

[Formula 2]

(Arbitrary hydrogen atoms on the aromatic rings of formulas (2) to (12) may be substituted,

R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

W ¹ and W ² are each independently a single bond, -CR ⁹⁵ R ⁹⁶ - (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (provided that they form a ring ), -C(=O)-, -O-, -S-, -S(=O)-, -SO ₂ -, or -NR ⁹⁷ - (R ⁹⁷ is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)

X ¹ and X ² are, independently of each other, a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y ₁ -Ph-Y ₂ - (Ph represents a phenylene group, and any hydrogen atom on the phenylene group may be substituted; And, Y ₁ and Y ₂ independently represent a single bond or an alkylene group having 1 to 10 carbon atoms).)

ADVANTAGE OF THE INVENTION According to this invention, since it has a high refractive index and does not have colorability, it provides the liquid crystal display element which has the liquid crystal aligning agent which forms the liquid crystal aligning film which has a high light transmittance, the liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film can Furthermore, in addition to the said characteristic, the liquid crystal display element which has the liquid crystal aligning agent which forms the liquid crystal aligning film which has high homeotropic alignment, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film can be provided.

1 is a graph showing measurement results of the ¹ H-NMR spectrum of compound T-1 synthesized in Examples.
Fig. 2 is a graph showing measurement results of the ¹ H-NMR spectrum of compound T-2 synthesized in Examples.

Hereinafter, although the liquid crystal display element which has the liquid crystal aligning agent of this invention, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film is demonstrated in detail, description of the structural requirements described below is one embodiment of this invention It is an example as , and is not specific to these contents.

(liquid crystal alignment agent)

The liquid crystal aligning agent of this invention contains the following (A) component and (B) component.

Component (A): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide product of the polyimide precursor (A)

Component (B): Contains the repeating unit structure represented by the formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is capped with an arylamino group having a crosslinking group. Polymer (B)

Each of the polymer (A) as component (A) and the polymer (B) as component (B) will be described in detail below.

<Polymer (A)>

The liquid crystal aligning agent of this invention contains at least 1 sort(s) of polymer (A) chosen from the group which consists of a polyimide precursor and the polyimide which is an imide product of this polyimide precursor. (A) The polymer constituting the component may be composed of one type or two or more types of polymers.

Examples of the polyimide precursor include polyamic acid, polyamic acid ester, or a polyamic acid-polyamic acid ester copolymer, and the polyimide precursor preferably polymerizes a diamine component and a tetracarboxylic acid component. obtained by reacting

<<diamine component>>

As a diamine component, diamine (a) which has at least 1 sort(s) selected from the group which consists of structures represented by following formula (S1) - (S3), p-phenylenediamine, m-phenylenediamine, 4-(2-) (methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or diamine represented by the following formulas (3b-1) to (3b-4) Diamine having a carboxyl group such as compounds, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Ether, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (4-amino Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane , 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4 -Aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl)ether, 4-amino-4' -(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl , 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 Diamine having a urea bond such as 2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenethyl)urea, 2-(2,4-diaminophenoxy)ethyl methacrylate , diamines having photopolymerizable groups such as 2,4-diamino-N,N-diallylaniline at the terminals, diamines having radical initiating functions such as the following formulas (R1) to (R5), and 4,4'-dia Minobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4-aminophenyl)fluorene Diamine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole having a photosensitizing function that exhibits a sensitizing effect by irradiation with light such as , N-methyl-3,6-diaminocarbazole, diamine having a heterocyclic ring such as the following formulas (z-1) to (z-18), the following formulas (Dp-1) to (Dp-9), etc. A diamine having a diphenylamine skeleton, a group "-N(D)-" such as the following formulas (5-1) to (5-10) (D represents a protecting group that is desorbed by heating and replaced with a hydrogen atom, preferably is a tert-butoxycarbonyl group.), and aromatic diamines such as diamines having oxazoline structures such as the following formulas (Ox-1) to (Ox-2), but are not limited thereto. The diamine component may be comprised of 1 type or 2 or more types of diamine.

[Formula 3]

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 - (a1 is an integer from 1 to 15, A ₁ represents an oxygen atom or -COO- , m ₁ is an integer of 1 to 2. When m ₁ is 2, a plurality of a1 and A ₁ each independently have the above definition.) G ¹ and G ² are each independently a carbon number represents a divalent cyclic group selected from a divalent aromatic group of 6 to 12 and a divalent alicyclic group of 3 to 8 carbon atoms, and any hydrogen atom on the cyclic group is an alkyl group of 1 to 3 carbon atoms or a divalent alicyclic group of 1 to 3 carbon atoms; It may be substituted with an alkoxy group, an alkyl group containing a fluorine atom of 1 to 3 carbon atoms, an alkoxy group containing a fluorine atom of 1 to 3 carbon atoms, or a fluorine atom. m and n are each independently an integer of 0 to 3, and m+n is 1 to 6 is an integer of, preferably, an integer of 1 to 4. R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen forming R ¹ The atom may be substituted with a fluorine atom.)

[Formula 4]

(X ³ represents a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.)

[Formula 5]

(X ⁴ represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-. R ³ represents a structure having a steroid skeleton.)

[Formula 6]

(In formula (3b-1), A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-, m1 and m2 are each independently an integer of 0 to 4, and m1+m2 is an integer of 1 to 4. In the formula (3b-2), m3 and m4 are each independently an integer of 1 to 5. In formula (3b-3), A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. Formula (3b-3) In -4), A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) _2- , -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, and m6 is an integer of 1 to 4.)

[Formula 7]

[Formula 8]

[Formula 9]

(In (R3) to (R5), n is an integer of 1 to 6.)

[Formula 10]

[Formula 11]

(Boc represents a tert-butoxycarbonyl group.)

[Formula 12]

As diamine (a), what has at least 1 benzene ring is preferable. As a more preferable specific example, the diamine represented by the following formula (d1) or formula (d2) is mentioned.

[Formula 13]

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m - O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) represents _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO- m is an integer of 1 to 8. Y is the formula (S1) to (S3 ) In formula (d2), two Y's may be the same as or different from each other).

As a preferable example of the diamine represented by the said formula (d1), the following formula (d1-1) - (d1-7) are mentioned. As a preferable example of the diamine represented by the said formula (d2), the following formula (d2-1) - (d2-6) are mentioned.

[Formula 14]

[Formula 15]

( ^Xv1 to ^Xv4 and ^Xp1 to ^Xp8 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ ) Represents -, -NH-, -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO-, and X ^V5 to X ^V6 and X ^s1 to X ^s4 are each independently , -O-, -CH ₂ O-, -COO- or -OCO- X ^v7 represents -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO-, or -OCO- X _a to X _f represent a single bond, -O-, -NH-, -O-(CH ₂ ) _m -O- (m is an integer of 1 to 8), R ^v1 to R ^v4 , R ^1a to R ^1h each independently represent -CnH _2n+1 (n is an integer from 1 to 20) or -OC _n H _2n+1 (n is an integer from 2 to 20).)

The diamine having a radical initiating function or the diamine having a photosensitizing function exhibiting a sensitizing function by light irradiation increases the response speed of a liquid crystal display element such as a PSA type liquid crystal display element or a liquid crystal display element for SC-PVA mode. Then, when manufacturing a polymer (A), you may use 1 type(s) or 2 or more types.

As said diamine component, p-phenylenediamine, 3,5- diamino benzoic acid, 4,4'- diamino diphenylmethane, 4,4'- from a viewpoint of obtaining the effect of this invention preferably among the above-mentioned Diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N- Diallylaniline, diamines represented by the formulas (R1) to (R5), diamines represented by the formulas (z-1) to (z-18), and diamines represented by the formulas (Dp-1) to (Dp-9) , diamines represented by the formulas (Ox-1) to (Ox-2) are preferable.

