JPWO2018124165A1 - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent containing the following components (A), (B) and (C): (A) polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, polyester, polyamide, and polymerizability At least one polymer selected from the group consisting of polymers of monomers having unsaturated bonds; (B) at least one compound selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols; And (C) an organic solvent. The liquid crystal aligning agent by this invention has favorable adhesiveness, even if low-temperature baking is performed, and can provide the liquid crystal aligning film obtained from this liquid crystal aligning agent. [Selection figure] None

Description

  The present invention relates to a liquid crystal aligning agent that exhibits good adhesion even when subjected to low-temperature firing, and a liquid crystal aligning film obtained from the liquid crystal aligning agent.

A flexible liquid crystal display element using a flexible resin film as a substrate has various advantages such as being thin and lightweight, or being foldable for storage and movement. Suitable for viewing content.
However, since the resin film has poor heat resistance, a low-temperature process for producing individual elements constituting the liquid crystal display element, for example, a liquid crystal alignment film has been proposed, and accordingly, a liquid crystal alignment film material capable of low-temperature baking is required. (International Publication WO2012 / 121259 (Patent Document 1)).
In addition, since the resin film is generally weaker to external impacts than the glass substrate, it is required that the adhesion between the alignment film and the resin film substrate is high.

  As a result of investigations by a liquid crystal aligning agent including a conventional crosslinking agent by the present inventors, it has been found that the adhesion of a liquid crystal aligning film obtained by low-temperature firing is significantly reduced. For this reason, development of the liquid crystal aligning agent and liquid crystal aligning film from which adhesiveness becomes favorable even if low-temperature baking is performed is desired.

  A composition suitable for forming a cured film having liquid crystal alignment is reported in, for example, International Publication No. WO2015 / 129890 (Patent Document 2). A liquid crystal alignment film containing polycarbonate as an essential component is disclosed, for example, in JP-A-11-119225 (Patent Document 3). However, these are not sufficient for the purpose of providing a liquid crystal aligning agent that exhibits good adhesion even when subjected to low-temperature firing.

International Publication WO2012 / 121259 Pamphlet International Publication WO2015 / 129890 Pamphlet JP 11-119225 A

  When the present inventors examined with the liquid crystal aligning agent containing the conventional crosslinking agent, it turned out that adhesiveness falls remarkably by the liquid crystal aligning film obtained by low-temperature baking. Then, an object of this invention is to provide the liquid crystal aligning agent and liquid crystal aligning film which become favorable adhesiveness even if low temperature baking is performed.

The present inventors have found an invention having the following <1>.
<1> (A) At least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, polyester, polyamide, and a polymer of monomers having a polymerizable unsaturated bond;
(B) At least one compound selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol; and (C) a liquid crystal aligning agent containing an organic solvent.

  According to the present invention, it is possible to provide a liquid crystal aligning agent and a liquid crystal alignment film that have good adhesion even when low-temperature firing is performed. The liquid crystal display element using the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can be used suitably for the display element of various liquid crystal modes. These elements are also useful in liquid crystal displays for display purposes, and in light control windows and optical shutters for controlling transmission and blocking of light.

The liquid crystal aligning agent of this invention is a liquid crystal aligning agent characterized by containing above-described (A) component, (B) component, and (C) component.
Hereinafter, each constituent requirement of the present invention will be described in detail.

<(A) component: specific polymer>
The specific polymer of the component (A) in the present invention, as described above, is a group consisting of a polymer of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, polyester, polyamide, and a monomer having a polymerizable unsaturated bond. It is at least one polymer selected from the above.

[Polyamic acid]
The polyamic acid used in the present invention can be obtained by reacting a diamine compound with tetracarboxylic dianhydride.

<Diamine>
The diamine used for the polymerization of the polyamic acid of the present invention can be generalized by the following formula (1).

A1 and A2 in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms; ₁ is a divalent organic group. From the viewpoint of liquid crystal alignment, A1 and A2 are preferably a hydrogen atom or a methyl group.

  As a preferred embodiment of the formula (1), a diamine of the following formula (DA-1) is used as the diamine.

In the above formula (DA-1), _Yd is a divalent organic group represented by the following formulas (Y-1) to (Y-171).

In formula (Y-87), X ¹ is a sulfur atom, an oxygen atom or —NH—, R ⁸ and R ⁹ are each independently a divalent organic group, and at least of R ⁸ and R ⁹ One has an aromatic ring, and at least one bond in “—CO—X ¹ —” is bonded to the aromatic ring, preferably described in paragraphs [0047] to [0048] of JP-A-2015-135464. This is a group obtained by removing two amino groups from the compounds corresponding to formulas (b-1) to (b-42).

In the formula (Y-139), R 1 and R 2 are each an ethylene group, —COO—, —OCO—, —NHCO—, —N (CH ₃ ) CO—.

  In said formula, n is an integer of 1-6.

  One preferred embodiment of the diamine that can be used in the present invention is a diamine having an alkyl group or a fluorine-containing alkyl group in the side chain represented by the following formula [Sd-1] to [Sd-4]. .

Wherein, ^{A 1} each independently represent an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms having 1 to 22 carbon atoms.

  As another preferred embodiment of the diamine that can be used in the present invention, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4′-diaminobiphenyl-3, 3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4 ' -Dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4 ' -Diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether , 3'-dicarboxylic acid, a diamine having a structure shown by the formula [4a-1] ~ [4a-6] below. The diamine is preferable in terms of accelerating the curing rate of the liquid crystal alignment film, and more preferably used in combination with a diamine that imparts vertical alignment described later. These diamines are preferably at least 10 mol%, more preferably at least 20 mol%, based on the total diamine component used in the liquid crystal aligning agent.

  As another preferred embodiment of the diamine that can be used in the present invention, the following formulas [2a-1] to [2a-9] (wherein n independently represents an integer of 2 to 12). The diamine shown by this is mentioned.

  Another preferred embodiment of the diamine that can be used in the present invention includes a diamine having a heterocyclic ring represented by the following formula (bs).

In the above formula [bs],
X ₁ is at least one divalent organic group selected from the group consisting of —O—, —NQ 1 —, —CONQ 1 —, —NQ 1 CO—, —CH ₂ O—, and —OCO—, and Q 1 is A hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
X ₂ represents a single bond or at least one divalent organic group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. And
X ₃ represents a single bond, or —O—, —NQ 2 —, —CONQ 2 —, —NQ 2 CO—, —COO—, —OCO—, and —O (CH ₂ ) m — (m is an integer of 1 to 5). At least one divalent organic group selected from the group consisting of:
Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
X ₄ is a nitrogen-containing aromatic heterocycle, and n is an integer of 1 to 4, preferably a combination described in Tables 1 to 3 in paragraphs [0036] to [0038] of International Publication WO2009 / 093707 It is.

  Another preferred embodiment of the diamine that can be used in the present invention is a diamine having a photoreactive group represented by the following formula (PV-0).

In the above formula (PV-0), X ² represents a substituent, and is a group having a structure represented by the following formula (2A) or the following formula (2B).

In the above formula (2A) and the above formula (2B), R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (however, any hydrogen atom may be substituted with a fluorine atom), or An alkoxy group having 1 to 18 carbon atoms (however, an arbitrary hydrogen atom may be substituted with a fluorine atom). A and B each independently represent a single bond or any one of the ring structures represented by the following formulae. However, any hydrogen atom in the ring structure may be substituted with an alkoxy group having 1 to 10 carbon atoms. T ^{1 to} T ⁴ each independently represents a single bond, an ether, an ester, an amide, or a ketone bond. S represents a single bond or an alkylene group having 1 to 10 carbon atoms.

  In the case of imparting the vertical alignment property, the diamine that can be used in the present invention is represented by the formulas [2-1] to [2-31] described in paragraphs [0033] to [0042] of International Publication WO2013 / 125595. The diamines shown can be exemplified, and these diamines are preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 20 mol% or more with respect to the entire diamine component. preferable. From the viewpoint of increasing the curing rate, 90 mol% or less is preferable, and 80 mol% or less is more preferable. More preferable diamine is at least one selected from the following formulas [2a-24] to [2a-33].

In Formula (2a-32), when R ¹ is ortho to one of the amino groups, each R ¹ is independently —O—, —OCH ₂ —, —CH ₂ O—, or —COOCH _2. When at least one linking group selected from — and —CH ₂ OCO— is present and is meta-positioned to two amino groups, R ¹ represents —CONH—, —, in addition to the linking group shown above. At least one linking group selected from NHCO— and —CH ₂ —, wherein each R ² independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, or 1 to 22 carbon atoms; A linear or branched alkoxy group is shown, and Cy is a group selected from a 4,4′-biphenyldiyl group, a 4,4′-phenylcyclohexyl group, and a 4,4′-dicyclohexyl group.

In the above formula, R ₃ represents —O— or —CH ₂ O—, Cy ₂ has the same meaning as Cy, and R ⁷ each independently represents a linear or branched group having 3 to 12 carbon atoms. The cis-trans isomerism of 1,4-cyclohexylene indicates the trans isomer.

  In addition to the diamines listed above, 4- (2- (methylamino) ethyl) aniline or a diamine described in JP 2010-97188 A can be used.

  Among the photoreactive diamines, the following compounds are preferable from the viewpoint of photoreactivity and the like.

In the C _n H _{2n + 1} portion of the particularly preferred diamine compound exemplified in the above formulas, n represents an integer of 0 to 18.

<Tetracarboxylic dianhydride>
Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. Specific examples thereof include the following groups [1] to [5].

