JP2019119807A - Curable composition - Google Patents

Abstract

To provide a cured film that is excellent in the formability of a pattern body having a strong anchoring ability, and excellently shows weak anchoring properties in an area where the pattern body having a strong anchoring ability is not formed.SOLUTION: A curable composition contains a polyfunctional carboxyl compound (A), a polyfunctional epoxy compound (B), and a surfactant (C).SELECTED DRAWING: None

Description

  The present invention is a curable composition which provides a cured film capable of forming both anchoring layers having both a region having weak anchoring ability and a region having strong anchoring ability in a liquid crystal display device, and a cured film thereby. The present invention relates to a liquid crystal display device having both anchoring layers and both anchoring layers.

  Since liquid crystal display elements have characteristics such as thinness, lightness, and low power consumption, their application is being expanded to a wide range of display elements of mobile phones, computers, and televisions. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), etc. have been proposed as display principles of liquid crystal display elements, but most of them are liquid crystal molecules depending on the alignment substrate. The orientation direction needs to be regulated in advance.

  As a method of forcing the alignment direction of liquid crystal molecules, after forming an alignment film formed using a solution containing a polyimide or a polyimide precursor on a substrate, a roller wound with a cloth such as rayon or cotton is rotated at A method in which the surface of the alignment film is rubbed in one direction by rotating while keeping the distance between the roller and the substrate constant (rubbing method) or a method of generating anisotropy in molecular orientation of polyimide by irradiating linearly polarized ultraviolet light (Photo alignment method) etc. are adopted. By these alignment processes, liquid crystal molecules are strongly bound to the surface of the alignment film-attached substrate, and are aligned in a certain direction. Hereinafter, the direction in which the liquid crystal molecules are bound to the surface of the alignment film-attached substrate and aligned is referred to as “alignment easy axis”.

  In recent years, as an improvement measure for improving the low drive voltage property of a liquid crystal display element, a liquid crystal display element having a strong anchoring film on one side of the substrate and a weak anchoring film on the other side (see, for example, Patent Document 1) Proposed. In the present specification, a film that regulates the alignment direction of liquid crystal molecules, such as the alignment film described above, is referred to as “strong anchoring film”, and the ability to regulate is referred to as “strong anchoring ability”. Similarly, a film having weak alignment control force (anchoring) on the surface of the substrate and capable of changing the direction of liquid crystal molecules by an electric field or the like in the vicinity of the film is referred to as a "weak anchoring film". The ability to change the orientation of liquid crystal molecules is referred to as "weak anchoring ability". That is, the "strong anchoring membrane" is a "membrane having a strong anchoring ability". "Weak anchoring membrane" is a "membrane having weak anchoring ability". In addition, a material capable of forming a film having strong anchoring ability is referred to as "a material for forming a strong anchoring film", and a material capable of forming a film having a weak anchoring ability is a "material for forming weak anchoring film" write. Specific examples of the method for evaluating the strong anchoring ability and the weak anchoring ability are described in the following examples.

  In addition, a layer having both a region having weak anchoring ability and a region having strong anchoring ability is referred to as “both anchoring layers”. In addition, although the "alignment film" for liquid crystal display elements usually represents the above-mentioned strong anchoring film, in this specification, both anchoring layers also assume one form of an "alignment film".

  The example of Patent Document 1 describes a liquid crystal display device including a weak anchoring film in which a polymer brush is formed on the substrate surface on one side and a strong anchoring film which is a polyimide film on which the other is rubbed. . The weak anchoring film is weak in the alignment control power of liquid crystal molecules, so a liquid crystal display element provided with a weak anchoring film on one side and a strong anchoring film on the other side is a liquid crystal display element provided with a strong anchoring film on both sides In comparison, there is an advantage that the low drive voltage property is high, but at the same time there is a disadvantage that the display response at the time of voltage OFF is low.

  In the liquid crystal display element used for the information terminal, the area that emphasizes the display responsiveness at voltage OFF such as reproducing a moving image, and the display responsiveness at voltage OFF such as displaying time are not so important, but they are used There are areas where time is long and power saving is important.

  A liquid crystal display element provided with a strong anchoring film on both sides is effective for high display response when the voltage is off, and a strong anchoring film on one side and the other for excellent power saving. A liquid crystal display element provided with a weak anchoring film is effective.

  In general, in a single liquid crystal display element, when there are two types of regions that emphasize display responsiveness at the time of voltage OFF and power saving, priority is given to display responsiveness at the time of voltage OFF. A liquid crystal display element provided with a strong anchoring film is used. Therefore, although the merit of the low drive voltage property improvement of the liquid crystal display element by having a weak anchoring film was known, the display responsiveness fall at the time of voltage OFF becomes a barrier, and the existence of the field which emphasizes the characteristic In such a liquid crystal display element, a weak anchoring film can not be used.

  In a single liquid crystal display element, a configuration example of a liquid crystal display element including both a region having high low driving voltage and a region having high display response at the time of voltage OFF includes a facing first alignment substrate and An alignment having a liquid crystal layer sandwiched between a second alignment substrate, wherein the first alignment substrate has both a region having weak anchoring ability and a region having strong anchoring ability on a single substrate. The substrate is a substrate, and the second alignment substrate is a alignment substrate provided with a strong anchoring film.

  An example of the first alignment substrate used in this configuration example is an alignment having both pixels of a pixel in which a region having weak anchoring ability is a main and a pixel in which a region having strong anchoring ability is a main It is an alignment substrate provided with a substrate and a pixel in which a region having weak anchoring ability is main and a region having strong anchoring ability exists near the electrode region.

  The production method proposed in Patent Document 2 as a method for producing an alignment substrate having both a region having weak anchoring ability and a region having strong anchoring ability on a single substrate is a method using a strong anchoring film. A method of forming a pattern body of a polymer brush which is a pattern body having weak anchoring ability using a photolithography method; a polymer which is a pattern body having weak anchoring ability using an inkjet method on a strong anchoring film Method of forming a brush pattern body; a pattern body of a polymer brush which is a pattern body having weak anchoring ability by using a photolithography method, and a pattern body having strong anchoring ability so as to be repelled thereon It is a method of forming a polyimide pattern body.

  In these methods, a photolithography method or an inkjet method is used. In the manufacturing method using the photolithography method, when the rinse after development is insufficient, there is a risk of display failure due to the remaining component derived from the developer. On the other hand, in the manufacturing method using the inkjet method, the ink deposition position changes due to the influence of static electricity, and there is a risk of pattern shape change.

  In the specific manufacturing method for reducing the risk described above, a weak anchoring film forming step of forming a film having a weak anchoring ability on a substrate, and a step of irradiating ultraviolet rays to a part on the weak anchoring film. Of ultraviolet light irradiation process, a material application process of forming a strong anchoring film forming a material capable of forming a film having a strong anchoring ability, and a second ultraviolet irradiation process of irradiating linearly polarized ultraviolet light It is a method. In this manufacturing method, by performing the first ultraviolet irradiation on the weak anchoring film, it is possible to control the recoating property of the substrate with the weak anchoring film to the material for forming a strong anchoring film. Therefore, it is possible to make a product with a low risk of pattern shape change without performing the development step.

What is necessary for the material for forming a weak anchoring film used in the above-mentioned manufacturing method is that the formed film has a weak anchoring ability; recoating of the material for forming a strongly anchoring film of the formed film Property is poor; recoating property of the formed film to a material for forming a strong anchoring film is improved by ultraviolet irradiation; and the first ultraviolet irradiation process, the material application process for forming a strong anchoring film And, even after the three steps of the second ultraviolet irradiation step, it has weak anchoring ability in a region where a pattern body having strong anchoring ability is not formed.

  "Recoatability" in the present specification is the property of the film to the application of the coating solution on the film, and the film can not form a coating when the film repels the coating solution. The state of the film on which the coating liquid spreads on the film is high and the coating film can be formed is expressed as "good recoatability".

  The recoating property of the film forming material having the strong anchoring ability of the formed film is poor, and the recoating property of the film forming material having the strong anchoring ability of the formed film by ultraviolet irradiation In addition to the improvement, various characteristics of not inhibiting the strong anchoring ability of the pattern body formed by the material for forming a strong anchoring film are combined to obtain “pattern body forming property having strong anchoring ability” and write. In addition, the formed film described above has weak anchoring ability, and after the first ultraviolet irradiation step, the strong anchoring film forming material application step, and the second ultraviolet irradiation step Even in the case where the pattern body having strong anchoring ability is not formed, the various characteristics of having weak anchoring ability in the region where no pattern body having strong anchoring ability is formed are combined. It is described as "anchorability".

  Materials having excellent pattern forming ability with strong anchoring ability and excellent weak anchoring ability of the non-patterned part having strong anchoring ability have not been shown so far.

Japanese Patent Application Laid-Open No. 2017-010030 JP 2017-211566

  An object of the present invention is to provide a curable composition capable of forming a cured film which is excellent in pattern forming ability having strong anchoring ability and excellent in weak anchoring ability of a non-patterned body forming portion having strong anchoring ability. It is to be.