Moreover, as said diamine component, aliphatic diamines, such as metaxylenediamine, alicyclic diamine, such as 4, 4-methylene bis (cyclohexylamine), diamine of International Publication No. 2016/125870, etc. are mentioned.

<<tetracarboxylic acid component>>

The tetracarboxylic acid component refers to a component containing at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives. Examples of tetracarboxylic acid derivatives include tetracarboxylic acid dihalides, tetracarboxylic dianhydrides, tetracarboxylic acid diester dichlorides, and tetracarboxylic acid diesters. The tetracarboxylic acid component may be composed of one type or two or more types of tetracarboxylic acid and tetracarboxylic acid derivatives.

The tetracarboxylic acid component for producing the polymer (A) includes aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or derivatives thereof. Here, aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. Aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it is not necessary to be composed only of a chain-like hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Moreover, it is not necessary to be comprised only of an alicyclic structure, and may have a chain-like hydrocarbon structure or an aromatic ring structure in part.

The tetracarboxylic acid component preferably contains tetracarboxylic dianhydride represented by the following formula (S4).

[Formula 16]

(X represents a structure selected from the group consisting of (x-1) to (x-13) below.)

[Formula 17]

(R ¹ to R ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. R ⁵ and R ⁶ represents a hydrogen atom or a methyl group each independently, j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, -COO- , Represents a phenylene, sulfonyl, or amide bond. *1 is a binding hand binding to one acid anhydride group, and *2 is a binding hand binding to the other acid anhydride group.)

As more preferable specific examples of the formula (x-1), the following formulas (X1-1) to (X1-6) are exemplified. In the formula, * represents a bonding hand.

[Formula 18]

Preferred specific examples of the above (x-12) and (x-13) include the following formulas (x-14) to (x-29). In the formula, "*" represents a bond.

[Formula 19]

[Formula 20]

Preferable examples of the tetracarboxylic dianhydride or derivative thereof represented by the formula (S4) include formulas in which X is the formulas (x-1) to (x-7) and (x-11) to (x-13) Tetracarboxylic dianhydride represented by (3) or its derivative(s) is mentioned.

<Method for producing polymer (A)>

The polymer (A) used for this invention is compoundable by the well-known method described in international publication WO2013/157586, for example.

A polyimide can be obtained by ring-closing (imidating) the polyimide precursor obtained in the polymer (A). In addition, the imidation rate described in this specification is the ratio of the imide group to the total amount of the imide group derived from tetracarboxylic dianhydride or its derivative(s) and a carboxyl group (or its derivative(s)).

The molecular weight of the polymer (A) used in the present invention is 5,000 as a weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the liquid crystal alignment film obtained there, workability at the time of film formation, and coating film properties are considered. It is preferably to 1,000,000, more preferably 10,000 to 150,000.

<Polymer (B)>

The liquid crystal aligning agent of the present invention includes a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of this triazine ring terminal is capped with an arylamino group having a crosslinking group, It contains the polymer (B) characterized by being present. (B) The polymer constituting the component may be composed of one type or two or more types of polymers.

[Formula 21]

(R and R' represent, independently of each other, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group,

Ar represents at least 1 sort(s) chosen from the group represented by Formula (2)-(12).

[Formula 22]

(Arbitrary hydrogen atoms on the aromatic rings of formulas (2) to (12) may be substituted,

R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;

W ¹ and W ² are each independently a single bond, -CR ⁹⁵ R ⁹⁶ - (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (provided that they form a ring ), -C(=O)-, -O-, -S-, -S(=O)-, -SO ₂ -, or -NR ⁹⁷ - (R ⁹⁷ is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)

X ¹ and X ² are, independently of each other, a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y ₁ -Ph-Y ₂ - (Ph represents a phenylene group, and any hydrogen atom on the phenylene group may be substituted; And, Y ₁ and Y ₂ independently represent a single bond or an alkylene group having 1 to 10 carbon atoms).)

In the above formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, but from the viewpoint of further increasing the refractive index, both are preferably hydrogen atoms. .

In the present invention, the number of carbon atoms in the alkyl groups of R and R' in the formula (1) is not particularly limited, but is preferably 1 to 20, and in consideration of further increasing the heat resistance of the polymer, 1 to 10 carbon atoms are more preferable And, 1 to 3 are more preferable. In addition, the structure may be chain, branched, or cyclic.

Specific examples of the alkyl group represented by R and R' in the formula (1) include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-Methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n- Propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl -Cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2- Methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n- Butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1 -methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-Dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl -Cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl , 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3 -methyl-cyclopropyl group etc. are mentioned.

The number of carbon atoms of the alkoxy groups of R and R' in the formula (1) is not particularly limited, but is preferably 1 to 20, and in consideration of further increasing the heat resistance of the polymer, 1 to 10 carbon atoms are more preferable, and 1 to 3 more desirable than this. Further, the structure of the alkyl moiety may be chain, branched or cyclic.

Specific examples of the alkoxy groups of R and R' in the formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-part Toxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl -n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy , 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-part Toxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n - A propoxy group etc. are mentioned.

The number of carbon atoms of the aryl groups of R and R' in the above formula (1) is not particularly limited, but is preferably 6 to 40, and in consideration of further increasing the heat resistance of the polymer, 6 to 16 carbon atoms are more preferable, and 6 to 13 more desirable than this.

Specific examples of the aryl group represented by R and R' in the formula (1) include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o- Methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1 -Anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl group, etc. are mentioned.

The carbon number of the aralkyl group of R and R' in the formula (1) is not particularly limited, but preferably has 7 to 20 carbon atoms, and the alkyl moiety may be linear, branched or cyclic.

Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4 -Isobutylphenylmethyl, α-naphthylmethyl group, etc. are mentioned.

Arbitrary hydrogen atoms on the aromatic ring in the above formulas (2) to (12) are halogen atoms, carboxyl groups, sulfo groups, alkyl groups which may have branched structures of 1 to 10 carbon atoms, and branched structures of 1 to 10 carbon atoms. It may be substituted with the halogenated alkyl group which may be present, or the alkoxy group which may have a branched structure of 1 to 10 carbon atoms.

As a halogen atom which is a substituent on the aromatic ring in said formula (2)-(12), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Moreover, as an alkyl group and an alkoxy group which are substituents on the aromatic ring in the said formula (2) - (12), the thing similar to the structure illustrated by the said formula (1) is mentioned.

The halogenated alkyl group having 1 to 10 carbon atoms, which is a substituent on the aromatic ring in the above formulas (2) to (12), substitutes at least one hydrogen atom in the alkyl group which may have a branched structure of 1 to 10 carbon atoms with a halogen atom As one, specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3 -Pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4,4,4- Trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3, 3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3 ,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3, 4,4,5,5,6,6,6-nonafluorohexyl, and perfluorohexyl groups.

Examples of the alkylene group having 1 to 10 carbon atoms for X ¹ and X ² in the formula (11) include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene groups.

Any hydrogen atom on the phenylene group in the group "-Y ₁ -Ph-Y ₂ -" is a halogen atom, a carboxyl group, a sulfo group, an alkyl group that may have a branched structure of 1 to 10 carbon atoms, or 1 to 10 carbon atoms may be substituted with a halogenated alkyl group which may have a branched structure of or an alkoxy group which may have a branched structure of 1 to 10 carbon atoms.

When any hydrogen atom on the aromatic ring in the above formulas (2) to (12) and any hydrogen atom on the phenylene group in the group "-Y ₁ -Ph-Y ₂ -" are substituted, the above exemplified Among them, a halogen atom, a sulfo group, an alkyl group which may have a branched structure of 1 to 5 carbon atoms, a halogenated alkyl group which may have a branched structure of 1 to 5 carbon atoms, or an alkoxy group which may have a branched structure of 1 to 5 carbon atoms is used. desirable.