[1] Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride;

[2] As alicyclic tetracarboxylic dianhydride, for example, acid dianhydrides such as the following formulas (X1-1) to (X1-13),

(In the formulas (X1-1) to (X1-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, which may be the same or different;
In the above formula, R _M represents a hydrogen atom or a methyl group,
Xa is a tetravalent organic group represented by the following formulas (Xa-1) to (Xa-7));

[3] 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′ , 5′-dione), 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02]. , 6] undecane-3,5,8,10-tetraone, etc .;

[4] As aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid dianhydrides, acid dianhydrides represented by the following formulas (Xb-1) to (Xb-10), and the like, and

[5] Furthermore, acid dianhydrides represented by the formulas (X1-44) to (X1-52) and tetracarboxylic dianhydrides described in JP 2010-97188 A can be exemplified.

  In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

<Method for producing polyamic acid>
The polyamic acid used in the present invention can be synthesized by a known method (for example, see International Publication WO2014 / 034792).

  The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. It may be used. The concentration of the polymer is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight body is easily obtained.

[Polyamic acid ester]
The polyamic acid ester used in the present invention can be obtained as follows.

<Method for producing polyamic acid ester>
The polyamic acid ester used in the present invention is (1) synthesized from a polyamic acid, (2) synthesized a polyamic acid ester from a tetracarboxylic acid diester and a diamine, or (3) a tetracarboxylic acid diester dichloride and a diamine. In the case of synthesis by reaction, it can be synthesized by any known method (for example, see International Publication WO2014 / 034792).

The tetracarboxylic acid diester has the following reaction formula (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms, and A is a tetravalent organic group derived from the tetracarboxylic dianhydride). Can be produced by a known method of reacting the tetracarboxylic dianhydride with an alcohol having 1 to 5 carbon atoms represented by R ¹ OH (see, for example, International Publication No. 2010/092989). it can.

  The tetracarboxylic acid diester of the present invention is preferably a compound represented by [5-p-1] from the viewpoint of obtaining a high molecular weight and low-dispersion polyamic acid ester.

  Tetracarboxylic acid diester dichloride can be produced, for example, by a known method of chlorinating the tetracarboxylic acid dialkyl ester (see, for example, International Publication No. WO2010 / 092989).

  From the viewpoint of obtaining a high molecular weight and low-dispersion polyamic acid ester, tetracarboxylic acid diester dichloride is represented by the formula [5-Cl] (in the above formula (5-Cl), A is the same as A in the formula (5). Is preferred).

  The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the polyamic acid ester, and these may be used alone or in combination. The polymer concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body is easily obtained.

Among the methods for synthesizing the three polyamic acid esters, since a high molecular weight polyamic acid ester is obtained, the method (2) or the method (3) is particularly preferable.
[Polyimide]
The polyimide used in the present invention can be obtained by a known method (for example, see International Publication WO2013 / 125595).

  The polyimide may be a complete imidized product obtained by dehydrating and ring-closing all of the amic acid structure that the polyamic acid had or the amic acid ester structure that the polyamic acid ester had, and it may have an amic acid or amic acid ester structure. It may be a partially imidized product in which only a part is dehydrated and closed and an amic acid structure or an amic acid ester structure and an imide ring structure coexist. The polyimide to be used preferably has an imidization ratio of 20% or more, and is preferably 90% or less, and more preferably 60% or less, from the viewpoint of ensuring solubility in a solvent. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of amic acid structures or amic acid ester structures of polyimide and the number of imide ring structures, expressed as a percentage. Here, a part of the imide ring may be an isoimide ring.

<Polyorganosiloxane>
The polyorganosiloxane according to the present invention can be obtained, for example, by a known method (for example, see International Publication No. WO2009 / 025386) in which a hydrolyzable silane compound is hydrolyzed and condensed.

  Examples of silane compounds used for the synthesis of polyorganosiloxane include alkoxysilane compounds such as tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane; 3-mercaptopropyltriethoxy Nitrogen / sulfur-containing alkoxysilane compounds such as silane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3- Epoxy group-containing silane compounds such as glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane ; Unsaturated silane-containing alkoxysilanes such as 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane Compound; trimethoxysilylpropyl succinic anhydride and the like. One of these hydrolyzable silane compounds can be used alone or in combination of two or more. Note that “(meth) acryloxy” means “acryloxy” and “methacryloxy”.

  Regarding the polyorganosiloxane of the present invention, the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably in the range of 100 to 50,000, and more preferably in the range of 200 to 10,000.

  In the polyorganosiloxane of the present invention, a polyorganosiloxane having a repeating unit represented by the following formula (P-Si-Ep) is preferable.

(In the formula (P-Si-Ep), X ¹ is an epoxy containing the following formula (X ¹ -1) or (X ¹ -2) (in the above formula, "*" represents a bond). Y ¹ is a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.)

  In the polyorganosiloxane of the present invention, it is desirable that the following cinnamic acid derivative (Cn-1) or (Cn-2) is used as the carboxylic acid having a liquid crystal aligning group from the viewpoint of the effects of the present invention.

<Polyester>
The polyester used in the present invention can be obtained, for example, by reacting a dicarboxylic acid with a diepoxy compound. Here, as the diepoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Examples include diepoxy compounds described in JP2013-113937A.

  The use ratio of the diepoxy compound and dicarboxylic acid compound used in the polyester synthesis reaction is preferably 0.2 to 2 equivalents of the epoxy group of the diepoxy compound with respect to 1 equivalent of the carboxy group contained in the dicarboxylic acid compound. .3 equivalents to 1.2 equivalents are more preferred.

  The reaction between the dicarboxylic acid and the diepoxy compound is preferably performed in the presence of an organic solvent. Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, Examples include aprotic polar solvents such as hexamethylphosphoric triamide; phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol.

  Thus, a solution containing the polyester as the polymer (A) can be obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyester contained in the reaction solution, or after the isolated polyester is purified. It may be used for the preparation of a liquid crystal aligning agent. Isolation and purification of the polyester can be performed according to a known method.

  The polyester obtained as described above has a polystyrene-equivalent number average molecular weight (Mn) measured by GPC, which improves the liquid crystal alignment of the liquid crystal alignment film to be formed and the stability of the liquid crystal alignment over time. From the standpoint of ensuring, it is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Polyamide>
The polyamide used in the present invention can be obtained by, for example, a method of reacting dicarboxylic acid and diamine. Here, the dicarboxylic acid is preferably subjected to a reaction with a diamine after acid chloride using an appropriate chlorinating agent such as thionyl chloride.

  Although it does not restrict | limit especially as dicarboxylic acid used for the synthesis | combination of polyamide, For example, aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid; cyclobutane dicarboxylic acid, cyclohexane Dicarboxylic acid having an alicyclic structure such as dicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-carbonyl And dicarboxylic acids having an aromatic ring such as dibenzoic acid, 4-carboxycinnamic acid and p-phenylenediacrylic acid. In addition, dicarboxylic acid can be used individually by 1 type or in combination of 2 or more types.

  As the diamine used when synthesizing the polyamide of the present invention, the diamine used for the polyimide precursor is used at least in part to obtain a polyamide. In the synthesis, other diamines may be used in combination as necessary. A diamine can be used individually by 1 type or in combination of 2 or more types.

The ratio of the dicarboxylic acid and diamine used in the polyamide synthesis reaction is preferably such that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine. The reaction between a dicarboxylic acid (preferably an acid-chloride dicarboxylic acid) and a diamine is preferably carried out in an organic solvent in the presence of a base. As the organic solvent, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used. The amount of the organic solvent used is preferably 400 to 900 parts by weight with respect to 100 parts by weight of the total amount of dicarboxylic acid and diamine. As the base used in the above reaction, for example, tertiary amines such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine can be preferably used. It is preferable that the usage-amount of a base shall be 2-4 mol with respect to 1 mol of diamines.
As described above, a reaction solution obtained by dissolving polyamide is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamide contained in the reaction solution.

  About the polyamide of this invention, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC becomes like this. Preferably it is 1,000-500,000, More preferably, it is 5,000-300,000.

<Polymer polymer having a polymerizable unsaturated bond>
In the polymer of a monomer having a polymerizable unsaturated bond (hereinafter also referred to as “polymer (PAc)”), examples of the polymerizable unsaturated bond possessed by the monomer include (meth) acryloyl group, vinyl group, and styryl group. And a maleimide group. Specific examples of such a monomer having a polymerizable unsaturated bond include, for example, (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, vinyl benzoic acid and other unsaturated carboxylic acids: (meth) acrylic acid Alkyl (meth) acrylate cycloalkyl, benzyl (meth) acrylate, 2-methylhexyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic Unsaturated carboxylic acid esters such as glycidyl acid, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4-hydroxybutyl glycidyl acrylate: (Meth) acrylic compounds such as saturated polycarboxylic acid anhydrides; Aromatic vinyl compounds such as len, methylstyrene and divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like And a maleimide group-containing compound. In addition, the monomer which has a polymerizable group unsaturated bond can be used individually by 1 type or in combination of 2 or more types.

  Among the above, the polymer (PAc) is preferably a monomer polymer containing a (meth) acrylic compound from the viewpoints of transparency and material strength. In the synthesis of the polymer (PAc), the proportion of the (meth) acrylic compound used is preferably 50 mol% or more, preferably 60 mol% or more, based on the total amount of monomers used for the synthesis. More preferably, it is more preferably 70 mol or more.

  In the case of producing a vertical alignment type liquid crystal display element, a monomer having photoreactivity represented by the structure of the following formula (3m) -1 may be used.