  As a result of intensive studies to solve the above problems, the present inventors achieve the above objects by a curable composition containing a polyfunctional carboxyl compound (A), a polyfunctional epoxy compound (B) and a surfactant (C). It can be found that the present invention has been completed.

The present invention includes the following configurations.
[1] A curable composition comprising a polyfunctional carboxyl compound (A), a polyfunctional epoxy compound (B) and a surfactant (C);
The polyfunctional carboxyl compound (A) is a compound having three or more carboxyl groups per molecule;
The polyfunctional epoxy compound (B) is a compound having three or more epoxy groups per molecule;
Curable composition whose content of the said surfactant (C) is 3-100 weight part with respect to 100 weight part of total amounts of the said polyfunctional carboxyl compound (A) and polyfunctional epoxy compound (B).

[2] The content of the surfactant (C) is 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B), [1] The curable composition as described in a term.

[3] The curable composition according to [1] or [2], wherein the surfactant (C) is a polymerizable surfactant.

[4] The curable composition according to [3], wherein the polymerizable surfactant is a reactive fluorine-containing oligomer.

[5] The curable composition according to [1], wherein the polyfunctional carboxyl compound (A) is at least one selected from polyesteramide acid (A1) and carboxyl group-containing polymer (A2).

[6] The curable composition according to [1], wherein the polyfunctional epoxy compound (B) is one or more selected from a glycidyl ether type epoxy compound (B1) and an epoxy group-containing polymer (B2) object.

[7] A cured film comprising the curable composition according to any one of [1] to [6].

[8] A liquid crystal display device provided with the cured film according to item [7];
The cured film is in contact with the liquid crystal layer;
A liquid crystal display device in which the direction of liquid crystal molecules can be changed by the influence of an electric field even in the vicinity of the cured film.

[9] An alignment substrate comprising the cured film according to the item [7] and a pattern body which regulates the alignment direction of liquid crystal molecules.

[10] A liquid crystal display device comprising the alignment substrate according to the item [9].

  The curable composition according to the preferred embodiment of the present invention is a curable composition which is excellent in pattern formability having strong anchoring ability and which is excellent in weak anchoring ability of a pattern non-formed portion having strong anchoring ability. Sex composition. By using the cured film, there is no risk of display failure due to the remaining component derived from the developer, and it becomes possible to reduce the risk of change in pattern shape when using the inkjet method.

It is sectional drawing which shows the outline of both anchoring layer formation processes. FIG. 1 is a cross-sectional view showing a schematic configuration of a first embodiment of a liquid crystal display element 10 of the present invention, a backlight unit 11 for display, a polarizing plate 12A, and a polarizing plate 12B. In both cases where both anchoring layers 13 are a region 13A having weak anchoring ability and a region 13B having strong anchoring ability, both cases are represented as shown in FIG. In the first embodiment, a liquid crystal using a liquid crystal compound Lp having a positive dielectric anisotropy and applying an electric field E, and in the case where both anchoring layers 13 are the region 13A having weak anchoring ability It is sectional drawing which shows distribution of the orientation direction of a molecule | numerator. In the first embodiment, a liquid crystal using a liquid crystal compound Lp having a positive dielectric anisotropy and applying an electric field E, and in the case where both anchoring layers 13 are the region 13B having strong anchoring ability It is sectional drawing which shows distribution of the orientation direction of a molecule | numerator. In the first embodiment, a plane showing the relationship between the wiring direction of the electrode lines and the alignment direction of the liquid crystal molecules in the vicinity of the weak anchoring film in the state where no electric field is applied using the liquid crystal compound Lp with positive dielectric anisotropy. FIG. In both cases where both anchoring layers 13 are the region 13A having weak anchoring ability and the region 13B having strong anchoring ability, they are represented as shown in FIG. In the first embodiment, an electrode using a liquid crystal compound Lp having a positive dielectric anisotropy and in the state where an electric field E is applied and in which both anchoring layers 13 are regions 13A having weak anchoring ability It is a top view which shows the relationship of the wiring direction of a line, and the orientation of a liquid crystal molecule. In the first embodiment, an electrode using a liquid crystal compound Lp with positive dielectric anisotropy and in the state where an electric field E is applied, and in the case where both anchoring layers 13 are regions 13B having strong anchoring ability, It is a top view which shows the relationship of the wiring direction of a line, and the orientation of a liquid crystal molecule. It is sectional drawing which shows schematic structure of 2nd Embodiment of the liquid crystal display element 10 of this invention, and the backlight unit 11 for a display, polarizing plate 12A, and polarizing plate 12B. It is a top view which shows two-section pattern shape regarding the arrangement | positioning of Cr comb-tooth electrode for IPS cells of an Example, and arrangement | positioning of both anchoring layers of a two-section pattern. Two pixels 18 are formed on one alignment substrate. The comb-tooth electrodes are arranged at regular intervals along the direction X in a plane parallel to the substrate. FIG. 13 is a plan view showing the relationship between the wiring direction of the electrode line 15A and the polarization direction of the polarizing plate 12A under the first condition in the method for determining the presence or absence of alignment when no voltage is applied in Example. FIG. 13 is a plan view showing the relationship between the wiring direction of the electrode wire 15A and the polarization direction of the polarizing plate 12A under the second condition in the method for determining the presence or absence of alignment when no voltage is applied in Example.

  In the present specification, in order to indicate one or both of "acrylic" and "methacrylic", it may be written as "(meth) acrylic". Similarly, it may be written as "(meth) acrylate" to indicate one or both of "acrylate" and "methacrylate", and to indicate one or both of "acryloxy" and "methacryloxy". It may be written as "(meth) acryloxy".

<1. Curable composition of the present invention>
The curable composition of the present invention is a curable composition containing a polyfunctional carboxyl compound (A), a polyfunctional epoxy compound (B) and a surfactant (C).

  The content of the surfactant (C) in the curable composition of the present invention is 3 to 100 parts by weight based on 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B). It is. When it is in this range, the recoatability of the portion not irradiated with ultraviolet light is poor in the recoatability of the curable composition of the present invention, and it is possible to improve the recoatability by ultraviolet irradiation. The content of the surfactant (C) in the curable composition of the present invention is 5 to 50 parts by weight based on 100 parts by weight of the total of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B). In the case of the above, it is further preferable because the change in recoatability by ultraviolet irradiation can be increased with a small exposure amount.

  The content of the polyfunctional epoxy compound (B) in the curable composition of the present invention is preferably 20 to 80 wt% of the total amount of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B). . Within this range, the cured film made of the curable composition of the present invention has good resistance to the solvent contained in the strong anchoring film-forming material. Therefore, when applying the material for forming a strong anchoring film, it is possible to prevent the penetration of the cured film into the region not irradiated with the ultraviolet light.

<1-1. Polyfunctional Carboxyl Compound (A)>
The polyfunctional carboxyl compound (A) used in the present invention is a compound having three or more carboxyl groups per molecule.

  The polyfunctional carboxyl compounds (A) may be used alone or in combination of two or more.

  Examples of polyfunctional carboxyl compounds (A) are polyesteramide acid (A1) and carboxyl group-containing polymer (A2). These polyfunctional carboxyl compounds (A) are easy to obtain raw materials and manufacture of compounds, and a curable composition containing the polyfunctional carboxyl compound (A) has a multifunctional epoxy compound (B) and surface activity. The compatibility with the agent (C) is good. Furthermore, since polyester amic acid (A1) has high ultraviolet absorptivity, it has an effect of reducing ultraviolet ray damage to the base in the ultraviolet irradiation step after forming a cured film of the present invention, polyester amic acid (A1) is particularly preferable. preferable.

<1-1-1. Polyester amic acid (A1)>
The polyesteramide acid (A1) used in the present invention is a reaction product obtained by reacting tetracarboxylic acid dianhydride (a11), diamine (a12) and polyvalent hydroxy compound (a13) as essential raw materials is there. Furthermore, in addition to these, one or more selected from a monohydric alcohol (a14) and a styrene-maleic anhydride copolymer (a15) may be added to the raw material.

  The method of adding polyesteramide acid (A1) to the curable composition of the present invention may add the solution after polymerization reaction as it is, or concentrate the solution to take out the solid content and add only the solid content. .

<1-1-1-1. Tetracarboxylic acid dianhydride (a11)>
Examples of tetracarboxylic acid dianhydrides (a11) used in the present invention are aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aliphatic tetracarboxylic acid dianhydrides.

  Specific examples of the aromatic tetracarboxylic acid dianhydride are 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2 3,3,3 ', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl sulfone tetracarboxylic acid Acid dianhydride, 2,3,3 ', 4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-Diphenylether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylethertetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluo Propane dianhydride, and ethylene glycol bis (anhydrotrimellitate); specific examples of alicyclic tetracarboxylic acid dianhydride are cyclobutane tetracarboxylic acid dianhydride, methyl cyclobutane tetracarboxylic acid dianhydride, Cyclopentane tetracarboxylic acid dianhydride and cyclohexane tetracarboxylic acid dianhydride; specific examples of aliphatic tetracarboxylic acid dianhydride are ethane tetracarboxylic acid dianhydride and butane tetracarboxylic acid dianhydride is there.