As Ar in the said formula (1), at least 1 sort(s) represented by formula (2), (5)-(12) is preferable, and formula (2), (5), (7), (8), (11) ) - at least 1 sort(s) represented by (12) is more preferable. Specific examples of the aryl group represented by the above formulas (2) to (12) include those represented by the following formulas (1-1) to (1-25), but are not limited thereto. In formula, Ph represents a phenyl group.

[Formula 23]

[Formula 24]

Among these, since a polymer with a higher refractive index can be obtained, the above formulas (1-1), (1-2), (1-5) to (1-15), (1-18) to (1-21) , The aryl group represented by (1-23) - (1-25) is more preferable.

In particular, considering the higher solubility of the polymer in organic solvents, Ar is preferably a m-phenylene group represented by the formula (21-a).

[Formula 25]

Further, the polymer (B) of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is capped with an arylamino group having a crosslinking group.

In addition, the polymer (B) of the present invention has at least one triazine ring terminal, but the triazine ring at this terminal usually has two halogen atoms substitutable with the arylamino group having the above crosslinking group. Therefore, the arylamino group having the crosslinking group may be bonded to the same triazine ring terminal, or when there are a plurality of triazine ring terminals, each may be bonded to different triazine ring terminals.

Examples of the aryl group of the arylamino group having a crosslinking group include the same ones as described above, but a phenyl group is particularly preferable.

Examples of the crosslinking group include a hydroxy-containing group, a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxy-containing group, a sulfo-containing group, a thiol-containing group, and a (meth)acryloyl-containing group. Considering improving the heat resistance of B), a hydroxy-containing group and a (meth)acryloyl-containing group are preferable.

As a hydroxyl-containing group, a hydroxyl group, a hydroxyalkyl group, etc. are mentioned. Although both a hydroxy group and a hydroxyalkyl group are preferable, a C1-C10 hydroxyalkyl group is more preferable.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and 7-hydroxyheptyl. , 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl , 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy carbon atoms bonded to hydroxyl groups such as oxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, and 4-hydroxy-3-methylbutyl groups are primary carbon atoms; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2- The carbon atom to which the hydroxy group such as hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl group is bonded is secondary or secondary. A tertiary carbon atom is exemplified.

In particular, in view of improving heat resistance and high temperature and high humidity resistance, it is preferable that the carbon atom to which the hydroxyl group bonds is a primary carbon atom, and among these, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable, and a carbon atom having 1 to 5 carbon atoms is particularly preferable. A 3-hydroxyalkyl group is more preferred, a hydroxymethyl group and a 2-hydroxyethyl group are more preferred, and a 2-hydroxyethyl group is most preferred.

Examples of the (meth)acryloyl-containing group include a (meth)acryloyl group, a (meth)acryloyloxyalkyl group, and a group represented by the following formula (i), but having an alkyl group of 1 to 10 carbon atoms (meth) ) An acryloyloxyalkyl group and a group represented by the following formula (i) are preferred, and a group represented by the following formula (i) is more preferred.

[Formula 26]

(In the formula, A ¹ represents an alkylene group having 1 to 10 carbon atoms, A ² represents a single bond or a group represented by the following formula (j), and A ³ represents a divalent or trivalent group which may be substituted with a hydroxyl group. represents an aliphatic hydrocarbon group, A ⁴ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond.)

[Formula 27]

(* indicates a bonding hand.)

Examples of the alkyl group contained in the (meth)acryloyloxyalkyl group having an alkyl group of 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n - A pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group, etc. are mentioned. Considering improving heat resistance and high temperature and high humidity resistance, among these, those having an alkyl group of 1 to 5 carbon atoms are preferable, those having an alkyl group of 1 to 3 carbon atoms are preferable, and those having an alkyl group of 1 or 2 carbon atoms are more preferable Do.

Specific examples of the (meth)acryloyloxyalkyl group include, for example, a (meth)acryloyloxymethyl group, a 2-(meth)acryloyloxyethyl group, and a 3-(meth)acryloyloxypropyl group. , 4-(meth)acryloyloxybutyl group.

In formula (i), A ¹ is an alkylene group of 1 to 10 carbon atoms, preferably an alkylene group of 1 to 5 carbon atoms, and more preferably a methylene group and an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene and pentamethylene.

A ² represents a single bond or a group represented by the formula (j), and a group represented by the formula (j) is preferable.

A ³ is a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and specific examples thereof include an alkylene group having 1 to 5 carbon atoms and the following formulas (k-1) to (k-3) ), a C1-C5 alkylene group is preferable, a C1-C3 alkylene group is more preferable, and a methylene group and an ethylene group are even more preferable. As the alkylene group for A ³ , among the alkylene groups exemplified for A ¹ , an alkylene group having 1 to 5 carbon atoms is exemplified.

[Formula 28]

(In the formula, * is the same as above.)

In formula (i), a represents 1 or 2, but 1 is preferable.

As a preferable aspect of group represented by formula (i), what is represented by following formula (i-1) is mentioned.

[Formula 29]

(In the formula, A ¹ , A ³ , A ⁴ and * are the same as above.)

As a more preferable aspect of group represented by formula (i), what is represented by the following formula (i-2) - (i-3) is mentioned.

[Formula 30]

(In the formula, * is the same as above.)

Examples of the vinyl-containing group include an alkenyl group having 2 to 10 carbon atoms having a vinyl group at the terminal. As a specific example, an ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl group, etc. are mentioned.

As an epoxy-containing group, an epoxy group, a glycidyl group, a glycidyl alkyl group, a glycidyloxy group, etc. are mentioned. As a specific example, glycidyl methyl, 2-glycidyl ethyl, 3-glycidyl propyl, 4-glycidyl butyl group etc. are mentioned.

As the oxetane-containing group, oxetan-3-yl, (oxetan-3-yl)methyl, 2-(oxetan-3-yl)ethyl, 3-(oxetan-3-yl)propyl, 4-( An oxetan-3-yl) butyl group etc. are mentioned.

As a carboxy-containing group, a carboxyl group and a carboxyalkyl group of 1 to 10 carbon atoms, etc. are mentioned. As the carboxyalkyl group having 1 to 10 carbon atoms, those to which the carbon atom to which the carboxyl group bonds are preferably primary carbon atoms, and specific examples include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and 4-carboxybutyl groups. can be heard

Examples of the sulfo-containing group include sulfo groups and sulfoalkyl groups of 1 to 10 carbon atoms. As for the sulfoalkyl group having 1 to 10 carbon atoms, it is preferable that the carbon atom to which the sulfo group is bonded is a primary carbon atom, and specific examples thereof include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl groups. can be heard

As a thiol-containing group, a thiol group, a C1-C10 mercaptoalkyl group, etc. are mentioned. As for the mercaptoalkyl group having 1 to 10 carbon atoms, it is preferable that the carbon atom to which the thiol group bonds is a primary carbon atom, and specific examples include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl and 4-mer A captobutyl group etc. are mentioned.

The number of crosslinking groups is not particularly limited and can be any number that can be substituted on the aryl group, but 1 to 4 are preferable, 1 to 2 are more preferable, and 1 is even more preferable.

As an arylamino group which has a preferable crosslinking group, what is represented by Formula (15) is mentioned, and what is represented by Formula (16) which has a crosslinking group at para-position with respect to an amino group is especially preferable.

[Formula 31]

(In the formula, R ¹⁵ represents a crosslinking group. * represents a bonding hand.)