In the formula (3m) -1, Mc represents a polymerizable unsaturated bond such as (meth) acryloyl, vinyl group, styryl group, maleimide group,
Sb is a linear or branched alkylene group having 1 to 10 carbon atoms, a divalent aromatic group or a divalent alicyclic group,
Md is a single bond, divalent heterocycle, trivalent heterocycle, tetravalent heterocycle, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, divalent aromatic group, trivalent Aromatic group, tetravalent aromatic ring, divalent alicyclic group, trivalent alicyclic group, tetravalent alicyclic group, divalent condensed cyclic group, trivalent condensed cyclic group Or a tetravalent fused cyclic group, each group is unsubstituted or one or more hydrogen atoms may be substituted by a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group,
d is an integer of 1 to 3, and Z is an oxygen atom or a sulfur atom.
Xa and Xb are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms,
R ₁ is a single bond, an oxygen atom, —COO— or —OCO—, preferably a single bond, —COO— or —OCO—;
R ₂ is a divalent aromatic group, divalent alicyclic group, divalent heterocyclic group or divalent condensed cyclic group, and R ₃ is a single bond, oxygen atom, —COO— or —OCO. −
R ₄ is a monovalent organic group having 3 to 40 carbon atoms including a linear or branched alkyl group having 1 to 40 carbon atoms or an alicyclic group,
R ₅ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom,
a is an integer of 0 to 3, and b is an integer of 0 to 4.

  Examples of the monomer represented by the formula (3m) -1 include, but are not limited to, the following.

  The proportion of the photoreactive monomer used is preferably 10 to 95 mol, more preferably 10 to 90 mol%, still more preferably 20 to 70 mol based on the total amount of monomers used for synthesis. %.

  The polymer (PAc) can be obtained, for example, by polymerizing a monomer having a polymerizable group unsaturated bond in the presence of a polymerization initiator. Examples of the polymerization initiator used include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2). , 4-dimethylvaleronitrile) and the like are preferred. It is preferable that the usage-amount of a polymerization initiator shall be 0.01-30 mass parts with respect to 100 mass parts of all the monomers used for reaction. The polymerization reaction is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds, and the like, and diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, and the like are preferable. The amount (a) of the organic solvent used is such that the total amount (b) of the monomers used in the reaction is 0.1 to 60% by mass with respect to the total amount (a + b) of the reaction solution. Is preferred.

  According to the preferable aspect of this invention, (A) component is at least 1 type of polymer chosen from the group which consists of a polymer of the monomer which has a polyimide, a polyamic acid, a polyamic acid ester, and a polymerizable unsaturated bond.

According to a more preferred embodiment of the present invention, the component (A) comprises at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dichloride, and a diamine. It is a polymer obtained by making these react. At this time, the tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dichloride are preferably the aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic It is preferable to include at least one structure selected from the group consisting of acid dianhydrides and their tetracarboxylic acid diesters and tetracarboxylic acid diester dichlorides.
More preferably, it includes a structure having at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, and a benzene ring structure. Specifically, from the viewpoint of the solubility of polyamic acid, polyamic acid ester, and polyimide obtained by imidizing them in a solvent, the above formulas (X1-1) to (X1-3), (X1-6) -(X1-12), (Xa-1)-(Xa-2), pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, (Xb-6)-(Xb- 8), (X1-44), (X1-47) to (X1-52) are preferred, more preferably (X1-1) to (X1-3), (X1-6) to (X1-12), (Xa-1) to (Xa-2), (Xb-6) to (Xb-8), (X1-44), and (X1-49).

  As a more preferable form of the tetracarboxylic acid derivative, compounds represented by the following formulas (X1-1-1) to (X1-1-6),

  Compounds represented by the above formulas (X1-6) to (X1-9), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride In particular, it contains at least one compound (T) selected from the group consisting of compounds, pyromellitic anhydride, compounds represented by (Xb-6), and tetracarboxylic acid diesters and tetracarboxylic acid diester dichlorides thereof. preferable.

  The amount of these preferred compounds (T) used (the total amount when two or more are used) is 10 mol% with respect to the total amount of tetracarboxylic dianhydride and its derivative used for the synthesis of polyamic acid. Preferably, the content is 20 mol% or more, and more preferably 30 mol% or more.

  The molecular weight of the polyamic acid, polyamic acid ester and polyimide described in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and even more preferably 10, in terms of weight average molecular weight. 000-100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

<< Amount of component (A) >>
The component (A) may be 1 to 15% by weight, preferably 1 to 8% by weight, and more preferably 1.5 to 7% by weight when the total amount of the liquid crystal aligning agent is 100% by weight.

<(B) component>
As described above, the component (B) in the present invention is at least one compound selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

  As the polyether polyol used as the component (B) of the present invention, for example, ethylene oxide, propylene oxide, ethylene oxide and propylene oxide obtained by using ethylene glycol, propylene glycol, glycerin, pentaerythritol and the like as an initiator. Examples thereof include a mixture and a ring-opening polymer such as tetrahydrofuran.

  The polyester polyol used as the component (B) of the present invention is an ester formation such as polyhydric alcohol and polycarboxylic acid having an amount less than the stoichiometric amount of the polyhydric alcohol or its ester, anhydride, halide, etc. Examples thereof include those obtained by direct esterification reaction and / or transesterification reaction with a functional derivative.

  Examples of the polyhydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1,3-propane. Diol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2 -Methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol Aliphatic diols such as triethylene glycol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; 3 such as trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, pentaerythritol, and tetramethylolpropane Mention may be made of alcohols having a higher value.

  Examples of the polyvalent carboxylic acid or its ester-forming derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid. Acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarbo Cycloaliphatic dicarboxylic acids such as acid, 1,4-dicarboxylic methylenecyclohexane, nadic acid, methyl nadic acid; polycarboxylic acids such as trimellitic acid, trimesic acid, trimer of castor oil fatty acid, etc .; these Polyhydric carboxylic acid anhydrides, halides such as chlorides and bromides of the polycarboxylic acids, methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, amyl esters, etc. of the polyvalent carboxylic acids Lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

  Examples of the polycarbonate polyol used as the component (B) in the present invention include compounds obtained by polycondensation reaction between a normal polyol component and a carbonylating agent. Examples of the polyol component include diols and polyhydric alcohols such as trivalent or higher alcohols. Examples of the diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, , 9-nonanediol, 1,10-decanediol and the like linear diols; 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1 , 6-hexanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4 -Branched diols such as trimethyl-1,3-pentanediol and 2-ethyl-1,3-hexanediol; 1,3-cyclohexanediol, 1,4 Examples include alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol; aromatic diols such as p-xylenediol and p-tetrachloroxylenediol; ether diols such as diethylene glycol and dipropylene glycol. These diols can be used alone or in combination of two or more. Examples of the trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, trimethylolpropane dimer, pentaerythritol, and the like.

  As the carbonylating agent, those known per se can be used, and specific examples thereof include alkylene carbonate, dialkyl carbonate, diallyl carbonate, phosgene and the like. It can be used in combination of more than one species.

  Examples of the polycaprolactone polyol used as the component (B) of the present invention include ring-opening polymerization products of caprolactone such as polycaprolactone diol.

  According to the preferable aspect of this invention, the number average molecular weight of the compound of (B) component is 300-10,000, Preferably it is 300-6000, More preferably, it is 300-4000, More preferably, it is 300. ~ 3000, most preferably 300-2000.

  According to a preferred embodiment of the present invention, the component (B) is at least one compound selected from the group consisting of compounds represented by the following formula (CL). By being following formula (CL), the liquid crystal aligning film excellent in adhesiveness and liquid crystal aligning property can be formed also at the time of low-temperature baking.

[Where:
Each R is independently a divalent aliphatic hydrocarbon group or a hydrocarbon group having a divalent alicyclic structure;
k is a number determined such that the number average molecular weight of the compound of the formula (CL) is 300 to 10,000. ]

  More preferably, the value of k is a number determined such that the number average molecular weight of the compound of formula (CL) is 300 to 6000, more preferably a number determined so as to be 300 to 4000, 300 -3000 is more preferable. Most preferably, it is 300-2000. In addition, the number average molecular weight of (CL) is a polystyrene equivalent number average molecular weight measured by a gel permeation chromatography (GPC) method.

R preferably has 1 to 12 carbon atoms, for example, — (CH ₂ ) m—, —CH ₂ CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH _2. A divalent aliphatic hydrocarbon group such as —, —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ —, etc., and a hydrocarbon group having a divalent alicyclic structure represented by the following formula (a), etc. Etc. However, m is 3-12 and 5-9 are preferable.

(In the above formula (a), R 'is a single bond or an alkanediyl group having 1 to 3 carbon atoms.)

Examples of the alkanediyl group as R ′ in the above formula (a) include —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, —CH ₂ —CH (CH ₃ ) —. .

Preferable specific examples of R include — (CH ₂ ) ₆ —, — (CH ₂ ) ₉ —, —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ — and the like. Two or more types of R may be contained in one molecule of the compound represented by the formula (CL).