  Among these, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3, 4-Dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate), and butanetetracarboxylic acid dianhydride are preferred, and 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic acid dianhydride, and butanetetracarboxylic acid dianhydride are particularly preferred. The cured film formed using the curable composition containing polyester amic acid (A1) which contains one or more selected from these as a raw material has high light transmittance.

  As the tetracarboxylic acid dianhydride (a11), the above compounds may be used alone, or two or more may be mixed and used.

<1-1-1-2. Diamine (a12)>
Examples of the diamine (a12) used in the present invention are diamines having two benzene rings and diamines having four benzene rings.

  Specific examples of diamines having two benzene rings are 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone and 3,4'-diaminodiphenyl sulfone; diamines having two benzene rings Specific examples thereof include bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4 4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane.

  Among these, 3,3'-diaminodiphenyl sulfone is preferable. The polyesteramide acid (A1) containing this as a raw material has good solubility in a solvent.

  As the diamine (a12), the above compounds may be used alone, or two or more may be mixed and used.

<1-1-1-3. Multivalent Hydroxy Compound (a13)>
Specific examples of the polyvalent hydroxy compound (a13) used in the present invention are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene Glycol, tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentane Diol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2. 2-hep Diol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1, 2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine, and triethanolamine.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol are preferable, Particular preference is given to 4-butanediol, 1,5-pentanediol and 1,6-hexanediol. The polyesteramide acid (A1) containing one or more selected from these as a raw material has good solubility in a solvent.

  As the polyvalent hydroxy compound (a13), the above compounds may be used alone, or two or more may be used as a mixture.

<1-1-1-4.1 valent alcohol (a14)>
In addition to tetracarboxylic acid dianhydride (a11), diamine (a12), and polyhydric hydroxy compound (a13), monohydric alcohol (a14) may be further reacted for synthesis of polyesteramide acid (A1) .

  Specific examples of the monohydric alcohol (a14) are methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, 3-ethyl-3-hydroxymethyl oxetane It is.

  Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are preferable, and benzyl alcohol is particularly preferable. The polyesteramide acid (A1) containing one or more selected from these as a raw material has good compatibility with the polyfunctional epoxy compound (B).

  As the monohydric alcohol (a14), the above-mentioned compounds may be used alone, or two or more may be mixed and used.

<1-1-1-5. Styrene-maleic anhydride copolymer (a15)>
In addition to tetracarboxylic acid dianhydride (a11), diamine (a12), and polyvalent hydroxy compound (a13) for the synthesis of polyesteramide acid (A1), a compound having three or more acid anhydride groups is further reacted You may

  A specific example of the compound having three or more acid anhydride groups is styrene-maleic anhydride copolymer (a15). By adding the styrene-maleic anhydride copolymer (a15), the compatibility of the polyesteramic acid (A1) with the polyfunctional epoxy compound (B) can be improved. The styrene / maleic anhydride molar ratio is from 0.5 to 4, preferably from 1 to 3, specifically about 1, about 2 or about 3 is more preferred, about 1 or about 2 is more preferred, about 1 is particularly preferred.

  Examples of commercial products of the styrene-maleic anhydride copolymer (a15) are SMA 1000, SMA 2000, and SMA 3000 (all trade names, Kawa Crude Oil Co., Ltd.). Among these, SMA 1000 having good solubility in a solvent is particularly preferable.

  As the styrene-maleic anhydride copolymer (a15), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-1-1-6. Method for Producing Polyester Amic Acid (A1)>
The polyesteramide acid (A1) used in the present invention is produced by a known production method (for example, described in JP-A-2015-163685). A preferred production method is solution polymerization using a solvent used for the polymerization reaction (hereinafter referred to as "polymerization solvent").

<1-1-2. Carboxyl group-containing polymer (A2)>
The carboxyl group-containing polymer (A2) used in the present invention is a copolymer of a radically polymerizable compound (a21) having a carboxyl group, and another radically polymerizable compound (a22) not having a carboxyl group and an epoxy group. It is.

<1-1-2-1. Radically polymerizable compound having a carboxyl group (a21)>
The radically polymerizable monomer (a21) having a carboxyl group is a compound having at least one carboxyl group in one molecule and having at least one radically polymerizable group.

  Specific examples of the radically polymerizable monomer (a21) having a carboxyl group used in the present invention are (meth) acrylic acid, itaconic acid, citraconic acid, fumaric acid and maleic acid.

  Among these, (meth) acrylic acid and itaconic acid are preferable, and (meth) acrylic acid is particularly preferable. The curable composition containing a carboxyl group-containing polymer (A2) obtained by polymerizing a mixture containing one or more selected from these is excellent in curability.

<1-1-2-2. Other radically polymerizable compound (a22)>
The other radically polymerizable monomer (a22) used in the present invention is a compound having no carboxyl group and no epoxy group and having at least one radically polymerizable group in one molecule.

Examples of such radically polymerizable monomers include (meth) acrylate compounds having an aliphatic group, (meth) acrylate compounds having an aromatic group, and (meth) a structure represented by the following formula (B-11) Acrylate compounds, other (meth) acrylate compounds, N-substituted maleimide compounds, macromonomers, styrene, methylstyrene, vinyltoluene, chloromethylstyrene, indene, (meth) acrylamide, and N-acryloylmorpholine.

  Specific examples of (meth) acrylate compounds having an aliphatic group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec -Butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) Specific examples of (meth) acrylate compounds having an aromatic group; and phenyl (meth) acrylates and benzyl (meth) acrylates; (meth) having a structure represented by Formula (B-11) Acrylate Specific examples of compounds are 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate and mono (meth) acryloxypropyl modified polydimethylsiloxane; specific examples of other (meth) acrylate compounds are Methoxy polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol mono (meth) acrylate. Specific examples of N-substituted maleimide compounds are N-phenyl maleimide and N-cyclohexyl maleimide. Specific examples of macromonomers are polystyrene macromonomers and polymethyl methacrylate macromonomers.

  Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) acrylate, and N-cyclohexyl maleimide are preferable, and methyl (meth) Acrylate, n-butyl (meth) acrylate and N-cyclohexyl maleimide are more preferred. The curable composition containing the carboxyl group-containing polymer (A2) obtained by polymerizing a mixture containing one or more selected from these is excellent in chemical resistance.

  As the other radical polymerizable monomer (a22) used in the present invention, the above-mentioned compounds may be used alone, or two or more may be mixed and used.

<1-1-2-3. Method for producing carboxyl group-containing polymer (A2)>
The carboxyl group-containing polymer (A2) used in the present invention is produced by a known production method. The preferred production method is a radical polymerization method in solution using a solvent. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but it is usually in the range of 50 to 150 ° C. The polymerization time is also not particularly limited, but is usually in the range of 1 to 24 hours. Also, the polymerization can be carried out under any pressure, reduced pressure or atmospheric pressure. The production method is solution polymerization using a polymerization solvent.

<1-2. Multifunctional Epoxy Compound (B)>
The polyfunctional epoxy compound (B) used in the present invention is a compound having three or more epoxy groups per molecule.

  The polyfunctional epoxy compounds (B) may be used alone or in combination of two or more.

  Examples of polyfunctional epoxy compounds (B) are phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, glycidyl ether type epoxy compounds (B1), bisphenol A novolac type epoxy compounds, aliphatic polyglycidyl ether, alicyclic aliphatic It is an epoxy compound and an epoxy group containing polymer (B2).

  Among these, glycidyl ether type epoxy compounds (B1) and epoxy group-containing polymers (B2) are preferable. The curable composition containing these polyfunctional epoxy compounds (B) has good compatibility in the composition with respect to the polyfunctional carboxyl compound (A) and the surfactant (C). Furthermore, a glycidyl ether type epoxy compound (B1) having high thermal decomposition resistance by heating at the time of forming a strong anchoring film after forming a cured film of the present invention is particularly preferable.

<1-2-1. Glycidyl ether type epoxy compound (B1)>
Preferred specific examples of the glycidyl ether type epoxy compound (B1) are 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4-]. (2,3-Epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [4- [4 1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane.

  Examples of commercial products of these glycidyl ether type epoxy compounds (B1) are Techmore VG3101L (trade name, PRINTEC CO., LTD.), EPPN-501H, 502H (all trade names, Nippon Kayaku Co., Ltd.) and jER 1032H60 (JAPAN) Brand name, Mitsubishi Chemical Corporation). Techmore VG 3101 L is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1 It is a mixture of -methylethyl] phenyl] ethyl] phenoxy] -2-propanol.