[Formula 32]

(In the formula, R ¹⁵ has the same meaning as above. * represents a bond.)

Specific examples of the arylamino group having a crosslinking group include those represented by the following formulas (16-1) to (16-13), but are not limited thereto. In the formula, * represents a bonding hand.

[Formula 33]

In addition, an arylamino group having a hydroxyalkyl group can be introduced using a corresponding hydroxyalkyl group-substituted arylamino compound in a production method described later.

Specific examples of the hydroxyalkyl group-substituted arylamino compound include (4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

The arylamino group having a (meth)acryloyloxyalkyl group can be obtained by using a corresponding (meth)acryloyloxyalkyl group-substituted arylamino compound or by introducing an arylamino group having a hydroxyalkyl group into the polymer (B). , It can be introduced by a method in which a (meth)acrylic acid halide or (meth)acrylate glycidyl acts on the hydroxyl group contained in the hydroxyalkyl group.

The arylamino group having a group represented by the formula (i) can be obtained by a method using an arylamino compound having a target crosslinking group or by introducing an arylamino group having a hydroxyalkyl group into the polymer (B), and then further using the hydroxyalkyl group It can introduce|transduce by the method of making the (meth)acrylic acid ester compound which has an isocyanate group represented by following formula (i') with respect to the hydroxyl group contained in .

[Formula 34]

(In the formula, A ³ , A ⁴ and a are the same as above.)

As a specific example of the (meth)acryloyloxyalkyl group-substituted arylamino compound, for example, (meth)acrylic acid halide or (meth)acrylate glycidyl is added to the hydroxyl group of the hydroxyalkyl group-substituted arylamino compound described above. The ester compound obtained by making it act is mentioned.

Examples of the (meth)acrylic acid halide include (meth)acrylic acid chloride, (meth)acrylic acid bromide and (meth)acrylic acid iodide.

Specific examples of the (meth)acrylic acid ester compound having an isocyanate group represented by the formula (i') include, for example, 2-isocyanate ethyl acrylate, 2-isocyanatoethyl methacrylate, and 1,1- (Bisacryloyloxymethyl) ethyl isocyanate is mentioned.

In this invention, what contains the repeating unit represented by Formula (18) - (21) as an especially preferable polymer (B) is mentioned.

[Formula 35]

(In the formula, R, R', and R ¹⁵ represent the same meanings as above. R ¹ to R ⁴ may have a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, or a branched structure of 1 to 10 carbon atoms. represents an alkyl group, a halogenated alkyl group which may have a branched structure of 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure of 1 to 10 carbon atoms (except for the case where R and R' are both hydrogen atoms).

[Formula 36]

(In the formula, R ¹⁵ has the same meaning as described above. R ¹ to R ⁴ have the same meaning as in the formula (18). Except for the case where all of R ¹ to R ⁴ are hydrogen atoms.)

[Formula 37]

(In the formula, R ¹⁵ represents the same meaning as described above.)

[Formula 38]

(In the formula, R ¹⁵ represents the same meaning as described above.)

The weight average molecular weight of the polymer (B) in the present invention is not particularly limited, but is preferably from 500 to 500,000, more preferably from 500 to 100,000, while further improving heat resistance and lowering the shrinkage rate, 2,000 or more is preferable, and 50,000 or less is preferable, 30,000 or less is more preferable, 15,000 or less is still more preferable, and 10,000 or less is particularly preferable from the viewpoint of further increasing the solubility and reducing the viscosity of the obtained solution.

In addition, the weight average molecular weight in the present invention is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.

The polymer (B) (hyper-branched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010/128661 described above.

That is, after reacting a trihalogenated triazine compound and an allyldiamino compound in an organic solvent, for example, an arylamino compound having a hydroxyalkyl group (hydroxy-containing group), an acryloyloxyalkyl group (acryl Polymer (B) of the present invention by reacting with at least one arylamino compound selected from arylamino compounds having a loyl-containing group) and arylamino compounds having a group represented by formula (i) (acryloyl-containing group) can be obtained.

For example, as shown in Scheme 1 below, the polymer (B) (20') reacts the triazine compound (22) and the aryldiamino compound (23) in an appropriate organic solvent, and then reacts with a hydra, which is an end capping agent. It can be obtained by making it react with the at least 1 sort(s) of arylamino compound (24) chosen from the arylamino compound which has a oxyalkyl group, and the arylamino compound which has a group represented by Formula (i).

[Formula 39]

(In the formula, X represents a halogen atom independently of each other, and Ra represents a hydroxyalkyl group or a group represented by formula (i).)

In the above reaction, the addition ratio of the aryldiamino compound (23) is arbitrary as long as the target polymer is obtained, but 0.01 to 10 equivalents of the aryldiamino compound (23) are preferred relative to 1 equivalent of the triazine compound (22). And, 1 to 5 equivalents are more preferable.

The aryldiamino compound (23) may be added as nitro or as a solution dissolved in an organic solvent, but the latter method is preferred in view of ease of operation and reaction control.

The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is particularly preferably about -30 to 150°C, and more preferably -10 to 100°C.

As another aspect, the method shown in following scheme 2 is mentioned. In this technique, the polymer (B) (20') is prepared by reacting a triazine compound (22) and an aryldiamino compound (23) in an appropriate organic solvent, and then forming an arylamino compound (24) having a hydroxyalkyl group as an end capping agent. ') to obtain a polymer (B) (20'') (first step), and then to the hydroxyl group of the hydroxyalkyl group further contained in the polymer (B) (20'') It can obtain by making the (meth)acrylic acid ester compound which has an isocyanate group represented by formula (i') act (2nd step).

In the case where the polymer (B) (20'') is the target object, the reaction in the second step may not be carried out, and the reaction in the first step may be completed.

[Formula 40]

(In the formula, R ^a1 represents a hydroxyalkyl group, and X, A ³ , A ⁴ , R ^a and a represent the same meaning as described above.)

In the above reaction, the input ratio and addition method of the aryldiamino compound (23) in the first step and the reaction temperature in the reaction until obtaining the polymer (B) (20'') are those described in Scheme 1. You can do the same.

Moreover, in the 2nd step, the preparation ratio of the (meth)acrylic acid ester compound which has an isocyanate group represented by formula (i') with respect to polymer (B) (20'') is hydroxyalkyl group and group represented by formula (i) It can be set arbitrarily according to the ratio of, and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, and even more preferably 0.7 to 3 equivalents relative to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. , more preferably 0.9 to 1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the polymer (B) (20'') are groups represented by formula (i), the input ratio is, relative to 1 equivalent of the arylamino compound having a hydroxyalkyl group used, The amount of the (meth)acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0 to 1.5 equivalents.

The reaction temperature in this reaction is the same as the reaction temperature in the reaction for obtaining the polymer (B) (20''), but considering that the (meth)acryloyl group does not cause polymerization during the reaction, it is 30 to 80 degreeC is preferable, 40-70 degreeC is more preferable, and 50-60 degreeC is still more preferable.

As the organic solvent, various solvents commonly used in this kind of reaction can be used, and examples thereof include tetrahydrofuran (THF), 1,4-dioxane, and dimethyl sulfoxide; N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N- Dimethylethyleneurea, N,N,N',N'-tetramethylmalonic acid amide, N-methyl-ε-caprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2 -amide solvents such as pyrrolidone, N,N-dimethylpropionic acid amide, N,N-dimethylisobutylamide, N-methylformamide, and N,N'-dimethylpropylene urea, and mixed solvents thereof. there is.

Among them, N,N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and mixtures thereof are preferred, and N,N-dimethylacetamide, N-methyl-2-pyrrolidone is preferred.

In addition, in the reaction of the first step of the above Scheme 1, various bases commonly used during or after polymerization may be added.

Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, hydroxide Barium, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpipery Deine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, etc. are mentioned.

The addition amount of the base is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (22). In addition, you may use these bases as an aqueous solution.

It is preferable that no raw material components remain in the resulting polymer, but some raw materials may remain as long as the effect of the present invention is not impaired.

After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

A known method may be employed as a method for terminal capping using an arylamino compound having a crosslinking group.

In this case, the amount of end capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and 0.5 to 5 equivalents, relative to 1 equivalent of halogen atoms derived from the excess triazine compound not used in the polymerization reaction. 2 equivalents are even more preferred.

As the reaction solvent and reaction temperature, the same conditions as those described for the reaction in the first stage of the scheme 1 can be used, and the terminal blocker may be introduced simultaneously with the aryldiamino compound (23).

Alternatively, an unsubstituted arylamino compound having no crosslinking group may be used, and end-capping may be performed with two or more types of groups. Examples of the aryl group of this unsubstituted arylamino compound include the same ones as described above.

Although what is represented by following formula (26) is mentioned as a specific unsubstituted arylamino group, It is not limited to this.

[Formula 41]

In addition, an unsubstituted arylamino group can be introduced using a corresponding unsubstituted arylamino compound in a production method described later.

Aniline etc. are mentioned as a specific example of an unsubstituted arylamino compound.

Further, when an unsubstituted arylamino group is introduced, the ratio of the arylamino compound having a crosslinking group and the unsubstituted arylamino compound is the arylamino compound having a crosslinking group 1 With respect to moles, 0.1 to 1.0 moles of the unsubstituted arylamino compound are preferred, 0.1 to 0.5 moles are more preferred, and 0.1 to 0.3 moles are still more preferred.

(liquid crystal alignment agent)

A liquid crystal aligning agent is used in order to produce a liquid crystal aligning film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing said polymer component and an organic solvent. In that case, the concentration of the polymer component in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the point of forming a uniform and defect-free coating film, 0.5 mass % or more is preferable, and from a viewpoint of storage stability of a solution, 15 mass % or less is preferable. A particularly preferable concentration of the polymer component is 1 to 10% by mass.

From a viewpoint of improving liquid-crystal orientation, the content ratio of (A) component and (B) component contained in the liquid crystal aligning agent of this invention is 10/90 - mass ratio of [(A) component]/[(B) component] It may be 90/10, it may be 20/80 to 90/10, or it may be 20/80 to 80/20.

Moreover, as for the liquid crystal aligning agent used for manufacture of a liquid crystal aligning film, the polymer component may mix a polymer (A), a polymer (B), and other polymers other than these again. In that case, content of another polymer is 0.5 mass % - 15 mass % of the total amount of polymer components, Preferably they are 1 mass % - 10 mass %. Examples of other polymers include acrylic polymers, methacrylic polymers, polystyrenes, polyamides, or polysiloxanes.

The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer (A) and the polymer (B), and examples thereof include lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(t- Butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methyl lactam solvents such as toxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, amide solvents such as 3-hexyloxy-N,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, and n-butoxy-N-isopropyl-propionamide; 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisobutyl ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isobaric acid lactate Wheat, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, di Ethylene 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, propylene glycol monomethyl ether acetate, Propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisopentyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1,2-ethanediol, 2,6-dimethyl-4-heptanol (diisobutylcarbinol), and propylene carbonate. there is. These can be used individually or in mixture of 2 or more types.

Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, and N-methyl-2 -Pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4 -Hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2- Pentanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl- 2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4- Hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisobutyl ketone, N-methyl-2-p Rolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl carbinol, N- Methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and the like. The kind and content of such a solvent are suitably selected according to the application apparatus of a liquid crystal aligning agent, application conditions, application environment, etc.

＜Other ingredients＞

The liquid crystal aligning agent of this invention may add other components other than the above, for example, a crosslinkable compound, a functional silane compound, surfactant, and the compound which has a photopolymerizable group etc. as needed.

A crosslinkable compound can be used for the purpose of enhancing the strength of the liquid crystal aligning film. As such a crosslinkable compound, at least one selected from the group consisting of compounds having an isocyanate group or a cyclocarbonate group described in paragraphs [0109] to [0113] of International Publication WO2016/047771, or a lower alkoxyalkyl group. In addition to the compound having a group, a compound having a block isocyanate group and the like are exemplified.

The block isocyanate compound can be obtained as a commercial item, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Milionate MS-50 (above, manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals), etc. can be used preferably.

As a specific example of a preferable crosslinkable compound, the compound represented by the following formula (CL-1) - (CL-11) is mentioned.

[Formula 42]

The above is an example of a crosslinkable compound, and is not limited to these. Moreover, 1 type may be sufficient as the crosslinkable compound used for the liquid crystal aligning agent of this invention, and you may combine it 2 or more types.

Content of other crosslinkable compounds in the liquid crystal aligning agent of this invention is 0.1-150 mass parts, or 0.1-100 mass parts, or 1-50 mass parts with respect to 100 mass parts of all polymer components.

A functional silane compound can be used for the purpose of improving the adhesiveness of a liquid crystal aligning film and a base substrate. As a specific example, the silane compound of international publication 2014/119682 Paragraph [0019] is mentioned. The content of the functional silane compound is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass with respect to 100 parts by mass of all polymer components.

Surfactant can be used for the purpose of improving the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film. As surfactant, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. Specific examples thereof include the surfactant described in paragraph [0117] of International Publication WO2016/047771. The amount of surfactant used is preferably from 0.01 to 2 parts by mass, more preferably from 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent.

The compound having a photopolymerizable group is a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in a molecule, for example, a compound represented by the following formulas (M-1) to (M-7). can

[Formula 43]

Further, in the liquid crystal aligning agent of the present invention, paragraphs [0194] to [0200] of International Publication WO2011/132751 (published on October 27, 2011) as a compound that promotes charge transfer in a liquid crystal aligning film and promotes charge omission of an element. , nitrogen-containing heterocyclic amine compounds represented by formula [M1] to formula [M156], more preferably 3-picorylamine or 4-picorylamine can be added. Although this amine compound may be added directly to a liquid crystal aligning agent, it is a density|concentration of 0.1-10 mass %, It is preferable to add, after setting it as a 1-7 mass % solution preferably. This solvent is not particularly limited as long as it dissolves the polymer component.

You may add an imidation promoter etc. to the liquid crystal aligning agent of this invention for the purpose of advancing imidation by heating efficiently, when baking a coating film.

The solid content concentration (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) in the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 0.5 to 15 It is mass %, More preferably, it is the range of 1-10 mass %.

The range of a particularly preferable solid content concentration differs according to the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of using the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s.

(liquid crystal alignment film/liquid crystal display element)

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. The liquid crystal alignment film of the present invention can be used for a liquid crystal alignment film of a horizontal alignment type or a vertical alignment type, but is particularly suitable for a liquid crystal display element of a vertical alignment type such as a VA type liquid crystal display element or a PSA type liquid crystal display element. The liquid crystal display element of this invention is equipped with the said liquid crystal aligning film. The liquid crystal display element of this invention can be manufactured by the method including the following process (1)-(3) or process (1)-(4), for example. In addition, the liquid crystal alignment film of the present invention is coated on a pair of substrates having a conductive film to form a coating film, the coating film is disposed facing each other through a layer of liquid crystal molecules to form a liquid crystal cell, and a liquid crystal cell is formed. It can be suitably used for a liquid crystal display element obtained by a manufacturing method of a liquid crystal display element in which light is irradiated to the liquid crystal cell in a state where a voltage is applied between the conductive films. More specifically, it is a PSA type liquid crystal display element described later or a liquid crystal display element for SC-PVA mode.