Among them, as the polycarbonate diol represented by the above formula (CL),
In the formula (CL), compounds wherein R is — (CH ₂ ) ₆ — and the number average molecular weight is 2000,
In the formula (CL), R is a compound in which — (CH ₂ ) ₅ — and — (CH ₂ ) ₆ — are in a molar ratio of 1: 1, and the number average molecular weight is 500,
In the formula (CL), a compound in which R is — (CH ₂ ) ₅ — and — (CH ₂ ) ₆ — in a molar ratio of 1: 1 and a number average molecular weight of 2000,
In the formula (CL), a compound in which R is — (CH ₂ ) ₃ — and —CH ₂ CH (CH ₃ ) CH ₂ — in a molar ratio of 1: 1 and a number average molecular weight of 2000,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₃ — and —CH ₂ CH (CH ₃ ) CH ₂ — in a molar ratio of 1: 1, and the number average molecular weight is 800,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₆ — and the number average molecular weight is 500,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₆ — and the number average molecular weight is 1000,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₆ — and the number average molecular weight is 2000,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₆ — and the number average molecular weight is 3000,
In the formula (CL), a compound in which R is — (CH ₂ ) ₆ — and — ((CH ₂ ) ₅ CO ₂ ) m (CH ₂ ) 6 —1 in a molar ratio, and the number average molecular weight is 2000,
In the formula (CL), a compound in which R is — (CH ₂ ) ₆ — and — ((CH ₂ ) ₅ CO ₂ ) m (CH ₂ ) 6 —1 in a molar ratio, and the number average molecular weight is 1000,
In the formula (CL), R is a compound wherein R ′ is —CH ₂ — in the formula (a) and the number average molecular weight is 1000,
In the formula (CL), a compound in which R is the structure in which R ′ is —CH ₂ — in the formula (a) and — (CH 2) 6 — is 1: 1 in terms of a molar ratio, and the number average molecular weight is 900,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₉ — and —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ — in a molar ratio of 65:35, and the number average molecular weight is 1000,
In formula (CL), R is — (CH ₂ ) ₉ — and —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ — in a molar ratio of 65:35 and a number average molecular weight of 2000,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₉ — and —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ — in a molar ratio of 15:85, and the number average molecular weight is 1000,
In the formula (CL), compounds wherein R is — (CH ₂ ) ₉ — and —CH ₂ C (CH ₃ ) H (CH ₂ ) ₆ — in a molar ratio of 15:85, and the number average molecular weight is 2000,
In the formula (CL), compounds wherein R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — are in a molar ratio of 9: 1, and the number average molecular weight is 500,
In the formula (CL), compounds wherein R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — are in a molar ratio of 9: 1 and the number average molecular weight is 1000,
In the formula (CL), R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 9: 1, a compound having a number average molecular weight of 2000,
In the formula (CL), R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 9: 1, a compound having a number average molecular weight of 3000,
In the formula (CL), R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 9: 1, a compound having a number average molecular weight of 4000,
In the formula (CL), R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 9: 1, a compound having a number average molecular weight of 5000,
In the formula (CL), R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 1: 1, a compound having a number average molecular weight of 1000, and In the formula (CL), a compound in which R is —CH ₂ CH ₂ C (CH ₃ ) HCH ₂ CH ₂ — and — (CH ₂ ) ₆ — in a molar ratio of 1: 1 and a number average molecular weight of 2000 is preferable. .

<< Amount of component (B) >>
In the liquid crystal aligning agent of the present application, the blending amount of component (B) (the total amount when blending two or more components) is 0.5 to 50 parts by weight, preferably 100 parts by weight of component (A), preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight.

<(C) component: organic solvent>
The liquid crystal aligning agent of this application contains an organic solvent as (C) component.
An organic solvent will not be specifically limited if it has the characteristic to melt | dissolve the above-mentioned (A) component and (B) component.
The organic solvent is preferably a solvent that is suitable for a low-temperature baking process.

  Examples of the organic solvent of the component (C) of the present application include, but are not limited to, solvents belonging to the following groups A and B. One or more of these may be used, or a combination thereof may be used.

<Group A>
Solvents belonging to Group A are shown below when it is desired to increase the solubility of the above-mentioned polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, polyester, polyamide, and a polymer of a monomer having a polymerizable unsaturated bond. It is preferable to use such a solvent (also referred to as Group A).

  For example, N-methyl-2-pyrrolidone, a compound represented by the following formula (NP), a compound represented by the following (NAm), γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolide It is at least one solvent selected from the group consisting of non.

In the formula (NP), R ¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group.
In the formula (NAm), R ² and R ³ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or “—O—” between carbon-carbon bonds of the hydrocarbon group. R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.
These solvents dissolve the polymer in the liquid crystal aligning agent.

  Specific examples of the compound represented by the formula (NP) include N-ethyl-2-pyrrolidone, 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 -Methoxybutyl-2-pyrrolidone and the like.

  Specific examples of the compound represented by the above formula (NAm) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N- Examples include dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, and n-butoxy-N-isopropyl-propionamide.

  Among the solvent A group, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-butoxy-N, N-dimethylpropanamide, Selected from the group consisting of 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide And more preferably at least one compound selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidinone.

<Group B>
The liquid crystal aligning agent which concerns on this invention can improve the applicability | paintability with respect to the board | substrate of a liquid crystal aligning agent also in low-temperature baking, and the compound represented by a following formula (Sol-1) by the point which raises the drying rate of a liquid crystal aligning agent, Formula (Sol-2), solvent represented by the following formula (a), methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 1-butanol, tert-butyl alcohol, 1-pen Tanol, 2-methyl-1-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol , Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexa , Dipropyl ether, dibutyl ether, dihexyl ether, dioxane, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2 -At least one selected from the group consisting of compounds represented by ethylhexyl acetate, propylene carbonate, ethylene carbonate, furfuryl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, methyl pyruvate, ethyl pyruvate, diisobutyl ketone It is preferable to contain a compound (hereinafter referred to as group B). It is preferable to include at least one compound selected from the group consisting of a compound represented by the following formula (Sol-1) and a compound represented by the following formula (Sol-2).

[In the formula (Sol-1),
Ys ⁷ and Ys ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. And monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms. More preferably, it is a C1-C6 alkyl group.
Xs ¹ is an oxygen atom or —COO—.
Xs ² is a single bond or a carbonyl group,
Rs ⁷ is an alkanediyl group having 2 to 4 carbon atoms, and the alkanediyl group of R _S ⁷ may be linear or branched. For example, methylene group, ethylene group, 1,3-propanediyl group, 1, Examples include 2-propanediyl group, 1,4-butanediyl group, 1,3-butanediyl group and the like. R _s ⁷ is preferably an ethylene group, a 1,3-propanediyl group or a 1,4-butanediyl group.
ns ¹ is an integer of 1 to 3, and when ns ¹ is 2 or 3, a plurality of Rs ⁷ may be the same or different, and preferably 1 or 2.
In the formula (Sol-2),
Zs ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkanediyl group, such as a methylene group, an ethylene group, a 1,3-propanediyl group, or a 1,4-butanediyl group. Etc.
Ys ⁹ and Ys ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. And monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms. More preferably, it is a C1-C6 alkyl group. ].

(Where
R _{1 and} R ₂ are each independently a linear or branched alkyl group having 1 to 8 carbon atoms. However, R ₁ + R ₂ is an integer greater than 3. )

Among the group B, the compound represented by the above formula (Sol-1), the above formula (Sol-2), the solvent represented by the above formula (a), methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4 -Methyl-2-pentanone, 1-butanol, tert-butyl alcohol, 1-pentanol, 2-methyl-1-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-ethyl- 1-butanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, dipropyl ether, dibutyl ether, dihexyl ether , Dioxane, 2-pentanone, 3-pe Thanone, 2-hexanone, 2-heptanone, 4-heptanone, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propylene carbonate, ethylene carbonate, furfuryl alcohol, n-butyl acetate, pyruvin Preferred is at least one compound selected from the group consisting of compounds represented by methyl acid, ethyl pyruvate, diisobutyl ketone,
Compound represented by formula (Sol-1), formula (Sol-2), formula (a), methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, dipropyl ether Dibutyl ether, dihexyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propylene carbonate, At least one compound selected from the group consisting of compounds represented by ethylene carbonate diisobutyl ketone is more preferred. Most preferred is at least one compound selected from the group consisting of a compound represented by the above formula (Sol-1) and a compound represented by the above formula (Sol-2).

Specific examples of the solvent represented by the formula (Sol-1) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether ( Butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether Ether acetate, di Tylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-ethoxybutyl Such as acetate;
Specific examples of the solvent represented by (Sol-2) include, for example, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3. -Methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate and the like;
Each can be mentioned.

  Preferred specific examples of the formulas (Sol-1) to (Sol-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether. (Butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol Call dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate.

  A preferable solvent of the above formula (a) is diisobutyl carbinol.

  It is preferable that the liquid crystal aligning agent of this invention uses A group and B group together, In that case, B group is 5-95 mass% or less of the whole solvent contained in a liquid crystal aligning agent, 5-80 mass% The following is more preferable, and more preferably 30 to 80% by mass or less. Moreover, 5 to 95 mass% of the whole solvent contained in a liquid crystal aligning agent of A group is preferable, 20 to 95 mass% is more preferable, and 20 to 70 mass% or less is more preferable.

<< Components other than (A) Component to (C) Component >>
The liquid crystal aligning agent of this application may contain suitably components other than the above-mentioned (A) component-(C) component suitably.

<Crosslinkable compound>
As a component other than the component (A) to the component (C), a compound having an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group according to paragraphs [0109] to [0113] of International Publication WO2016 / 047771, Or a compound having a block isocyanate group in addition to a compound having at least one group selected from the group consisting of a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group (these are also collectively referred to as other crosslinkable compounds). .) Can be used.

  Examples of the compound having a blocked isocyanate group include the following formulas (bl-1) to (bl-3).

  The above is an example of other crosslinkable compounds, but is not limited thereto. Moreover, the other crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, or may be combined 2 or more types.