<1-2-2. Epoxy group-containing polymer (B2)>
The epoxy group-containing polymer (B2) used in the present invention is a polymer containing a radically polymerizable compound (b21) having an epoxy group as a raw material.

  Among polymers containing the radically polymerizable compound (b21) having an epoxy group as a raw material, a radically polymerizable compound (b21) having an epoxy group, and other radically polymerizable compounds having no carboxyl group and no epoxy group ( The copolymer of b22) is preferable because of high compatibility with the polyfunctional carboxyl compound (A) and the surfactant (C).

<1-2-2-1. Radically Polymerizable Compound Having an Epoxy Group (b21)>
The radically polymerizable monomer (b21) having an epoxy group is a compound having at least one epoxy group in one molecule and having at least one radically polymerizable group.

  Specific examples of the radically polymerizable monomer (a21) having a carboxyl group used in the present invention are glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.

  Among these, glycidyl (meth) acrylate is preferable, and glycidyl methacrylate is particularly preferable. The curable composition containing the epoxy group-containing polymer (B2) obtained by polymerizing a mixture containing one or more selected from these is excellent in curability.

<1-2-2-2. Other radically polymerizable compounds (b22)>
Another radically polymerizable compound (b22) is a compound which does not have a carboxyl group and an epoxy group, and has one or more radically polymerizable groups per molecule.

  The specific example of another radically polymerizable compound (b22) is a compound as described in the specific example of the above-mentioned other radically polymerizable compound (a22).

  Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) acrylate, and N-cyclohexyl maleimide are preferable, and methyl (meth) Acrylate, n-butyl (meth) acrylate and N-cyclohexyl maleimide are more preferred. The curable composition containing the carboxyl group-containing polymer (B2) obtained by polymerizing a mixture containing one or more selected from these is excellent in chemical resistance.

<1-2-2-3. Method of producing epoxy group-containing polymer (B2)>
The epoxy group-containing polymer (B2) used in the present invention is produced by a known production method. The preferred production method is a radical polymerization method in solution using a solvent. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but it is usually in the range of 50 to 150 ° C. The polymerization time is also not particularly limited, but is usually in the range of 1 to 24 hours. Also, the polymerization can be carried out under any pressure, reduced pressure or atmospheric pressure. The production method is solution polymerization using a polymerization solvent.

<1-3. Surfactant (C)>
Examples of the surfactant (C) used in the present invention are anionic, cationic, nonionic and fluorinated surfactants.

  An alignment substrate provided with a cured film made of the curable composition of the present invention is produced through the step of applying a material for forming a strong anchoring film after the formation of the cured film of the present invention. Therefore, the surfactant (C) used for the curable composition of the present invention is preferably a polymerizable surfactant which gives a cured film having a good resistance to the solvent contained in the material for forming a strong anchoring film. Such properties are obtained because the polymerizable surfactant is polymerized by heating and ultraviolet irradiation.

  Examples of the polymerizable surfactant are a reactive fluorine-containing oligomer, a fluorine-containing prepolymer, and a silicon polyether acrylate.

  A commercial example of a solution containing a reactive fluorine-containing oligomer is Megafuck RS-72-K (trade name, DIC Corporation), and a commercial example of a solution containing a fluorine-containing prepolymer is Tergent 601 AD. (Trade name, Neos Co., Ltd.), and a commercial example of silicone polyether acrylate is TEGO Rad 2200N (trade name, Evonik Japan Ltd.).

  Among these polymerizable surfactants, reactive fluorine-containing oligomers giving a curable composition capable of suppressing streak unevenness caused by a difference in level during application of a curable composition, and excellent in slip property of a cured film, and curing with less damage It is particularly preferable to use a silicone polyether acrylate which gives a liquid composition, because it can reduce the display defect area at the time of mass production of liquid crystal display elements.

<1-4. Additive (D)>
Various additives (D) may be added to the curable composition of the present invention to improve adhesion, heat resistance, curability, resistance to ultraviolet light degradation, curability, scratch resistance, and low temperature curability. it can. Examples of the additive (D) include coupling agents such as silane coupling agents, antioxidants such as hindered phenols, hindered amines, phosphorus and sulfur compounds, epoxy curing agents, ultraviolet light absorbers, thermal crosslinking agents And epoxy compounds other than polyfunctional epoxy compounds (B), polyfunctional (meth) acrylate compounds, and photopolymerization initiators.

<1-4-1. Coupling agent>
The curable composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion of the formed cured film and the substrate.

  Specific examples of such coupling agents are 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (eg, trade name; Thyraace S510, JNC Co., Ltd.) ), 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Thyraace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name: Thyraace S810, JNC Corporation) And silane-based coupling agents such as polymers of 3-glycidyloxypropyltrimethoxysilane (eg, trade name; COATOSIL MP 200, Momentive Performance Materials GK); Mini um aluminum coupling agent diisopropylate; and tetraisopropyl bis (dioctyl phosphite) is a titanate coupling agents such as titanates.

  Among these, a polymer of 3-glycidyl oxypropyl trimethoxysilane is preferable because the effect of improving the adhesion is large.

  The content of the coupling agent is 0.01 parts by weight or more and 10 parts by weight with respect to 100 parts by weight in total of the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C). The following is preferable because the adhesion of the formed cured film and the substrate is improved while maintaining other properties.

<1-4-2. Antioxidant>
The curable composition of the present invention may further contain an antioxidant from the viewpoint of improving heat resistance.

  To the curable composition of the present invention, an antioxidant such as a hindered phenol type, hindered amine type, phosphorus type or sulfur type compound may be added. Among these, hindered phenols are preferred from the viewpoint of weatherability. Specific examples of the antioxidant include Irganox 1010, Irganox 1010 FF, Irganox 1035, Irganox 1035 FF, Irganox 1076, Irganox 1076 FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1526, Irganox 1520 L, Irganox 24510, Uhrivatives Japan KK), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all trade names, ADEK Co., Ltd.) A). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

  The antioxidant is added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C).

1-4-3. Epoxy curing agent>
The curable composition of the present invention may further contain an epoxy curing agent from the viewpoint of further improving the curability.

  Examples of epoxy curing agents are acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, etc. Acid anhydride-based curing agent or imidazole-based curing agent, which is highly heat-sensitive acid generator, highly compatible with polyfunctional carboxyl compound (A), multifunctional epoxy compound (B) and surfactant (C) .

  Specific examples of the acid anhydride curing agent are maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and aliphatic dicarboxylic acid anhydrides such as hexahydrotrimellitic acid anhydride; And aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride are particularly preferable, which can improve the curability while maintaining other properties.

  Specific examples of the imidazole-based curing agent are 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a Benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these, 2-undecylimidazole, which has good compatibility with the polyfunctional carboxyl compound (A), is particularly preferable.

  The preferable ratio of the epoxy curing agent to the polyfunctional epoxy compound (B) is 0.1 to 60 parts by weight of the epoxy curing agent to 100 parts by weight of the polyfunctional epoxy compound (B).

1-4-4. UV absorber>
The curable composition of the present invention may further contain an ultraviolet absorber, from the viewpoint of further improving the ultraviolet deterioration resistance of the formed cured film.

  Specific examples of UV absorbers are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571 and TINUVIN 765 (all trade names, BASF Japan Ltd.).

  The ultraviolet absorber is used by adding 0.01 to 10 parts by weight to 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C).

1-4-5. Thermal crosslinker>
The curable composition of the present invention may further contain a thermal crosslinking agent from the viewpoint of further improving the curability and heat resistance.

  Specific examples of commercially available thermal crosslinking agents include Nikalac MW-30HM, Nikalac MW-100LM, Nikalac MX-270, Nikalac MX-280, Nikalac MX-290, Nikalac MW-390, Nikalac MW-750LM (all of which are commercial products) Name, Sanwa Chemical Co., Ltd.).

  The thermal crosslinking agent is used by adding 0.1 to 10 parts by weight to 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C).

1-4-6. Epoxy compounds other than polyfunctional epoxy compounds (B)>
The curable composition of the present invention may further contain an epoxy compound other than the polyfunctional epoxy compound (B) from the viewpoint of improving the curability.

  It is preferable to add 50 parts by weight or less of an epoxy compound other than the polyfunctional epoxy compound (B) with respect to 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B).

  Examples of epoxy compounds other than the polyfunctional epoxy compound (B) are bisphenol A epoxy compounds and bisphenol F epoxy compounds.

  Specific examples of commercial products of bisphenol A type epoxy compounds are jER 828, 1004, 1009 (all are trade names, Mitsubishi Chemical Corporation); specific examples of commercial products of bisphenol F type epoxy compounds are jER 806, 4005P (All trade names are Mitsubishi Chemical Corporation).

1-4-7. Multifunctional (Meth) Acrylate Compound>
The curable composition of the present invention may further contain a polyfunctional acrylate compound from the viewpoint of improving the scratch resistance.

  The polyfunctional (meth) acrylate compound is preferably added in an amount of 20 to 200 parts by weight or less based on 100 parts by weight of the total amount of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B).