(1) Process of applying a liquid crystal aligning agent on a substrate

The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is formed, for example, by a suitable coating method such as a roll coater method, spin coat method, printing method, or inkjet method. Here, the substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate or a silicon nitride substrate. Further, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is used for only one substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.

(2) Process of firing the coating film

After application of the liquid crystal aligning agent, for the purpose of preventing the liquid sag of the applied alignment agent or the like, preheating (prebaking) is preferably performed first. The prebake temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C, and the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 ~ 5 minutes. And, in order to completely remove the solvent, it is preferable to additionally perform a heating (post-bake) process.

This post-baking temperature is preferably 80 to 300°C, more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

Although the coating film formed in the said process (1) can be used as a liquid crystal aligning film as it is, you may perform an orientation ability providing process about the coating film. Examples of the orientation ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and an optical alignment treatment in which polarized or non-polarized radiation is irradiated to the coating film, and the like. can

In the photo-alignment treatment, as the radiation applied to the coating film, 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. Further, when the radiation to be used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination thereof may be performed. In the case of irradiating unpolarized radiation, the irradiation direction is an oblique direction.

(3) Step of forming a liquid crystal layer

(3-1) In case of VA type liquid crystal display element

As mentioned above, two board|substrates on which the liquid crystal aligning film was formed are prepared, and a liquid crystal is arrange|positioned between two board|substrates arrange|positioned facing. Specifically, the following two methods are mentioned. The first method is a conventionally known method. First, the board|substrates of 2 sheets are opposingly arranged with a clearance gap (cell gap) so that each liquid crystal aligning film may oppose. Next, the peripheral portions of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected and filled into the substrate surface and the cell gap partitioned by the sealant to bring them into contact with the film surfaces, and then the injection holes are sealed.

In addition, the second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet light-curable sealing agent is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is dropped onto several predetermined points on the liquid crystal alignment film surface. Then, the other board|substrate is bonded together so that the liquid crystal aligning film may oppose, the liquid crystal composition is pressed and diffused to the whole surface of a board|substrate, and it is made to contact a film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing compound. In any case, it is preferable to further remove the flow alignment during liquid crystal charging by gradually cooling to room temperature after heating to a temperature at which the used liquid crystal composition assumes an isotropic phase.

(3-2) In the case of manufacturing a PSA type liquid crystal display element

Except for injecting or dropping the liquid crystal composition containing the polymerizable compound, it is the same as the above (3-1). As a polymeric compound, the polymeric compound represented by the said formula (M-1) - (M-7) is mentioned, for example.

(3-3) When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group (liquid crystal display element for SC-PVA mode)

After carrying out similarly to the said (3-1), you may employ|adopt the method of manufacturing a liquid crystal display element through the process of irradiating an ultraviolet-ray mentioned later. According to this method, a liquid crystal display element excellent in response speed can be obtained with a small light irradiation amount, similarly to the case of manufacturing the PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group represented by the above formulas (M-1) to (M-7) in a molecule, and the content thereof is It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components, More preferably, it is 1-20 mass parts. Moreover, the said polymeric group may have the polymer used for a liquid crystal aligning agent, and as such a polymer, the polymer obtained by using for reaction the diamine component containing the diamine which has the said photopolymerizable group at the terminal, for example is mentioned. can

(4) Step of irradiating ultraviolet rays

The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (3-2) or (3-3). The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Further, as the light to be irradiated, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, 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, an excimer laser, or the like can be used. As an irradiation amount of light, Preferably it is 1,000-200,000 J/m<2>, More preferably, it is 1,000-100,000 J/m<2>.

And a liquid crystal display element can be obtained by bonding a polarizing plate together to the outer surface of a liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between protective films of cellulose acetate or a polarizing plate made of the H film itself. there is.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used for various display devices, such as various monitors, liquid crystal televisions, and information displays.

[Example]

The present invention will be described in more detail by way of examples below, but the present invention is not limited thereto. The meaning of the symbol of the compound used in the Example is shown below.

(specific diamine)

DA-1 to DA-5: Compounds represented by the following formulas [DA-1] to [DA-5], respectively

[Formula 44]

(Tetracarboxylic acid component)

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

D3: benzene-1,2,4,5-tetracarboxylic acid anhydride

[Formula 45]

(additive component)

A-1: Compound represented by the following formula [A-1]

[Formula 46]

(triazine ring-containing polymer)

T-1: A compound having a repeating unit structure represented by the following formula [T-1]

T-2: A compound having a repeating unit structure represented by the following formula [T-2]

[Formula 47]

(menstruum)

NMP: N-methyl-2-pyrrolidone

BCS: ethylene glycol monobutyl ether

THF: tetrahydrofuran

DMAc: N,N-dimethylacetamide

(Molecular Weight Measurement of Polymer (A))

The molecular weight of the polymer (A) in the Synthesis Example was as follows using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex. was measured.

Column temperature: 50 ℃

Eluent: N,N-dimethylformamide (As an additive, lithium bromide monohydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) is 10 ml / ℓ)

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory.

(Synthesis of Polymer (A))

<Synthesis Example 1>

Tetracarboxylic dianhydride D2 (15.01 g), diamine component DA-1 (15.65 g, molar ratio 0.3 with respect to all diamine components), DA-2 (8.33 g, molar ratio 0.35 with respect to all diamine components), DA- 3 (5.95 g, molar ratio 0.2 with respect to all diamine components) and DA-4 (5.81 g, molar ratio 0.15 with respect to all diamine components) were mixed in an NMP solvent (203.00 g), and reacted at 60 ° C. for 3 hours , D1 (11.30 g), which is tetracarboxylic dianhydride, and NMP (44.24 g) were added and mixed, and a polyamic acid solution (A) was obtained by reacting at 40°C for 12 hours. The number average molecular weight of this polyamic acid polymer was 9,600, and the weight average molecular weight was 22,900.

<Synthesis Example 2>

tetracarboxylic dianhydride D1 (14.43 g), diamine component DA-2 (9.12 g, molar ratio 0.4 to total diamine components), DA-3 (8.36 g, molar ratio 0.3 to total diamine components), and DA -5 (14.16 g, molar ratio 0.3 to all diamine components) was mixed in NMP solvent (221.94 g), and after reacting at room temperature for 1 hour, tetracarboxylic dianhydride D3 (7.52 g) and NMP (81.79 g) g) was added and mixed, and polyamic acid solution (B) was obtained by making it react at room temperature for 12 hours. The number average molecular weight of this polyamic acid polymer was 10,800, and the weight average molecular weight was 32,500.

(Synthesis of Polymer (B))

<Preparation of triazine ring-containing polymer solution>

<Synthesis Example 3>

[Formula 48]

1,3-phenylenediamine [2] (42.22 g, 0.390 mol, manufactured by Amino-Chem) and DMAc (672.62 g, manufactured by Kanto Chemical Co., Ltd.) were added to a 1,000 ml four-necked flask, followed by nitrogen substitution, Stirring dissolved 1,3-phenylenediamine [2] in DMAc. After that, it was cooled to -10°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (60.00 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added. It injected|threw-in while confirming that the internal temperature would not become 0 degreeC or more. After stirring for 30 minutes, the temperature of the reaction solution was raised to an internal temperature of 85 ± 5 °C by setting an oil bath to 90 to 100 °C. After stirring at an internal temperature of 85°C for 1 hour, aniline [6] (18.18 g, 0.195 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-(4-aminophenyl)ethanol [3] (26.78 g, 0.195 mol, manufactured by Oakwood Co., Ltd.) It was added dropwise after dissolving in DMAc (42.93 g) beforehand, and stirred for 3 hours. Then, 2-aminoethanol (59.62 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, the temperature was lowered to room temperature, and stirring was stopped after stirring for 30 minutes. To the reaction solution, THF (369 g), ammonium acetate (415 g) and ion-exchanged water (415 g) were added, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separatory funnel, and the organic layer was recovered by dividing into an organic layer and an aqueous layer. The recovered organic layer was added dropwise to a mixture of methanol (461 g) and ion-exchanged water (1,845 g) to cause reprecipitation. The obtained precipitate was separated by filtration and dried at 120°C for 8 hours using a vacuum dryer to obtain 89.3 g of the target polymer compound [10] (hereinafter referred to as T-1). The measurement result of the ¹ H-NMR spectrum of compound T-1 is shown in FIG.