  The content of the other crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components. Especially, in order for a crosslinking reaction to advance and to express the target effect, 0.1-100 mass parts is preferable with respect to 100 mass parts of polymer components. More preferred is 1 to 50 parts by mass.

<Other optional components>
The liquid crystal aligning agent of this invention can use the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply | coating a liquid crystal aligning agent, and surface smoothness.
Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these include surfactants described in paragraph [0117] of International Publication No. WO2016 / 047771. The amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 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.

  Furthermore, as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the device, the liquid crystal aligning agent is disclosed in International Publication No. WO2011 / 132751 (published 2011.10.27), pages 69-73. The nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed, can also be added. The amine compound may be added directly to the liquid crystal aligning agent, but it is preferable to add the amine compound after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as the specific polymer (A) is dissolved.

  The liquid crystal aligning agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, resin film or compound that improves the film thickness uniformity and surface smoothness of the liquid crystal aligning film, and a compound that promotes charge removal. Polymer other than the polymer described in the invention, silane coupling agent for the purpose of improving the adhesion between the alignment film and the substrate, and further imidation by heating the polyimide precursor efficiently when the coating film is baked An imidization accelerator or the like for the purpose may be added.

The liquid crystal aligning agent of this application has the form of the solution containing the above-mentioned (A) component-(C) component.
The liquid crystal aligning agent used in the present invention has a form of a solution in which a polymer having a specific structure is dissolved in an organic solvent.

  The concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but it is 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film. It is preferable to be 10% by weight or less from the viewpoint of storage stability of the solution.

  The liquid crystal aligning agent of this application changes suitably solid content concentration (ratio which the total weight of components other than (C) component of a liquid crystal aligning agent accounts to the total weight of a liquid crystal aligning agent) by the setting of the thickness of the coating film to form. However, it is preferably 1% by weight or more from the viewpoint of forming a uniform and defect-free coating film, and preferably 10% by weight or less from the viewpoint of storage stability of the solution.

The particularly preferable solid content concentration range varies depending on the method of applying the liquid crystal aligning agent to the substrate.
For example, when the spinner method is used, the polymer concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.

  According to another aspect of the present invention, a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention is provided.

  According to still another aspect of the present invention, the step of applying the liquid crystal aligning agent of the present invention onto a substrate to form a coating film, and the coating film is not in contact with the liquid crystal layer or the liquid crystal layer There is provided a method for producing a liquid crystal alignment film, comprising a step of irradiating the coating film with light in contact.

  Furthermore, according to another aspect of the present invention, there is provided a liquid crystal display device comprising the liquid crystal alignment film according to the present invention or the liquid crystal alignment film obtained by the production method of the present invention. Details are shown below.

<Liquid crystal alignment film and liquid crystal display element>
By using the liquid crystal alignment agent, a liquid crystal alignment film can be produced. Moreover, the liquid crystal display element which concerns on this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element according to the present invention is not particularly limited. For example, a TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type. (IPS type), FFS (Fringe Field Switching) type, optical compensation bend type (OCB type) and the like can be applied.

  The liquid crystal display element which concerns on this invention can be manufactured according to the process containing the following processes (1-1)-(1-3), for example. In the step (1-1), a substrate to be used is different depending on a desired operation mode. Step (1-2) and step (1-3) are common to each operation mode.

[Step (1-1): Formation of coating film]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.

(1-1A)
For example, when manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is formed on each transparent conductive film forming surface, The liquid crystal aligning agent prepared in (1) is preferably applied by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (cycloaliphatic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching; a method of using a mask having a desired pattern when forming a transparent conductive film; And so on. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or a functional titanium compound is formed on the surface of the substrate surface on which the coating film is formed. It is also possible to perform a pretreatment to apply the above in advance.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The firing temperature (post-bake temperature) at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

(1-1B)
When manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape, and a counter substrate provided with no electrode A liquid crystal aligning agent is apply | coated to one surface, respectively, Then, a coating film is formed by heating each application surface. Regarding the material used for the substrate and the transparent conductive film, the coating method, the heating conditions after coating, the patterning method for the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the coating film to be formed The same as (1-1A). As the metal film, for example, a film made of a metal such as chromium can be used.

  In both cases (1-1A) and (1-1B), after applying a liquid crystal aligning agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a liquid crystal alignment film. The At this time, by further heating after the coating film is formed, the dehydration ring-closing reaction of the polyamic acid, polyamic acid ester and polyimide compounded in the liquid crystal aligning agent according to the present invention may be advanced to obtain a more imidized coating film. .

[Step (1-2): Orientation ability imparting treatment]
When manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, the process which provides liquid crystal aligning ability to the coating film formed at the said process (1-1) is implemented. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. Examples of the alignment ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment in which the coating film is irradiated with polarized or non-polarized radiation. Processing. On the other hand, when manufacturing a VA type liquid crystal display element, the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film. May be.

  When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation applied to the coating film. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, an oblique direction, or a combination thereof. When irradiating non-polarized radiation, the direction of irradiation is an oblique direction.

As a light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. Ultraviolet rays in a preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating. The radiation dose is preferably 10 to 5,000 mJ / cm ² , more preferably 30 to 2,000 mJ / cm 2.

  Moreover, you may perform light irradiation with respect to a coating film, heating a coating film, in order to improve the reactivity. The temperature at the time of heating is 30-250 degreeC normally, Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC.

  In addition, when using ultraviolet light containing light having a wavelength of 150 to 800 nm, the light irradiation film obtained in the above step can be used as a liquid crystal alignment film as it is. Also good. The firing temperature at this time is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The firing time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The photo-alignment process here corresponds to a light irradiation process in a state where it is not in contact with the liquid crystal layer.

  Note that the liquid crystal alignment film after the rubbing treatment is further subjected to a process for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays, A resist film is formed on the part, and a rubbing process is performed in a direction different from the previous rubbing process, followed by a process of removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. A liquid crystal alignment film suitable for a VA liquid crystal display element can also be suitably used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step (1-3): Construction of liquid crystal cell]
(1-3A)
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell is manufactured by injecting and filling the liquid crystal into the cell gap partitioned by the step of sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped at predetermined locations on the liquid crystal alignment film surface. After that, the other substrate is bonded so that the liquid crystal alignment films face each other and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. . Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

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

  Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl. Cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck) A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used. The liquid crystal can also contain additional anisotropic dyes. The term “dye” can refer to a substance that can intensively absorb or deform light in the visible light region, eg, at least a portion or the entire range in the 400 nm to 700 nm wavelength range. The “isotropic dye” may mean a substance capable of anisotropic absorption of light in at least a part or the entire range of the visible light region. The color sensation of the liquid crystal cell can be adjusted through the use of the dye as described above. The kind of the anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used. The ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the intended physical properties. For example, the anisotropic dye is a ratio of 0.01 part by weight to 5 parts by weight with respect to 100 parts by weight of the liquid crystal compound. However, the above ratio can be changed to an appropriate range if necessary.

(1-3B)
When manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in the above (1-3A) except that a photopolymerizable compound is injected or dropped together with a liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Moreover, as light to irradiate, the ultraviolet-ray and visible light which contain light with a wavelength of 150-800 nm can be used, for example, However, The ultraviolet-ray containing light with a wavelength of 300-400 nm is preferable. As a light source of 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. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter diffraction grating. The irradiation dose of light, preferably less than 100 mJ / cm ² or more 20,000mJ / cm ^2, more preferably 100~10,000mJ / cm ^2.

(1-3C)
When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a photopolymerizable group (polymer or additive), a liquid crystal cell is constructed in the same manner as (1-3A) above, You may employ | adopt the method of manufacturing a liquid crystal display element by passing through the process of light-irradiating a liquid crystal cell in the state which applied the voltage between the electrically conductive films which a pair of board | substrate has. According to this method, the PSA mode can be realized with a small amount of light irradiation. The light irradiation to the liquid crystal cell may be performed in a state where the liquid crystal is driven by applying a voltage, or may be performed in a state where a low voltage is applied so as not to drive the liquid crystal. The applied voltage can be, for example, 0.1 to 30 V direct current or alternating current. The description of (1-3B) above can be applied to the conditions of light to be irradiated. The light irradiation process here corresponds to a light irradiation process in a state of contact with the liquid crystal layer.

  And the liquid crystal display element which concerns on this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

  The liquid crystal display device according to 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, smartphones. It can be used in various display devices such as various monitors, liquid crystal televisions, and information displays.

  As described above, by using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film having good adhesion even when low-temperature baking is performed.