Specific examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, glycerol tri (meth) acrylate, Glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, and ε-caprolactone modified tris- (2- (meth) acrylate Trifunctional (meth) acrylate compounds such as hydroxyethyl (isocyanurate);
Tetrafunctional (meta) such as ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, and diglycerin EO modified tetraacrylate ) Acrylate compounds;
A pentafunctional (meth) acrylate compound such as dipentaerythritol penta (meth) acrylate;
Hexafunctional (meth) acrylate compounds such as dipentaerythritol hexaacrylate;
And polyfunctional (meth) acrylate compounds having a carboxyl group. One or more of these can be used.

Among these specific examples, a tetrafunctional (meth) acrylate compound, a pentafunctional (meth) acrylate compound, a hexafunctional (meth) acrylate compound, and a polyfunctional (meth) compound having a carboxyl group are highly effective in improving the scratch resistance. Acrylate compounds are preferred, and pentafunctional (meth) acrylate compounds and hexafunctional (meth) acrylate compounds are more preferred.
1-4-8. Photopolymerization initiator>
The curable composition of the present invention may further contain a photopolymerization initiator from the viewpoint of improving the low temperature curability. When adding a photoinitiator, it can be used together with a polyfunctional (meth) acrylate compound, and can reduce a calcination temperature by performing an ultraviolet irradiation process.

Specific examples of the photopolymerization initiator are benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2 -Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (eg, trade name; IRG) CURE 907, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (eg, trade name; IRGACURE 369, BASF Japan Ltd.), 4-dimethylaminobenzoic acid Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (for example, trade name; IRGACURE OXE01, BASF Japan Ltd.), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-Carbazol-3-yl] -1- (O-acetylene) Oxime (for example, trade name; IRGACURE OXE 02, BASF Japan Ltd.), IRGACURE OXE 03 (trade name, BASF Japan Ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) Phenylthio] phenyl] -2- (O-acetyloxime) (for example, trade name; Adeka Cruz NCI-930, ADEKA Corporation), Adeka Arcules NCI-831 (trade name, ADEKA Corporation), Adeka Optomer N -1919 (trade name, ADEKA Co., Ltd.), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]- 2,6-Di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- ( 4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercap Benzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1, 2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl) -2-Dimethylaminopropionyl) carbazole, 3,6-bi (2-Methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-) Difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. One or more of these can be used.

  Among the specific examples of these photopolymerization initiators, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and 1,2-propanedione, 1- [4 When one or more selected from-[4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is used, the effect of improving the low temperature curability of the curable composition is less Expressed in quantity. The addition amount of the photopolymerization initiator suitable for expressing this effect is 1 with respect to 100 parts by weight in total of the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C). To 20 parts by weight.

<1-5. Solvent optionally added to the curable composition>
A solvent may be added to the curable composition of the present invention in addition to the polymerization solvent. The solvent optionally added to the curable composition of the present invention (hereinafter referred to as “solvent for dilution (E)”, hereinafter the polymerization solvent and the solvent for dilution (E) are generically referred to as “solvent for composition” Preferably, the solvent can dissolve the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B) and the surfactant (C). When the curable composition contains the above-mentioned additive (D), the solvent for dilution (E) is preferably a solvent capable of further dissolving the additive (D).

  The diluting solvent (E) is preferably a mixed solvent containing at least one of compounds having a boiling point of 100 to 200 ° C. or 20% by weight or more of the compound. Specific examples of the compound having a boiling point of 100 to 200 ° C. are 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, oxy oxy Ethyl acetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxy Propion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monob Ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Tyrene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, and N, N-dimethylacetamide.

  Among these, PGMEA having good spreadability at the time of application of the curable composition and high versatility is preferable.

<1-6. Storage of Curable Composition>
When the curable composition of the present invention is stored in the dark at a temperature of -30 ° C to 25 ° C, the stability over time of the composition becomes good, which is preferable. It is more preferable to store at -10 ° C to 20 ° C.

<2. Cured film obtained from curable composition>
The curable composition of the present invention mixes the polyfunctional carboxyl compound (A), the polyfunctional epoxy compound (B), and the surfactant (C), and further, according to the intended properties, further additives (D) and The solvent for dilution (E) can be selected and added if necessary, and they can be obtained by mixing and dissolving them uniformly.

  By applying the curable composition obtained as described above to the surface of the substrate, when the curable composition contains a solvent for the composition, the solvent for the composition is further subjected to steps such as a heating step and a pressure reducing step. The coating film can be formed by removing the Specific examples of the method of applying the curable composition to the substrate surface are a spin coating method, a roll coating method, a dipping method, and a slit coating method. The coating is then prebaked in a hot plate, an oven or the like. Pre-bake conditions vary depending on the types and blending proportions of the components, but are usually 70 to 150 ° C., 1 to 5 minutes for a hot plate, and 5 to 15 minutes for an oven.

  Finally, the cured film may be obtained by heat treatment at 100 to 250 ° C., preferably 120 to 230 ° C., for a hot plate for 5 to 60 minutes, or for an oven for 20 to 90 minutes to completely cure the coating. it can.

  The cured film thus obtained is excellent in weak anchoring property due to the surface free energy reducing ability of the surfactant (C), and the recoating property of the material for forming a strong anchoring film on the cured film is poor. is there. Furthermore, it is possible to improve the recoat property of the material for strong anchoring film formation with respect to a cured film by irradiating an ultraviolet-ray. Hereinafter, the region of the cured film irradiated with ultraviolet light is referred to as "exposed part", and the region of the cured film not irradiated is referred to as "unexposed part".

  Further, the cured film thus obtained has high chemical resistance due to intermolecular crosslinking by curing of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B). Therefore, when the material for forming a strong anchoring film is applied onto the cured film, the weak anchoring property is reduced due to the solvent (for example, N-methylpyrrolidone) contained in the material for forming a strong anchoring film touching the cured film. It is possible to suppress. Furthermore, the recoatability of the material for strong anchoring film formation with respect to a cured film is improved by the alcoholic hydroxyl group which a carboxyl group and an epoxy group produce by reaction. Therefore, the recoatability of the exposed area is improved.

  As described above, the unexposed area of the cured film has high weak anchoring property and poor recoatability. The exposed portion has good recoatability. Both the unexposed area and the exposed area have high solvent resistance. Therefore, it is possible to increase the difference in recoatability on the unexposed area and the exposed area of the cured film, and the cured film is excellent in pattern formation ability with strong anchoring ability and strong anchoring ability. Since the non-patterned portion having the above-mentioned structure withstands the solvent of the material for forming a strong anchoring film, the weak anchoring property is excellent.

<3. Substrate with Both Anchoring Layers>
A single substrate is obtained by performing a pattern forming step with strong anchoring ability including the following steps (P1) to (P3) on the substrate on which the cured film is formed (hereinafter referred to as "substrate with cured film") A substrate (hereinafter referred to as “substrate with both anchoring layers”) having regions of both the region having weak anchoring ability and the region having strong anchoring ability can be obtained.
(P1) a first ultraviolet irradiation step of irradiating a part of the cured film (101) with ultraviolet light (201);
(P2) applying a material for forming a strong anchoring film on the cured film (101);
(P3) A second ultraviolet irradiation step of irradiating linearly polarized ultraviolet light (202).

  Although the order of the said process (P1)-(P3) may include another process on the way, it is performed in order of (P1), (P2), (P3).

  The schematic of process (P1)-(P3) is shown in FIG.

  The step (P1) is a first ultraviolet irradiation step of irradiating a part of the weak anchoring film with ultraviolet rays, and forms an exposed portion (101A) and an unexposed portion (101B) of the ultraviolet rays (201). An example of a method of irradiating a part of the weak anchoring film with ultraviolet light is a method of using a photomask.

  The step (P2) is a step of applying a material for forming a strong anchoring film on the film (101). The strong anchoring film can be formed by a known method of forming a liquid crystal alignment film. That is, the liquid crystal aligning agent is the above-mentioned strong anchoring film forming material.

  The example of the formation method of a liquid crystal aligning film is the above-mentioned rubbing method and the photo-alignment method. Among these two methods, preferred is the photoalignment method capable of suppressing the decrease in the weak anchoring ability of the region of the alignment substrate of the present invention having weak anchoring ability in the alignment treatment step (P4). The second ultraviolet irradiation step (P3) is an alignment treatment step of the photoalignment method.

  Examples of the photoalignment method include a method using a photoisomerization-type material (for example, JP-A-2005-275364), a method using a photodimerization-type material (for example, JP-A-10-251646), and a photolysis type The method of using the material of (For example, Unexamined-Japanese-Patent No. 9-297313). In order to maintain weak anchoring ability of the region having weak anchoring ability, a method using a photoisomer type material having high sensitivity at an exposure wavelength of 300 nm or more and a light dimerization type material among these light alignment methods The method to be used is preferable, and the method to use a photoisomerizable material having high sensitivity at an exposure wavelength of 350 nm or more is particularly preferable. In the following examples, a method of using a photoisomerization type material is used.