The weight average molecular weight Mw of compound T-1 measured in terms of polystyrene by GPC was 23,350, and the polydispersity Mw/Mn was 6.5.

The triazine ring-containing polymer (T-1) (5.00 g) and the NMP solvent (20.0 g) were stirred and dissolved at 40°C for 12 hours to obtain a triazine ring-containing polymer solution (C).

<Synthesis Example 4>

[Formula 49]

To a 1,000 mL four-necked flask, 1,3-phenylenediamine [2] (45.15 g, 0.418 mol) and DMAc (685.16 g) were added, nitrogen substitution was performed, followed by stirring to obtain 1,3-phenylenediamine [ 2] was dissolved in DMAc. After that, it was cooled to -10 ° C by an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (70.00 g, 0.380 mol) was prepared at an internal temperature of 0 ° C or higher. It was inserted while checking that this does not happen. After stirring for 30 minutes, the entire reaction vessel was transferred to an oil bath set at 90 to 110°C, and the reaction solution was heated up until the internal temperature reached 85 ± 5°C. After stirring for 1 hour, 3-aminophenol [3] (49.71 g, 0.456 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in DMAc (120.91 g) was added dropwise, and the mixture was stirred for 3 hours. Then, 2-aminoethanol (69.56 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and stirring was stopped after stirring for 30 minutes. To the reaction solution, THF (416 g), ammonium acetate (468.2 g) and ion-exchanged water (468.2 g) were added, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separatory funnel, and the organic layer was recovered by dividing into an organic layer and an aqueous layer. The recovered organic layer was added dropwise to a mixture of methanol (1,040 g) and ion-exchanged water (1,561 g) to cause reprecipitation. The obtained precipitate was separated by filtration and dried at 120°C for 8 hours using a vacuum dryer to obtain 95.1 g of the target polymer compound [5] (hereinafter referred to as T-2).

The weight average molecular weight Mw of compound T-2 measured in terms of polystyrene by GPC was 12,384, and the polydispersity Mw/Mn was 3.3. The measurement results of the ¹ H-NMR spectrum of compound T-2 are shown in FIG. 2 .

The triazine ring-containing polymer (T-2) (5.00 g) and the NMP solvent (20.0 g) were stirred and dissolved at 40°C for 12 hours to obtain a triazine ring-containing polymer solution (D).

<Preparation of liquid crystal aligning agent>

<Example 1>

To the polyamic acid solution (A) (1.8 g) obtained in Synthesis Example 1, the triazine ring-containing polymer solution (C) (4.2 g) obtained in Synthesis Example 3, and the additive [A-1] (0.12 g), NMP ( 3.88g) and BCS (10.0g) were added, and liquid crystal aligning agent [1] of Example 1 was obtained by stirring for 5 hours. Abnormality, such as muddiness and precipitation, was not looked at by this liquid crystal aligning agent, but it was confirmed that the resin component was melt|dissolving uniformly.

<Examples 2 to 6, Comparative Examples 1 and 2>

In Example 1, the liquid crystal orientation of Examples 2-6 liquid crystal aligning agent [2]-[6] and Comparative Examples 1 and 2 followed the method of Example 1 except having changed into the compounding quantity shown in following Table 1 [7] and [8] were obtained. Abnormality, such as muddiness and precipitation, was not looked at by these liquid crystal aligning agents, but it was confirmed that the resin component was dissolved uniformly.

(Measurement of refractive index)

After spin-coating the liquid crystal aligning agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above on a silicon substrate and firing on a hot plate at 70 ° C. for 90 seconds, firing in a 230 ° C. infrared heating furnace for 20 minutes It performed and produced the liquid crystal aligning agent coated Si substrate of 100 nm of film thickness.

Next, the refractive index was measured with M-2000 by J.A. Woram Japan Co., Ltd., and the refractive index at 550 nm was compared.

The refractive index measurement results in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2 below.

(measurement of transmittance)

The liquid crystal aligning agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were spin-coated on a quartz substrate, fired on a hot plate at 70 ° C. for 90 seconds, and then fired in a 230 ° C. infrared heating furnace for 20 minutes. It performed, and the liquid crystal aligning agent coating quartz substrate of 100 nm of film thickness was produced.

Next, the transmittance|permeability of the visible region (380 nm - 780 nm) was measured with UV-2600 by Shimadzu Corporation using the quartz substrate before liquid crystal aligning agent application|coating as a reference. Then, the average transmittance Y in the XYZ color system determined by CIE was calculated, and it was set as the luminous average transmittance.

The transmittance|permeability measurement results in Examples 1-6 and Comparative Examples 1 and 2 are shown in Table 2 below.

As shown in Table 2, it was confirmed that the refractive index was 1.64 or less in Comparative Examples 1 and 2, whereas the refractive index was as high as 1.66 or more in Examples 1 to 6. Further, in Examples 1 to 6, it was confirmed that the luminous average transmittance also showed a high transmittance of 95% or more while ensuring a high refractive index.

(Evaluation of voltage retention)

<Preparation of liquid crystal cell for voltage retention evaluation>

Glass substrates with ITO (30 mm in length, 40 mm in width, 0.7 mm in thickness) obtained by washing the liquid crystal aligning agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above with pure water and IPA (isopropyl alcohol), respectively. was spin-coated on the ITO surface, fired on a hot plate at 70°C for 90 seconds, and then fired in a 230°C infrared furnace for 20 minutes to prepare a polyimide-coated substrate having a film thickness of 100 nm.

After producing two liquid crystal aligning agent coated substrates by the above method and spreading a 4 µm bead spacer on the liquid crystal alignment film surface of one substrate, a thermosetting sealing agent (XN-1500T manufactured by Kyoritz Chemical Industries, Ltd.) was applied thereon. printed. Then, after making the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside and bonding together with the previous board|substrate, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-3023 (manufactured by Merck & Co., Ltd.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced-pressure injection method to prepare a liquid crystal cell. The voltage retention of this liquid crystal cell was measured.

Next, 10 J/cm<2> of UV which passed through the 325 nm cut-off filter from the outside of this liquid crystal cell was irradiated (it is also called the 1st PSA process) in the state which applied the DC voltage of 15V to this liquid crystal cell. In addition, UV illuminance was measured using ORC UV-MO3A.

After that, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A -1) for 30 minutes (referred to as the second PSA treatment). After that, the voltage retention was measured.

<Measurement of voltage retention>

Using the liquid crystal cell produced above, a voltage of 1 V was applied for 60 μs in a hot air circulation oven at 60 ° C., and then the voltage after 1667 msec was measured. ) was calculated as For the measurement of voltage retention, VHR-1 manufactured by Toyo Technica was used.

The measurement results of the voltage retention in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 3 below.

As shown in Table 3, in Examples 1 to 6, the VHR after the secondary PSA treatment was all around 90%, and it was confirmed that they were equivalent to those of the comparative examples.

It was confirmed that the liquid crystal elements of Examples 1 to 6 exhibited practically good voltage retention.