  The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

Abbreviations of the compounds used are as follows.
(liquid crystal)
LC-V1: MLC-6608 (Merck)
LC-I1: MLC-2041 (Merck)
LC-I2: MLC-7026-100 (Merck)

(Diamine component)
A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: the above formula [2a -26] A5: 1,3-diamino-4-octadecyloxybenzene A6: 1,3-diamino-4-hexadecyloxybenzene A8: N- (2,4-diaminophenyl) -4- (Trans-4-heptylcyclohexyl) benzamide

B1: 3,5-Diaminobenzoic acid B2: 2,4-Diamino-N, N-diallylaniline

C1: p-phenylenediamine C2: m-phenylenediamine C3: 1,5-bis (4-aminophenoxy) pentane C4: 1,3-bis (4-aminophenethyl) urea C5: 4- (2- (methylamino) ) Ethyl) aniline C6: Compound represented by the above formula [Y-159] C7: 1,2-bis (4-aminophenoxy) ethane C8: 4,4′-diaminodiphenylmethane DA-N-A6: 4,4 '-Diaminodiphenylamine DA-NA7: Bis (4-aminophenyl) -N-methylamine

(Tetracarboxylic acid component)
D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride D3: the above formula [X1- tetracarboxylic acid dianhydride represented by 6] D4: the formula [X1-8] with the tetracarboxylic dianhydride _{R M} is a hydrogen atom D5: tetra represented by the formula [X1-1-2] Carboxylic dianhydride D6: 1,2,3,4-butanetetracarboxylic dianhydride D7: Pyromellitic anhydride D8: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride D9: 2,4-bis (methoxycarbonyl) cyclobutane-1,3-dicarboxylic acid D10: 2,5-bis (methoxycarbonyl) benzene-1,4-dicarboxylic acid

(Condensing agent)
DMT-MM: 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholin-4-nium

(Adhesive compound)
C-M1: C-590 (Kuraray Co., Ltd. polycarbonate diol, number average molecular weight = 500)
C-M2: C-1090 (Kuraray Co., Ltd. polycarbonate diol number average molecular weight = 1,000)
C-M3: CD220 (a polycarbonate diol manufactured by Daicel Corporation, number average molecular weight = 2,000)
C-M4: UH-3000 (Ube Industries, Ltd. polycarbonate diol number average molecular weight = 3,000)
C-M5: C-5090 (Kuraray Co., Ltd. polycarbonate diol number average molecular weight = 5,000)

(Other adhesive compounds)
K1: TM-BIP-A (methylol compound, manufactured by Asahi Organic Materials Co., Ltd.)
K2: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd.)

(solvent)
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL (GBL): γ-butyrolactone DMI: 1,3-dimethyl-2-imidazolidinone PGME: propylene glycol monomethyl ether ECS: ethylene Glycol monoethyl ether BCS: Ethylene glycol monobutyl ether PB: Propylene glycol monobutyl ether EC: Diethylene glycol monoethyl ether EEP: Ethyl-3-ethoxypropionate DDE: Diethylene glycol diethyl ether DME: Dipropylene glycol dimethyl ether DME: Diethylene glycol dimethyl ether DPM: Di Propylene glycol monomethyl ether

(Molecular weight measurement)
The molecular weights of the polyimide precursor and polyimide are as follows: normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK), column (Shodex ^R KD-803, Shodex ^R KD-805) (Showa Denko KK) And manufactured as follows.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, 10 ml / L of tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; (About 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization ratio of polyimide)
20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane). ) Mixture) (0.53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

[Synthesis of polyimide polymer]
<Synthesis Example 1>
D1 (3.32 g, 16.9 mmol) as the tetracarboxylic acid component, A1 (3.26 g, 8.57 mmol), B1 (1.04 g, 6.84 mmol) and C2 (0.19 g, 1.76 mmol) as the diamine component ) Was mixed in NEP (23.4 g) and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25 mass%. The number average molecular weight of this polyamic acid was 23,200, and the weight average molecular weight was 70,100.

<Synthesis Example 2>
Mix D2 (4.29 g, 17.1 mmol) as the tetracarboxylic acid component and A2 (6.76 g, 17.1 mmol) and B1 (2.61 g, 17.1 mmol) as the diamine component in NMP (33.9 g). Then, after reacting at 50 ° C. for 2 hours, tetracarboxylic acid component D1 (3.29 g, 16.8 mmol) and NMP (17.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a resin solid concentration of 25 A mass% polyamic acid solution (2) was obtained. The number average molecular weight of this polyamic acid was 23,800, and the weight average molecular weight was 69,500.

<Synthesis Example 3>
After adding NMP to the polyamic acid solution (2) (30.5 g) obtained by the synthesis method of Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (3.90 g) and pyridine (2. 41 g) was added and reacted at 70 ° C. for 2 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 61%, the number average molecular weight was 21,900, and the weight average molecular weight was 59,900.

<Synthesis Example 4> to Synthesis Example <11>
Except having changed into the composition shown in Table 1, it carried out similarly to the synthesis example 2 and the synthesis example 3, polyimide powder (4)-(9), (11), and the polyamic acid solution whose resin solid content concentration is 25 mass% ( 10) was obtained.

  Table 1 shows the polyimide polymers obtained in Synthesis Examples 1 to 11 as described above. In addition, in the polyimide powders of Synthesis Examples 4 to 11, the number average molecular weight and the weight average molecular weight are shown in Table 2, respectively.

<Synthesis Example 12>
D1 (19.61 g, 0.1 mol) as a tetracarboxylic acid component and DA-NA6 (18.73 g, 0.094 mol) as a diamine component were mixed in NMP (345.1 g) and reacted at room temperature for 5 hours. Thus, a polyamic acid solution (12) having a resin solid content concentration of 10% by mass was obtained. The number average molecular weight of this polyamic acid was 14,100, and the weight average molecular weight was 29,500.

<Synthesis Example 13>
A polyamic acid solution (13) having a resin solid content concentration of 10% by mass was obtained in the same manner as in Synthesis Example 12 so that the composition shown in Table 3 was obtained. The number average molecular weight of this polyamic acid was 13,300, and the weight average molecular weight was 27,800.

<Synthesis Example 14>
As tetracarboxylic acid, D9 (2.03 g, 7.80 mmol), D10 (1.02 g, 3.60 mmol), and as the diamine component, C4 (1.07 g, 3.60 mmol), C1 (0.79 g, 7.60 mmol). 20 mmol), A8 (0.49 g, 1.20 mmol), triethylamine (0.61 g, 0.0060 mol) as the base, DMT-MM (9.96 g, 36.0 mmol) as the condensing agent, and NMP (84.4 g). ) For 3.5 hours at room temperature to obtain a polyamic acid ester solution.

This polyamic acid ester solution was put into 550 g of methanol, and the precipitated solid was recovered. The solid was washed several times with methanol and dried under reduced pressure at 100 ° C. to obtain a polyamic acid ester powder (14). The number average molecular weight of this polyamic acid ester was 16,478, and the weight average molecular weight was 39,754.

<Synthesis Example 15>
A polyamic acid solution (15) having a resin solid content concentration of 10% by mass was obtained in the same manner as in Synthesis Example 12 so that the composition shown in Table 3 was obtained. The number average molecular weight of this polyamic acid was 15,600, and the weight average molecular weight was 38,400.

<Synthesis Example 16>
A polyamic acid solution (16) having a resin solid content concentration of 10% by mass was obtained in the same manner as in Synthesis Example 12 so that the composition shown in Table 3 was obtained. The number average molecular weight of this polyamic acid was 12629, and the weight average molecular weight was 29521.

<Synthesis Example 17>
As a diamine component, C7 (79.4 g, 0.33 mol) and DA-N-A6 (64.8 g, 0.33 mol) were added to NMP (911 g) and GBL (911 g) and stirred while feeding nitrogen. And dissolved. While stirring this diamine solution, tetracarboxylic acid component D1 (65.0 g, 0.33 mol) was added, and after stirring for 2 hours at room temperature, D8 (86.1 g, 0.29 mol) was added. NMP (390 g) and GBL (390 g) were added and stirred at 40 ° C. for 30 hours under a nitrogen atmosphere to obtain a polyamic acid solution (17) having a resin solid content concentration of 10 mass%. This polyamic acid solution had a number average molecular weight of 15,773 and a weight average molecular weight of 31,242.

  Table 3 shows the polyimide polymers obtained in Synthesis Examples 12 to 17 as described above.

<Synthesis Example 18>
As a diamine component, D4 is (30.03 g, 0.100 mol) as a tetracarboxylic acid component, C1 is (9.19 g, 0.085 mol), and A6 is (5.23 g, 0.015 mol) as a diamine component. Was reacted in NMP (252 g) at 50 ° C. for 24 hours to prepare a polyamic acid solution having a resin solid content concentration of 15 mass%.

  NMP was added to 50 g of this polyamic acid solution to dilute to 5% by mass, pyridine (8.0 g) and acetic anhydride (17.2 g) were further added as an imidization catalyst, and the mixture was reacted at 40 ° C. for 3 hours. This solution was put into 600 ml of methanol, and the resulting precipitate was separated by filtration and dried to obtain white polyimide powder (18). The imidation ratio of this polyimide was 83%, the number average molecular weight was 9,834 and the weight average molecular weight was 21,659.

<Synthesis Example 19>
As a tetracarboxylic acid component, D1 (9.81 g, 0.05 mol), D7 (9.60 g, 0.044 mol), and as a diamine component, C8 (19.83 g, 0.100 mol), The reaction was carried out in NMP (222 g) at room temperature for 5 hours to prepare a polyamic acid solution (19) having a resin solid content concentration of 15% by mass. This polyamic acid had a number average molecular weight of 10,893 and a weight average molecular weight of 25,972.

  Table 4 shows the polyimide polymers obtained in Synthesis Examples 18 and 19 as described above.

[Preparation of liquid crystal aligning agent]
In the following Examples and Comparative Examples, a liquid crystal aligning agent is prepared, and the obtained liquid crystal aligning agent is used for each of the following “production of liquid crystal display element”, “evaluation of liquid crystal alignment”, “liquid crystal alignment”. Evaluation was performed according to each procedure of "Evaluation of film adhesion" or "Peel test".

[Production of liquid crystal display elements]
(Production of vertical alignment type liquid crystal display device)
Liquid crystal aligning agents (V-1) to (V-6), (V-14) to (V-17) obtained in Examples and liquid crystal aligning agents (R-V1) to (R) obtained in Comparative Examples. -V2) was filtered under pressure through a membrane filter having a pore diameter of 1 μm. The obtained solution was spin-coated on the ITO surface of a 100 × 100 mm glass substrate with an ITO electrode (length: 100 mm, width: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), Heat treatment was performed at 100 ° C. for 2 minutes on a hot plate and at 210 ° C. for 10 minutes in a thermal circulation clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 μm spacer was applied to the liquid crystal alignment film surface of one of the substrates.