  A known application method can be used as the application method in the step (P2). Examples of known coating methods are spin coating, slit coating, gravure offset printing, flexographic printing, and inkjet.

  Since a difference in recoatability on the unexposed area (101B) and the exposed area (101A) is generated by the above-mentioned process (P1), a coating film is easily formed on the exposed area (101A). Spin-coating method capable of removing the liquid applied on the unexposed portion (101B) by centrifugal force, and gravure offset printing method, flexographic printing method, and inkjet method capable of selectively applying on the exposed portion (101A) Is preferred.

  The linearly polarized ultraviolet light (202) in the step (P3) is preferably light with a wavelength of 250 nm or more and 450 nm or less, and more preferably light with a wavelength of 300 nm or more and 400 nm or less. The reason is to suppress the decrease in weak anchoring ability of the unexposed area (101B) by the linearly polarized ultraviolet light (202) to be irradiated and to prevent the exposure under visible light.

  In addition to the above steps (P1) to (P3), a coating film formed by applying a material for forming a strong anchoring film between the steps (P2) and (P3) or after the step (P3) It is desirable to include the step (P4) of heating and firing (102). By carrying out the step (P4), the scratch resistance of the pattern body (103) having strong anchoring ability is improved. In general, when the photoalignment method is a method using a photodimerization type material or a method using a photolytic type material, step (P4) is performed between steps (P2) and (P3). When the photoalignment method is a method using a photoisomerization type material, the step (P4) is carried out after the step (P3). In the embodiment described later, the step (P4) is carried out after the step (P3).

<3. Liquid Crystal Display Device Having Substrates with Both Anchoring Layers>
The liquid crystal compounds include a positive type in which the dielectric anisotropy is positive and a negative type in which the dielectric anisotropy is negative. In the positive type liquid crystal compound, dielectric properties are large in the long axis direction of liquid crystal molecules and small in the direction orthogonal to the long axis direction. In a negative liquid crystal compound, dielectric properties are small in the long axis direction of liquid crystal molecules and large in the direction orthogonal to the long axis direction. In the following description of the liquid crystal display element, an example using a positive liquid crystal compound will be described.

  In the liquid crystal display element, the above-mentioned strong anchoring film, the above-mentioned weak anchoring film, and the above-mentioned both anchoring layers are present as an alignment film for controlling the alignment direction of liquid crystal molecules. In the liquid crystal display element of the present invention, one of two alignment films facing each other is a strong anchoring film, and the other is both anchoring layers.

  A cured film formed using the curable composition of the present invention can be used as a weak anchoring film.

<3-1. First embodiment>
FIG. 2 is a cross-sectional view showing a schematic configuration of the first embodiment of the liquid crystal display element 10 of the present invention, the backlight unit 11 for display, the polarizing plate 12A, and the polarizing plate 12B. FIG. 3 is a view showing a distribution of alignment directions of liquid crystal molecules in a state where an electric field E is applied, using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment. FIG. 4 shows the wiring directions of the electrode lines and the alignment directions of liquid crystal molecules in the vicinity of both anchoring layers in the state where no electric field is applied, using the liquid crystal compound Lp having positive dielectric anisotropy in the first embodiment. It is a figure which shows a relation. FIG. 5 is a view showing the relationship between the wiring directions of electrode lines and the alignment of liquid crystal molecules in the state where an electric field E is applied using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment. .

  As shown in FIG. 2, the liquid crystal display device of the present invention is disposed opposite to the first substrate (LCP-1) on which both anchoring layers 13 are formed and the both anchoring layers with an interval. It is disposed between the second substrate (LCP-2) on which the strong anchoring film 14 is formed, the two anchoring layers and the strong anchoring film, and transmits or blocks the light by driving liquid crystal molecules. A liquid crystal layer (LCP-3), and a drive electrode layer (LCP-4) for applying an electric field in a direction along the first substrate (LCP-1) and the second substrate (LCP-2) to the liquid crystal molecules ing.

  The first substrate (LCP-1) and the second substrate (LCP-2) are each made of a substrate such as glass and are arranged in parallel with each other at a predetermined interval.

  The polarizing plates 12A and 12B are disposed in cross nicol. For example, the polarization direction of the polarizing plate 12A is the direction Y, and the polarization direction of the polarizing plate 12B is the direction X.

  The drive electrode layer (LCP-4) is provided on one of the first substrate (LCP-1) and the second substrate (LCP-2). As shown in FIG. 2, in the first embodiment, the drive electrode layer (LCP-4) is provided on the first substrate (LCP-1). The drive electrode layer (LCP-4) is formed by arranging a plurality of electrode lines 15A along the surface of the first substrate (LCP-1). In FIG. 2, each electrode line 15A is formed in a straight line so that the wiring direction extends in the direction Y in a plane parallel to the surface of the first substrate (LCP-1). In the drive electrode layer (LCP-4), such electrode lines 15A are arranged at regular intervals along the direction X in a plane parallel to the surface of the first substrate (LCP-1).

<3-2. Second embodiment>
In the second embodiment, as shown in FIG. 8, a drive electrode layer (LCP-4) is provided on the second substrate (LCP-2). The other configuration is the same as that of the first embodiment.

  Next, the present invention will be specifically described by way of Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited at all by these Examples.

  The compounds used in Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples are described for each component.

Tetracarboxylic acid dianhydride (a11):
a11-1: butanetetracarboxylic acid dianhydride (trade name: RIKACID BT-100, Shin Nippon Rika Co., Ltd., hereinafter abbreviated as “BT-100”)
Diamine (a12):
a12-1: 3,3'-diaminodiphenyl sulfone (hereinafter referred to as "DDS")
Polyvalent hydroxy compound (a13):
a13-1: 1,4-butanediol
Monohydric alcohol (a14):
a14-1: benzyl alcohol
Styrene-maleic anhydride copolymer (a15):
a15-1: SMA 1000 (manufactured by Kawa Crude Oil Co., Ltd.)
Polymerization solvent used for the reaction of polyesteramide acid (A1):
PGMEA

Carboxyl group-containing polymer (A2):
A2-1: solid content concentration of 30% by weight PGMEA solution (hereinafter referred to as “co-weight”: copolymer of methacrylic acid and butyl methacrylate (raw material weight ratio methacrylic acid / n-butyl methacrylate = 20/80, weight average molecular weight 10,000) Described as combined solution (A2-1)

Trifunctional or higher glycidyl ether type epoxy compound (B1):
B1-1: Techmore VG3101L (trade name, PRINTEC, Inc., hereinafter abbreviated as "VG3101L")

Epoxy group-containing polymer (B2):
B2-1: solid content concentration of 30 wt% PGMEA solution (hereinafter "co-weight": copolymer of glycidyl methacrylate and butyl methacrylate (raw material weight ratio glycidyl methacrylate / n-butyl methacrylate = 20/80, weight average molecular weight 10,000) Described as combined solution (B2-1)

Surfactant (C):
C-1: A solution containing a reactive fluorine-containing oligomer, Megafuck RS-72-K (trade name, DIC Corporation, hereinafter abbreviated as "RS-72-K", active ingredient 30% by weight, solvent PGMEA)
C-2: a solution containing a fluorine-containing prepolymer, Ftergent 601 AD (trade name, Neos, Inc., hereinafter abbreviated as “601 AD”, 25 wt% of active ingredient, solvent PGMEA)
C-3: TEGO Rad 2200 N (trade name, Evonik Japan Ltd., hereinafter abbreviated as “Rad 2200 N”), which is a silicone polyether acrylate

Additive (D):
D-1: COATOSIL MP 200 (trade name, Momentive Performance Materials GK) which is a polymer of 3-glycidyl oxypropyl trimethoxysilane
D-2: Alonix M-402 (trade name, Toagosei Co., Ltd., "M-" below, which is a mixture of dipentaerythritol pentaacrylate which is a pentafunctional acrylate and dipentaerythritol hexaacrylate which is a hexafunctional acrylate Abbreviated as "402"
D-3: 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) and Adekarkles NCI-930 (trade name, ADEKA Corporation, hereafter abbreviated as "NCI-930")

  The weight average molecular weight in the present specification is a value in terms of polystyrene calculated by the GPC method (column temperature: 35 ° C., flow rate: 1 mL / min). Standard polystyrene includes polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 from Agilent Technologies, Inc.), and PLgel MIXED-D (trade name, Agilent Technologies, Inc.) for columns. It can be used and measured using tetrahydrofuran as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalog published value.