(Evaluation of pretilt angle)

<Production of liquid crystal cell for pretilt angle evaluation>

The liquid crystal aligning agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were washed with pure water and IPA (isopropyl alcohol), and ITO having a pixel size of 200 μm × 600 μm and a line/space of 3 μm, respectively An ITO electrode substrate on which an electrode pattern is formed (35 mm in length, 30 mm in width, 0.5 mm in thickness) and a glass substrate equipped with an ITO electrode on which a photo spacer with a height of 3.2 μm is patterned (35 mm in length, 30 mm in width, 0.7 mm in thickness) mm) on the ITO surface, respectively, fired on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared furnace at 230 ° C. for 20 minutes or 60 minutes to obtain a polyimide-coated substrate having a film thickness of 100 nm. produced.

In addition, the ITO electrode substrate on which this ITO electrode pattern is formed is divided into four parts in a cross checker (checkered pattern) shape, so that each of the four areas can be separately driven.

Two polyimide-coated substrates were produced by the above method, and a thermosetting sealing agent (XN-1500T manufactured by Kyoritz Chemical Industry Co., Ltd.) was printed thereon. Then, after making the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside and bonding together with the previous board|substrate, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-3023 (manufactured by Merck & Co., Ltd.) containing a polymerizable compound for PSA was injected into this empty cell by a reduced-pressure injection method to prepare a liquid crystal cell. The voltage retention of this liquid crystal cell was measured.

Next, 10 J/cm<2> of UV which passed through the 325 nm cut-off filter from the outside of this liquid crystal cell was irradiated (it is also called the 1st PSA process) in the state which applied the DC voltage of 15V to this liquid crystal cell. In addition, UV illuminance was measured using ORC UV-MO3A.

Then, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32/A -1) for 30 minutes (referred to as the second PSA treatment). After that, the pretilt angle was measured.

<Measurement of pretilt angle>

The pretilt angle of the liquid crystal cell for pretilt angle evaluation produced above was measured using the LCD analyzer (LCA-LUV42A by Meiryo Technica company). The pretilt angle obtained by subtracting the pretilt angle measured using a polyimide coated substrate fired for 60 minutes from the pretilt angle measured using a polyimide coated substrate fired in an infrared heating furnace at 230 ° C. for 20 minutes was used as the pretilt angle difference. .

The measurement results of the pretilt angles in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 4 below.

As shown in Table 4, it was confirmed that Examples 1 to 6 exhibit tilt angle characteristics equivalent to those of Comparative Examples 1 and 2, and exhibit good homeotropic orientation.

Claims (14)

The liquid crystal aligning agent characterized by containing the following (A) component and (B) component.
Component (A): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide product of the polyimide precursor (A)
Component (B): It has a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and is characterized in that at least a part of the triazine ring terminal is capped with an arylamino group having a crosslinking group. Polymer (B)

(R and R' represent, independently of each other, a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group,
Ar represents at least one selected from the group represented by formulas (2) to (12).)

(Arbitrary hydrogen atoms on the aromatic rings of formulas (2) to (12) may be substituted,
R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
W ¹ and W ² are each independently a single bond, -CR ⁹⁵ R ⁹⁶ - (R ⁹⁵ and R ⁹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (provided that they form a ring ), -C(=O)-, -O-, -S-, -S(=O)-, -SO ₂ -, or -NR ⁹⁷ - (R ⁹⁷ is represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)
X ¹ and X ² are, independently of each other, a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y ₁ -Ph-Y ₂ - (Ph represents a phenylene group, and any hydrogen atom on the phenylene group may be substituted; And, Y ₁ and Y ₂ independently represent a single bond or an alkylene group having 1 to 10 carbon atoms).) According to claim 1,
The liquid crystal aligning agent in which the arylamino group which has the crosslinking group of the said polymer (B) is represented by Formula (15).

(In the formula, R ¹⁵ represents a crosslinking group.) According to claim 1 or 2,
A liquid crystal aligning agent in which the crosslinking group of the polymer (B) is a hydroxy-containing group or a (meth)acryloyl-containing group. According to any one of claims 1 to 3,
The crosslinking group of the polymer (B) is a hydroxyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and the following formula (i-2) to The liquid crystal aligning agent which is 1 or more types chosen from group represented by Formula (i-3).

According to any one of claims 1 to 4,
Furthermore, the liquid crystal aligning agent in which a part of the triazine ring terminal of the said polymer (B) is capped by the unsubstituted arylamino group. According to any one of claims 1 to 5,
The liquid crystal aligning agent obtained using the diamine component containing the diamine (a) which the said polymer (A) has at least 1 sort(s) chosen from the group which consists of structures represented by following formula (S1) - (S3).

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -COO-, -OCO- or -((CH ₂ ) _a1 -A ₁ ) _m1 - (a1 is an integer from 1 to 15, A ₁ represents an oxygen atom or -COO- , m ₁ is an integer of 1 to 2. When m ₁ is 2, a plurality of a1 and A ₁ each independently have the above definition.) G ¹ and G ² are each independently a carbon number represents a divalent cyclic group selected from a divalent aromatic group of 6 to 12 and a divalent alicyclic group of 3 to 8 carbon atoms, and any hydrogen atom on the cyclic group is an alkyl group of 1 to 3 carbon atoms or a divalent alicyclic group of 1 to 3 carbon atoms; It may be substituted with an alkoxy group, an alkyl group containing a fluorine atom of 1 to 3 carbon atoms, an alkoxy group containing a fluorine atom of 1 to 3 carbon atoms, or a fluorine atom. m and n are each independently an integer of 0 to 3, and m+n is 1 to 6 R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ¹ may be substituted with a fluorine atom.)

(X ³ represents a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.)

(X ⁴ represents -CONH-, -NHCO-, -O-, -CH ₂ O-, -COO- or -OCO-. R ³ represents a structure having a steroid skeleton.) According to any one of claims 1 to 6,
A liquid crystal aligning agent in which the diamine (a) is diamine represented by the following formula (d1) or formula (d2).

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m - O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m represents a divalent organic group of -OCO- m is an integer of 1 to 8. Y is the formula (S1 ) to (S3). In the formula (d2), two Ys may be the same or different.) According to any one of claims 1 to 7,
The liquid crystal aligning agent obtained using the tetracarboxylic acid component in which the said polymer (A) contains tetracarboxylic dianhydride represented by following formula (S4) or its derivative(s).

(X represents a structure selected from the group consisting of (x-1) to (x-13) below.)

(R ¹ to R ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. R ⁵ and R ⁶ represents a hydrogen atom or a methyl group, j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, -O-, -CO-, -COO-, phenylene; Represents a sulfonyl or amide bond. *1 is a binding hand binding to one acid anhydride group, and *2 is a binding hand binding to the other acid anhydride group.) According to claim 8,
The tetracarboxylic dianhydride or derivative thereof represented by the formula (S4) is a tetracarboxylic acid in which X is the formula (x-1) to (x-7) or (x-11) to (x-13) The liquid crystal aligning agent which is dianhydride or its derivative(s). According to any one of claims 1 to 9,
The liquid crystal aligning agent whose content ratio of said (A) component and (B) component is 10/90 - 90/10 in mass ratio of [component (A)]/[component (B)]. The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-10. A liquid crystal display element provided with the liquid crystal aligning film of Claim 11. The manufacturing method of a liquid crystal display element including the process of apply|coating the liquid crystal aligning agent in any one of Claims 1-10 on a board|substrate. According to claim 13,
A liquid crystal cell by applying the liquid crystal aligning agent according to any one of claims 1 to 10 on a pair of substrates having a conductive film to form a coating film, and arranging the coating film to face each other through a layer of liquid crystal molecules, and irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates.

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