  Next, the periphery was apply | coated with the sealing agent (Kyoritsu Chemical XN-1500T). Thereafter, the liquid crystal composition (LC-V1) is dropped on the liquid crystal alignment film surface of the substrate by an ODF (One Drop Filling) method, and then bonded so that the liquid crystal alignment film interface of the other substrate faces. Then, the sealant was cured to obtain a vertical alignment type liquid crystal display element. The obtained liquid crystal display element was heated at 110 ° C. for 1 hour and allowed to stand at room temperature overnight before being used for each evaluation.

(Production of FFS type liquid crystal display element)
<Rubbing alignment treatment>
Liquid crystal aligning agents (I-7) to (I-10), (I-12) to (I-13) obtained in Examples and liquid crystal aligning agents (R-I3) to (R) obtained in Comparative Examples -I5) was filtered under pressure through a membrane filter having a pore diameter of 1 μm.
Next, a glass substrate having a substrate with electrodes and a columnar spacer with a height of 4 μm on which an ITO film is formed on the back surface described in Paragraphs 0060 to 0062 of International Publication (WO2014-084364) is prepared. And washed with IPA (isopropyl alcohol).

  The pressure-filtered liquid crystal aligning agent is spin-coated on the substrate, and heat-treated on a hot plate at 80 ° C. for 2 minutes and in a heat-circulating clean oven at 230 ° C. for 30 minutes. A 100 nm coated substrate was obtained.

The coated substrate is rubbed with a rayon cloth (YA-20R manufactured by Yoshikawa Chemical Industries) (roller diameter: 120 nm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), and then into pure water. The substrate was cleaned by ultrasonic treatment for 1 minute, water droplets were removed by air blow, and then dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
After the above-mentioned two substrates are combined into one set, a sealing agent is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, The sealant was cured. Next, the liquid crystal composition (LC-I1) was injected by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal display element. The obtained liquid crystal display element was heated at 110 ° C. for 1 hour and allowed to stand at room temperature overnight before being used for each evaluation.

<Photo-alignment treatment>
The liquid crystal aligning agent (I-11) obtained in the examples was filtered under pressure through a membrane filter having a pore diameter of 1 μm.
Next, a glass substrate having a substrate with electrodes and a columnar spacer with a height of 4 μm on which an ITO film is formed on the back surface described in Paragraphs 0060 to 0062 of International Publication (WO2014-084364) is prepared. And washed with IPA (isopropyl alcohol).

The pressure-filtered liquid crystal aligning agent is spin-coated on the substrate, and heat-treated on a hot plate at 80 ° C. for 2 minutes and in a heat-circulating clean oven at 230 ° C. for 30 minutes. A 100 nm coated substrate was obtained.
The coated film surface of this coated film substrate was irradiated with 800 mJ / cm ^{2 of} 254 nm linearly polarized ultraviolet light having an extinction ratio of 26: 1 through a polarizing plate. This substrate was heat-treated at 230 ° C. for 30 minutes in a thermal circulation clean oven to obtain a substrate with a liquid crystal alignment film. After the above-mentioned two substrates are combined into one set, a sealing agent is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, The sealant was cured. Next, liquid crystal (LC-I2) was injected by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal display element. Thereafter, the obtained liquid crystal display element was heated at 110 ° C. for 1 hour and allowed to stand at room temperature overnight before being used for each evaluation.

[Evaluation of liquid crystal display elements]
(Liquid crystal orientation)
The liquid crystal orientation of the liquid crystal display element was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), and it was confirmed whether the liquid crystal was aligned horizontally or vertically. Specifically, those in which defects due to liquid crystal flow were not observed were determined to be good.
The results of the evaluation of the liquid crystal orientation of the liquid crystal display element are shown in Tables 5 and 6.

(Adhesion of liquid crystal alignment film)
Obtained in the liquid crystal aligning agents (V-1) to (V-6), (V-14) to (V-17), (I-7) to (I-13) obtained in Examples and Comparative Examples. The liquid crystal aligning agents (R-V1) to (R-V2) and (R-I3) to (R-I5) were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm. The liquid crystal aligning agent was applied on a 100 × 100 mm glass substrate with an ITO electrode (vertical: 100 mm, horizontal: 100 mm, thickness: 0.7 mm) washed with pure water and IPA (isopropyl alcohol), and then on a hot plate. 2 minutes at 80 ° C., except for Comparative Examples 3 and 7, heat treatment at 120 ° C. for 10 minutes in a heat-circulating clean oven, and heat treatment at 210 ° C. for 10 minutes for Comparative Examples 3 and 7, Two ITO substrates with a liquid crystal alignment film having a thickness of 100 nm were prepared. A 6 μm bead spacer is applied to one substrate, and a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) is printed on the liquid crystal alignment film of the other substrate. The overlapping width of the substrates is 1 cm. Bonding was performed so that it might become. At that time, the amount of the sealing agent was adjusted so that the diameter of the sealing agent after bonding was 3 mm. The two bonded substrates were fixed with a clip and then thermally cured at 150 ° C. for 1 hour to produce a test sample substrate for this evaluation.

  Then, this test sample board is pushed in from the upper part of the center of the board after fixing the edge part of the upper and lower boards with a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation). The pressure (N) during peeling, that is, the peeling pressure (N) was measured.

Evaluation shows that the larger the value of the peeling stress (N), the better the adhesion with the sealing agent and the base substrate.
Tables 5 and 6 show the values of peel stress (N) as evaluation results of the adhesion of the liquid crystal alignment film.

(Peel test)
The liquid crystal aligning agents obtained in Examples and Comparative Examples were filtered under pressure with a membrane filter having a pore size of 1 μm.
After apply | coating the said liquid crystal aligning agent on a PET film board | substrate (length: 100mm, width: 100mm, thickness: 50um) with an ITO electrode of 100x100mm, and heat-processing for 5 minutes at 120 degreeC on a hotplate. Two ITO substrates with a liquid crystal alignment film with a film thickness of 100 nm were cut out to a size of 100 × 20 mm.

A 30-um bead spacer was applied to one of the substrates, and a sealing agent (723 K1 manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of the other substrate, and these substrates were bonded to overlap each other. At that time, the amount of the sealing agent was adjusted so that the area of the sealing agent after bonding was 50 × 10 mm. After the two bonded substrates were fixed with a clip, ultraviolet light was irradiated at 3 J / cm ² , and then heat cured at 120 ° C. for 1 hour to prepare a test sample substrate for this evaluation.

  After that, the test sample substrate is fixed with the table top precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation), and then the stress (N / 25 mm), that is, peel strength (N / 25 mm) was measured.

Evaluation shows that the larger the value of the peel strength (N / 25 mm), the better the adhesion with the sealing agent and the base substrate).
As evaluation results of the peel test, values of peel strength (N / 25 mm) are shown in Tables 5 and 6.

<Example 1>
NEP (22.7 g) and BCS (20.8 g) are added to the polyamic acid solution (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, and the mixture is added at 50 ° C. for 5 hours. Stir. Then, C-M1 (0.56g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-1), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

  Similarly, for the following Examples 2 to 16 and Comparative Examples 1 to 8, production of liquid crystal display elements and various evaluations were performed. The results of Examples and Comparative Examples are collectively shown in Tables 5 and 6.

<Example 2>
NMP (27.3 g) and BCS (25.5 g) were added to the polyamic acid solution (2) (9.80 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and the mixture was added at 50 ° C. for 5 hours. Stir. Then, C-M1 (0.74g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-2), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 3>
A peel test was performed using the liquid crystal aligning agent obtained by the method of Example 2.

<Example 4>
NMP (35.4 g) and BCS (24.2 g) were added to the polyimide powder (3) (2.33 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. Then, C-M1 (0.47g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-3), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 5>
A peel test was performed using the liquid crystal aligning agent (V-3) obtained by the method of Example 4.

<Example 6>
NEP (32.8 g) and PB (18.2 g) were added to the polyimide powder (3) (1.86 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. Then, C-M1 (0.09g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-4), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 7>
Γ-BL (6.40 g) and PGME (42.5 g) were added to the polyimide powder (3) (1.65 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. Then, C-M1 (0.08g) and K1 (0.08g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-5), preparation of a liquid crystal display element, evaluation of liquid crystal aligning property, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 8>
NEP (34.0 g), BCS (12.4 g) and PB (14.6 g) are added to the polyimide powder (4) (2.55 g) obtained in Synthesis Example 4, and the mixture is stirred at 70 ° C. for 24 hours. Dissolved. Then, C-M1 (0.08g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (V-6). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (V-6), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 9>
A peel test was performed using the liquid crystal aligning agent (V-6) obtained by the method of Example 8.