[Preparation of a curable composition]
Synthesis Example 1
A solid content concentration of 30% by weight PGMEA solution (A1-1) of polyesteramide acid was synthesized as follows.
In a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging port, and a nitrogen gas inlet, 604.80 g of PGMEA dehydrated and purified as a polymerization solvent, and BT as a tetracarboxylic acid dianhydride (a11) 34.47 g of -100, 164.11 g of SMA 1000 as the styrene-maleic anhydride copolymer (a15), 50.17 g of benzyl alcohol as the monohydric alcohol (a14), 1,4 as the polyhydroxy compound (a13) 10.45 g of butanediol was charged and stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Thereafter, the solution after reaction is cooled to 25 ° C., 10.80 g of DDS and 25.20 g of PGMEA are added as diamine (a12), stirred at 20-30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour By cooling to 30 ° C. or less, a solid content concentration 30% by weight PGMEA solution (A1-1) of pale yellow transparent polyester amic acid was obtained. The weight average molecular weight of the solid content measured by GPC was 10,000.

Example 1
Solid content concentration of 30% by weight PGMEA solution (A1-1), VG3101L, RS-72-K, and PGMEA of polyesteramide acid obtained in Synthesis Example 1 in proportions (unit: g) described in Table 1-1 The mixture was dissolved and filtered through a membrane filter (0.2 μm) to obtain a curable composition.

  Incidentally, the total amount of the solvent contained in this curable composition is the polymerization solvent contained in the 30% by weight PGMEA solution (A1-1) having a solid content concentration of polyesteramide acid, the solvent contained in RS-72-K, and the dilution. The total amount of PGMEA for the solvent (E) was prepared so that the solid concentration would be about 2.5% by weight in this step. The same applies to the second embodiment and below and the comparative example.

[Fabrication of a cured comb electrode substrate]
The resulting curable composition is spin-coated at 2,000 rpm for 10 seconds on a glass substrate with Cr comb electrode for IPS cell (hereinafter referred to as "comb electrode substrate"), and heated for 2 minutes on a hot plate at 100 ° C. By prebaking, a coated comb electrode substrate was obtained. Next, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a cured film-attached comb electrode substrate having a film thickness of about 50 nm.

[Preparation of a material for forming a strong anchoring film (S1)]
In a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, 1.4184 g of 4,4'-diaminoazobenzene, 1,4-bis (4-aminophenyl) butane, 0.1. 5736 g, 0.1281 g of 1,4-bis (4-aminophenyl) piperazine, and 44.0 g of dehydrated N-methylpyrrolidone (hereinafter referred to as "NMP") were charged, and dissolved by stirring under a stream of dry nitrogen. Next, 3.8799 g of 1,8-bis (3,4-dicarboxylic acid) octane dianhydride and 20.0 g of dehydrated NMP were charged, and stirring was continued at room temperature for 24 hours to obtain a reaction solution. To the reaction solution was added 20.0 g of ethylene glycol monobutyl ether to obtain a polyamic acid solution having a solid concentration of 6% by weight. This polyamic acid solution is referred to as (PA1). The weight average molecular weight of the polyamic acid contained in (PA1) was 10,000.

  In a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, 1.9123 g of 1,4-bis (4-aminophenyl) piperazine, 4,4'-diaminodiphenyl ether 0. 8561 g, 0.3082 g of 1,4-phenylenediamine, and 44.0 g of dehydrated NMP were added, and dissolved by stirring under a stream of dry nitrogen. The mixture was charged with 1.8354 g of 1,2,3,4-butanetetracarboxylic acid dianhydride, 1.0880 g of pyromellitic dianhydride, and 20.0 g of dehydrated NMP, and stirring was continued at room temperature for 24 hours. To the reaction solution was added 30.0 g of ethylene glycol monobutyl ether to obtain a polyamic acid solution having a polymer solid concentration of 6% by weight. This polyamic acid solution is referred to as (PA2). The weight average molecular weight of the polyamic acid contained in (PA2) was 50,000.

A polyamic acid solution (PA1), a polyamic acid solution (PA2), and NMP were charged at the following weight, mixed and dissolved to prepare a material (S1) for forming a strong anchoring film having a polymer solid concentration of 4% by weight.

9.00 g of polyamic acid solution (PA1) with a solid concentration of 6% by weight
Polyamide acid solution (PA2) with a solid concentration of 6% by weight 21.00 g
NMP 15.00g

[Determination of presence or absence of coating film formation on unexposed area]
As a process (P1), the low pressure mercury lamp EUV200WS-60 (brand name, sen special light source Ltd.) which irradiates the ultraviolet-ray containing light with a wavelength of 185 nm and light with a wavelength of 254 nm The pattern exposure is performed using a photoexposure apparatus PHOTO SURFACE PROCESSOR PL 2003 N-12 (trade name, Sen Special Light Source Co., Ltd.) and a photomask of a two-section pattern, and a substrate with a pattern exposure film having different recoatability in exposed and unexposed areas. I got The exposure dose was measured with a UV integrated actinometer UIT-150 (trade name, Ushio Electric Co., Ltd.) and a light receiver UVD-S254 (trade name, Ushio Electric Co., Ltd.) and was 10 J / cm ^{2 in} light conversion at a wavelength of 254 nm. .

  Subsequently, as the step (P2), the material for forming the strong anchoring film (S1) is applied at 3,000 rpm on the comb-tooth electrode substrate with a pattern exposure film having different recoatability in the exposed area and unexposed area obtained. The film was spin-coated for 2 seconds and prebaked on a hot plate at 70 ° C. for 80 seconds to obtain a polyamic acid coating film and a comb electrode substrate with a pattern exposure film. Since the polyamide acid coating film was observed to have a yellow color, the presence or absence of the coating film formation on the unexposed area was visually confirmed. When the polyamide acid coating film is not formed on the unexposed area, it is judged that the coating film is not formed on the unexposed area, and the polyamide acid coating film is formed regardless of the unexposed area and the exposed area. It was judged that "unformed" was the film formation on the unexposed area. The judgment results are shown in Table 1-1.

[Production of Substrate 1 for Producing Liquid Crystal Display Element]
As a step (P3), using the multilight ML-501C / B (trade name, Ushio Inc.) equipped with an ultra-high pressure mercury lamp and a polarizing plate, the obtained polyamic acid coating film and a comb electrode substrate with a pattern exposure film The light was irradiated with linearly polarized ultraviolet light from the vertical direction. The exposure dose was measured with a UV integrated actinometer UIT-150 (trade name, Ushio Inc.) and a light receiver UVD-S365 (trade name, Ushio Inc.), and it was ² J / cm ^{2 in} light conversion at a wavelength of 365 nm. . Further, post-baking was performed in an oven at 230 ° C. for 20 minutes to obtain a pattern body having a strong anchoring ability and a comb electrode substrate with a cured film. Hereinafter, this substrate is referred to as “substrate 1 for producing a liquid crystal display element”. The polarization direction of the linearly polarized ultraviolet light was perpendicular to the wiring direction of the Cr comb electrode. In this direction, the alignment easy axis of the region having strong anchoring ability in both anchoring layers of the alignment substrate 1a with electrodes for manufacturing a liquid crystal display element manufactured is parallel to the wiring direction of the Cr comb electrode. It becomes.

[Production of Substrate 2 for Producing Liquid Crystal Display Element]
A strong anchoring film forming material (S1) was spin-coated at 2,000 rpm for 10 seconds on a glass substrate, and prebaked on a 70 ° C. hot plate for 80 seconds to obtain a coated glass substrate. Next, using a multilight ML-501C / B (trade name, Ushio Inc.) equipped with an ultra-high pressure mercury lamp and a polarizing plate, a linearly polarized ultraviolet ray was irradiated from the vertical direction to the coated glass substrate. The exposure dose was measured with a UV integrated actinometer UIT-150 (trade name, Ushio Inc.) and a light receiver UVD-S365 (trade name, Ushio Inc.), and it was ² J / cm ^{2 in} light conversion at a wavelength of 365 nm. . Further, the substrate was post-baked in an oven at 230 ° C. for 20 minutes to obtain a substrate with a strongly anchoring film having a film thickness of about 100 nm. Hereinafter, the obtained glass substrate with a strong anchoring film is referred to as “substrate 2 for producing a liquid crystal display element”.

[Preparation of positive-type liquid crystal composition (LC-1)]
The positive type liquid crystal composition (LC-1) was prepared by mixing and dissolving the compounds of the following general formulas (2-1) to (2-9) in the weight ratio described.

[Production of Liquid Crystal Display Device]
The liquid crystal display element manufacturing substrate 1 and the liquid crystal display element manufacturing substrate 2 face each other with the pattern body having strong anchoring ability and the cured film side and the strong anchoring film side facing each other, for manufacturing a liquid crystal display element The wiring direction of the Cr comb electrode of the substrate 1 and the easy alignment axis of the strong anchoring film of the substrate 2 for manufacturing a liquid crystal display element were arranged in parallel. By arranging in this way, of the two anchoring layers of the liquid crystal display element production substrate 1, the alignment easy axis of the region having strong anchoring ability and the alignment easy of the strong anchoring film of the liquid crystal display element production substrate 2 The axes are parallel. Further, an air gap for injecting a positive liquid crystal composition (LC-1) was formed between the two anchoring layers and the strong anchoring film, and they were bonded to each other to prepare an empty cell having a cell thickness of 4 μm. The positive type liquid crystal composition (LC-1) was vacuum-injected into the produced empty cell to produce a liquid crystal display element. Incidentally, when this liquid crystal display element is made to correspond to FIG. 2, the wiring direction of the electrode lines 15A and the alignment easy axis of the strong anchoring film 14 are the direction Y.