<Example 10>
GBL (6.00 g), DMI (6.00 g), and EEP (8.00 g) were added to the polyamic acid solution (12) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 12. In addition, the mixture was stirred at 50 ° C. for 5 hours. Then, C-M1 (0.60 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent (I-7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-7), preparation of a liquid crystal display element, evaluation of liquid crystal aligning property, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 11>
GBL (12.0 g) and DEDE (8.00 g) were added to the polyamic acid solution (13) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 13, and stirred at 50 ° C. for 5 hours. did. Then, C-M1 (0.40 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent (I-8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-8), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 12>
GBL (30.0 g) and DME (8.00 g) were added to the polyamic acid ester powder (14) (2.0 g) obtained in Synthesis Example 14, and the mixture was stirred at 50 ° C. for 5 hours. Then, C-M1 (0.20 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (I-9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-9), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 13>
GBL (12.0 g) and DEME (8.00 g) were added to the polyamic acid solution (15) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 15, and stirred at 50 ° C. for 5 hours. did. Then, C-M1 (0.20g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid crystal aligning agent (I-10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-10), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 14>
GBL (12.0 g) and DEME (8.00 g) were added to the polyamic acid solution (16) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 16, and the mixture was stirred at 50 ° C. for 5 hours. did. Thereafter, C-M1 (0.10 g) was added to this solution and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (I-11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-11), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of the liquid crystal alignment film were performed.

<Example 15>
GBL (16.0 g) and DPM (4.00 g) were added to the polyamic acid solution (17) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 17, and stirred at 50 ° C. for 5 hours. did. Thereafter, C-M1 (0.10 g) was added to this solution and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (I-12). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-12), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 16>
GBL (16.0 g) and DPM (4.00 g) were added to the polyamic acid solution (17) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 17, and stirred at 50 ° C. for 5 hours. did. Thereafter, C-M1 (0.10 g) and K1 (0.10 g) were added to this solution, followed by stirring at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (I-13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (I-13), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 17> to <Example 20>
Liquid crystal aligning agents (V-14) to (V-17) were obtained in the same manner as in Example 4 except that the adhesive compounds were (C-M2) to (C-M5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agents (V-14) to (V-17), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 21>
A liquid crystal aligning agent (V-18) was obtained in the same manner as in Example 7 except that the other adhesive compound was changed to K2.
Abnormalities such as turbidity and precipitation were not observed in the liquid crystal aligning agent, and it was confirmed that the liquid crystal alignment agent was a uniform solution.
Using the obtained liquid crystal aligning agent (V-18), preparation of a liquid crystal display element, evaluation of liquid crystal aligning property, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 22>
A liquid crystal aligning agent (V-19) was obtained in the same manner as in Example 16 except that other adhesive compounds were changed to K2.
Abnormalities such as turbidity and precipitation were not observed in the liquid crystal aligning agent, and it was confirmed that the liquid crystal alignment agent was a uniform solution.
Using the obtained liquid crystal aligning agent (V-19), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Example 23>
3.00 g of the polyimide powder (18) obtained in Synthesis Example 18 was dissolved in GBL (34.50 g) by stirring at 50 ° C. for 20 hours at 50 ° C.
Further, GBL (12.50 g) was added so that the polyimide concentration in the solution was 6% by mass, and the mixture was stirred at 50 ° C. for 20 hours.
NMP, GBL, and BCS are added to the polyamic acid solution (19) (40.0 g) having a resin solid content concentration of 15% by mass obtained in Synthesis Example 19, polyamic acid is 6% by mass, NMP is 20% by mass, GBL was prepared at 59% by mass and BCS was prepared at 15% by mass.

20 g of the polyimide solution prepared above and 80 g of a dilute solution of polyamic acid are mixed, stirred at room temperature for 20 hours, and further added so that C-M1 is 5% by mass with respect to the solid content of the polymer. An aligning agent (T-20) was obtained. Abnormalities such as turbidity and precipitation were not observed in the liquid crystal aligning agent, and it was confirmed that the liquid crystal alignment agent was a uniform solution.
Using the obtained liquid crystal aligning agent (T-20), a liquid crystal display element and an adhesion evaluation substrate were obtained in the same manner as in Example 16 except that the alignment was performed so that the alignment direction was 90 °. Evaluation of liquid crystal alignment and adhesion of liquid crystal alignment film were performed.

<Comparative Example 1>
NEP (22.7 g) and BCS (20.8 g) are added to the polyamic acid solution (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, and the mixture is added at 50 ° C. for 5 hours. The liquid crystal aligning agent (R-V1) was obtained by stirring. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (R-V1), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Comparative example 2>
NEP (22.7 g) and BCS (20.8 g) are added to the polyamic acid solution (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, and the mixture is added at 50 ° C. for 5 hours. Stir. Then, K1 (0.18g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (R-V2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (R-V2), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 3>
Except for heat treatment for 10 minutes with the temperature of the heat-circulating clean oven set at 210 ° C., in the same manner as in Comparative Example 2, production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed. went.

<Comparative example 4>
A peel test was performed using the liquid crystal aligning agent obtained by the method of Comparative Example 1.

<Comparative Example 5>
GBL (6.00 g), DMI (6.00 g), and EEP (8.00 g) were added to the polyamic acid solution (12) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 12. In addition, the mixture was stirred at 50 ° C. for 5 hours to obtain a liquid crystal aligning agent (R-I3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
A peel test was performed using the obtained liquid crystal aligning agent (R-I3).

<Comparative Example 6>
GBL (6.00 g), DMI (6.00 g), and EEP (8.00 g) were added to the polyamic acid solution (12) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 12. In addition, the mixture was stirred at 50 ° C. for 5 hours. Then, K1 (0.20g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (R-I4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (R-I4), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 7>
Except for heat treatment for 10 minutes with the temperature of the heat-circulating clean oven set at 210 ° C., in the same manner as in Comparative Example 6, production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed. went.

<Comparative Example 8>
GBL (6.00 g), DMI (6.00 g), and EEP (8.00 g) were added to the polyamic acid solution (12) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 12. In addition, the mixture was stirred at 50 ° C. for 5 hours. Then, K1 (0.60g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid crystal aligning agent (R-I5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity and precipitation.
Using the obtained liquid crystal aligning agent (R-I5), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

<Comparative Example 9>
A liquid crystal aligning agent (R-T1) was prepared in the same manner as in Example 23 except that C-M1 was not added. Using the obtained liquid crystal aligning agent (R-T1), preparation of a liquid crystal display element, evaluation of liquid crystal alignability, and evaluation of the adhesiveness of a liquid crystal aligning film were performed.

  As can be seen from the above results, the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has good liquid crystal alignment, and the liquid crystal alignment film also has the liquid crystal alignment of the comparative example. Compared to the liquid crystal alignment film obtained from the alignment agent, the results were high.

Specifically, in a comparison between an example including the adhesive compound of the present invention and a comparative example not including, that is, a comparison between Example 1 and Comparative Example 1, and a comparison between Example 10 and Comparative Examples 6-8. is there.
In addition, compared with a liquid crystal alignment film obtained from a liquid crystal alignment agent using a vertical alignment diamine (in the table, side chain diamine), a liquid crystal alignment using a horizontal alignment diamine (main chain diamine). As a result, the adhesion of the liquid crystal alignment film obtained from the agent was high. Specifically, it is a comparison between Example 1 and Example 10.
In addition, when other adhesive compounds were introduced into the liquid crystal aligning agent of the present invention, a liquid crystal display device having better adhesiveness with the liquid crystal alignment film was obtained. Specifically, it is a comparison between Example 15 and Example 16.

The liquid crystal display element using the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can be used suitably for the display element of various liquid crystal modes. These elements are also useful in liquid crystal displays for display purposes, and in light control windows and optical shutters for controlling transmission and blocking of light.

Claims (9)

(A) at least one polymer selected from the group consisting of polyimide, polyamic acid, polyamic acid ester, polyorganosiloxane, polyester, polyamide, and a polymer of a monomer having a polymerizable unsaturated bond;
(B) At least one compound selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol; and (C) a liquid crystal aligning agent containing an organic solvent.   The liquid crystal aligning agent of Claim 1 whose number average molecular weights of the compound of the said (B) component are 300-10,000. The liquid crystal aligning agent of Claim 1 or 2 whose said (B) component is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by a following formula (CL).

[Where:
Each R is independently a divalent aliphatic hydrocarbon group or a hydrocarbon group having a divalent alicyclic structure;
k is a number determined such that the number average molecular weight of the compound of the formula (CL) is 300 to 10,000].   The component (A) is at least one polymer selected from the group consisting of a polymer of a monomer having a polyimide, a polyamic acid, a polyamic acid ester, and a polymerizable unsaturated bond. The liquid crystal aligning agent of one term. A polymer obtained by reacting a diamine with a tetracarboxylic acid derivative, wherein the component (A) is at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester and tetracarboxylic diester dichloride And
The said tetracarboxylic acid derivative | guide_body contains the structure which has at least 1 type chosen from the group which consists of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, and a benzene ring structure. Liquid crystal aligning agent. The liquid crystal aligning agent as described in any one of Claims 1-5 whose said (C) component is an organic solvent containing the solvent represented by a following formula (Sol-1) or (Sol-2).

[In the formula (Sol-1),
Ys ⁷ and Ys ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
Xs ¹ is an oxygen atom or —COO—,
Xs ² is a single bond or a carbonyl group,
Rs ⁷ is an alkanediyl group having 2 to 4 carbon atoms,
ns ¹ is an integer of 1 to 3, and when ns ¹ is 2 or 3, a plurality of Rs ⁷ may be the same or different,
In the formula (Sol-2),
Zs ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms,
Ys ⁹ and Ys ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms].   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1-6.   The process of apply | coating the liquid crystal aligning agent as described in any one of Claims 1-6 on a board | substrate, and forming a coating film, The state in which the said coating film is not in contact with the liquid crystal layer, or was in contact with the liquid crystal layer And a step of irradiating the coating film with light in a state. A liquid crystal display element comprising the liquid crystal alignment film according to claim 7 or the liquid crystal alignment film obtained by the production method according to claim 8.