[Determination of orientation]
On a light viewer 7000PRO (trade name, Hakuba Photographic Industries, Ltd., hereinafter referred to as "backlight device"), a liquid crystal display element produced was sandwiched between two polarizing plates arranged in cross nicol. Subsequently, the backlight device was turned on, and the light passing through the above-described two polarizing plates and the manufactured liquid crystal display element was visually observed under two conditions. The first condition is that the wiring direction of the comb electrode of the manufactured liquid crystal display element, that is, the easy alignment axis of the strong anchoring film of the substrate 2 for manufacturing a liquid crystal display element is parallel to the polarization direction of the polarizer. . If this condition corresponds to FIG. 2, the polarization direction of the polarizing plate 12A on the backlight device side is the direction Y, and the polarization direction of the other polarizing plate 12B is the direction X. The relationship between the wiring direction of the electrode line 15A and the polarization direction of the polarizing plate 12A is shown in FIG. The second condition is a condition in which the two polarizing plates 12A and 12B of the first condition are rotated 45 degrees counterclockwise in the XY plane. That is, under the second condition, the wiring direction of the comb electrode, that is, the angle between the easy orientation axis of the strong anchoring film of the liquid crystal display element manufacturing substrate 2 and the polarization direction of the polarizing plate on the back light device side is 45 °. is there. The relationship between the wiring direction of the electrode wire 15A and the polarization direction of the polarizing plate 12A is shown in FIG.

  In each of the pattern body forming portion having strong anchoring ability (T1 in FIG. 9) and the pattern body non-forming portion having strong anchoring ability (T2 in FIG. 9), there is no light leakage under the first condition, and When light transmission is observed under the second condition, it is determined that the orientation is "present", and one or more cases where light leakage is observed under the first condition and light transmission is not observed under the second condition The case was judged to be orientation "none". The judgment results are shown in Table 1-1.

<Method of evaluating pattern formability having strong anchoring ability>
Strong when judged as "No" in the judgment of the presence or absence of the coating film formation on the above-mentioned unexposed part, and in the judgment of the presence or absence of the orientation of the pattern forming part having the strong anchoring ability. It was evaluated that the pattern forming ability "A" having the anchoring ability was obtained, and the other cases were evaluated as "P" forming ability having the strong anchoring ability.

<Method of evaluating weak anchoring property of non-patterned area having strong anchoring ability>
In the case where the cured film is not anisotropic on the surface of the cured film by the above-mentioned method such as rubbing method and photo alignment method, if the anchoring of the cured film is strong, the liquid crystal molecules in the vicinity of the cured film will be random. Light leakage is observed in the process of determining the orientation of the non-patterned portion having the strong anchoring ability as described above. Therefore, the weak anchoring property of the non-patterned portion having strong anchoring ability, "○", and the above-mentioned strongness, when it is judged that the orientation of the non-patterned portion having strong anchoring ability is "Yes". The case where it was judged that the orientation of the non-patterned portion having anchoring ability was "absent" was evaluated as the weak anchoring property "X" of the non-patterned portion having strong anchoring ability.

[Examples 2 to 11 and Comparative Examples 1 to 3]
Each component was mixed and dissolved in proportions (unit: g) described in Tables 1-1 and 1-2 according to the method of Example 1 to obtain a curable composition. According to the method of Example 1, the presence or absence of the coating film formation on the unexposed area, the presence or absence of the orientation of the pattern body forming part having strong anchoring ability, and the presence or absence of the pattern body non-formation part having strong anchoring ability The weak anchoring property of the non-patterned part having a strong anchoring ability and the pattern forming ability with a strong anchoring ability is evaluated, and the results are shown in Table 1-1 and Table 1-2. Indicated. However, when it is judged that there is no film formation on the unexposed area “No”, the steps (P1) and (P2) are omitted instead of the liquid crystal display element production substrate 1 for the production of the liquid crystal display element. The liquid crystal display element provided with the produced comb-tooth electrode substrate with a cured film was produced, and according to the method of Example 1, the reference evaluation of weak anchoring property was performed. As a reference evaluation result, “(○)” corresponding to weak anchoring property “「 ”of the patterned body non-formed portion having strong anchoring ability, or weak anchoring property of the patterned body non-formed portion having strong anchoring ability It described as "(x)" corresponding to "x."

However, in Example 4, a process for preparing a substrate for evaluation of pattern formability having strong anchoring ability is prebaked on a hot plate at 100 ° C. for 2 minutes, and then an exposure step is added, and the oven temperature is from 230 ° C. The production method was changed to 200 ° C. In the process of exposure, a proximity exposure machine TME-150PRC (trade name, Topcon Co., Ltd.) equipped with an extra-high pressure mercury lamp is used in the air, and the exposure dose is an integrated actinometer UIT-102 (trade name, Ushio Electric Ltd., and a light receiver UVD-365PD (trade name, Ushio Electric Co., Ltd.), and it was 100 mJ / cm ^{2 in} light conversion at a wavelength of 365 nm.

  As is apparent from the above, all of Examples 1 to 11 have good pattern forming ability with strong anchoring ability and weak anchoring ability of the non-patterned portion having strong anchoring ability. On the other hand, Comparative Example 1 using a composition containing no polyfunctional epoxy compound (B) and Comparative Example 2 using a composition containing no polyfunctional carboxyl compound (A) have strong anchoring ability. Although the weak anchoring property of the non-patterned portion is good, the pattern forming property having strong anchoring ability is poor. In addition, Comparative Example 3 using a composition containing a small amount of surfactant (C) is weakly anchoring of a non-patterned portion having a strong anchoring ability and a patternable ability to form a strong anchoring ability. Both sex are bad.

  The cured film formed using the curable composition of the present invention is excellent in patternability with strong anchoring ability and excellent in weak anchoring ability of non-patterned portion with strong anchoring ability. Thus, it is possible to manufacture a liquid crystal display element in which a region having high display response when the voltage is off and a region having low driving voltage property exist in a single liquid crystal display device.

DESCRIPTION OF SYMBOLS 10 Liquid crystal display element 11 Backlight unit 12A, 12B Polarizer LCP-1 1st board | substrate LCP-2 2nd board | substrate LCP-3 Liquid crystal layer LCP-4 Driving electrode layer 13 Double anchoring layer 13A Weak anchoring of double anchoring layer Area 13B having a function of strong anchoring area 14 of both anchoring layers 14 having a strong anchoring film 15A electrode line 16 pixel electrode 17 common electrode 18 pixel 19 electrode area 20 non-electrode area Lp liquid crystal compound X, Y first substrate and Coordinate axis assumed on a plane parallel to the second substrate

100 substrate 101 weak anchoring film 101A exposed portion 101B unexposed portion 102 coating film 103 for material for forming strong anchoring film pattern body 201 having strong anchoring ability ultraviolet ray 202 linearly polarized ultraviolet ray 203 photomask

Claims (10)

A curable composition comprising a polyfunctional carboxyl compound (A), a polyfunctional epoxy compound (B) and a surfactant (C);
The polyfunctional carboxyl compound (A) is a compound having three or more carboxyl groups per molecule;
The polyfunctional epoxy compound (B) is a compound having three or more epoxy groups per molecule;
Curable composition whose content of the said surfactant (C) is 3-100 weight part with respect to 100 weight part of total amounts of the said polyfunctional carboxyl compound (A) and polyfunctional epoxy compound (B).   The content of the surfactant (C) is 5 to 50 parts by weight based on 100 parts by weight of the total of the polyfunctional carboxyl compound (A) and the polyfunctional epoxy compound (B). Curable composition.   The curable composition according to claim 1, wherein the surfactant (C) is a polymerizable surfactant.   The curable composition according to claim 3, wherein the polymerizable surfactant is a reactive fluorine-containing oligomer.   The curable composition according to claim 1, wherein the polyfunctional carboxyl compound (A) is one or more selected from a polyesteramide acid (A1) and a carboxyl group-containing polymer (A2).   The curable composition according to claim 1, wherein the polyfunctional epoxy compound (B) is at least one selected from a glycidyl ether type epoxy compound (B1) and an epoxy group-containing polymer (B2).   The cured film which consists of a curable composition of any one of Claims 1-6. A liquid crystal display device comprising the cured film according to claim 7;
The cured film is in contact with the liquid crystal layer;
A liquid crystal display device in which the direction of liquid crystal molecules can be changed by the influence of an electric field even in the vicinity of the cured film.   An alignment substrate comprising the cured film according to claim 7 and a pattern body for regulating the alignment direction of liquid crystal molecules.   The liquid crystal display element provided with the orientation board | substrate of Claim 9.

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