JP7218645B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition that provides a weak anchoring film in a liquid crystal display element, a cured film using the same, and a liquid crystal display element provided with the cured film.

Liquid crystal display devices have characteristics such as thinness, light weight, and low power consumption, and their applications are expanding in a wide range of fields such as display devices for mobile phones, computers, and televisions. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and FLC (Ferroelectric Liquid Crystal) have been proposed as the display principle of liquid crystal display elements. It is necessary to regulate the alignment direction in advance.

A rubbing treatment, a photo-alignment treatment, and the like are employed as a treatment (orientation treatment) for forcing the orientation direction of liquid crystal molecules for display. In the rubbing treatment, after forming a film of a polymer such as polyimide on the substrate, a roller wound with a cloth such as rayon or cotton is rotated while the number of rotations of the roller and the distance between the roller and the substrate are kept constant. This is a treatment in which the surface of the polymer film is rubbed in one direction. Photo-alignment treatment is a method of irradiating a polymer film with polarized ultraviolet rays to perform alignment treatment, and there are photo-alignment mechanisms such as a photodecomposition method, a photoisomerization method, a photodimerization method, and a photocrosslinking method. By these alignment treatments, the liquid crystal molecules are strongly bound to the surface of the substrate with the alignment film and oriented in a certain direction. Hereinafter, the direction in which the liquid crystal molecules are bound by the surface of the substrate with the alignment film and aligned will be referred to as the "axis of easy alignment".

In recent years, a liquid crystal display device having a strong anchoring film on one side of a substrate and a weak anchoring film on the other side (see, for example, Patent Document 1) has been proposed as an improvement measure for improving the low driving voltage property of a liquid crystal display device. Proposed. In this specification, a film that regulates the alignment direction of liquid crystal molecules, such as the alignment film described above, is referred to as a "strong anchoring film". Similarly, a film that has a weak alignment regulating force (anchoring) on the substrate surface and can change the orientation of liquid crystal molecules by an electric field or the like even in the vicinity of the film is referred to as a "weak anchoring film". A material capable of forming a film having a strong anchoring ability is referred to as a "strong anchoring film-forming material," and a material capable of forming a film having a weak anchoring ability is referred to as a "weak anchoring film-forming material." write.

An example of Patent Document 1 describes a liquid crystal display element having a weak anchoring film on one side of which a polymer brush is formed on the surface of a substrate and a strong anchoring film which is a rubbed polyimide film on the other side. . Since the weak anchoring film has a weak alignment regulating force of the liquid crystal molecules, a liquid crystal display element having a weak anchoring film on one side and a strong anchoring film on the other side is different from a liquid crystal display element having strong anchoring films on both sides. In comparison, there is an advantage that the driving voltage is low.

However, in the method of forming polymer brushes on the substrate surface described in Patent Document 1, it is necessary to immerse the substrate in a polymer brush forming solution, and there is room for improvement in productivity during mass production.

Patent Document 2 proposes a material that provides a cured film having weak anchoring properties by using the same raw material as the polymer brush of Patent Document 1 and that is capable of forming a weak anchoring film by coating. However, this weak anchoring film has a problem in scratch resistance, and there is room for improvement in reducing productivity due to scratches on the film during production.

Further, as a polymer-dispersed liquid crystal optical element with a low driving voltage, a liquid crystal display element using a fluorine-containing photocurable compound as a matrix resin of a polymer-dispersed liquid crystal has been proposed (for example, Patent Document 3). The purpose of using the fluorine-containing photocurable compound is to reduce the interaction at the interface between the polymeric substance and the liquid crystal material.

A curable composition containing a copolymer having fluorine and a carboxyl group and a cross-linking agent such as an epoxy compound as a curable composition capable of forming a fluorine-containing cured film, although it is not intended to reduce interaction with the liquid crystal material. has been proposed (for example, Patent Document 4). However, when this curable composition is used as a weak anchoring film, there is still room for improvement in the scratch resistance of the cured film.

Patent Document 4 further describes a curable composition containing a copolymer having fluorine and a carboxyl group, a cross-linking agent such as an epoxy compound, and a copolymer having no fluorine and a carboxyl group. However, this curable composition described has room for improvement in the scratch resistance of the cured film as described above.

Further, in Patent Document 5, on a substrate having comb-teeth electrodes, a weak anchoring film is provided on the comb-teeth electrodes, a strong anchoring film is provided between the comb-teeth electrodes, and a strong anchoring film is provided on a counter substrate. A liquid crystal display device is described. When both the weak anchoring film and the strong anchoring film are formed on one substrate as in this liquid crystal display device, the solvent contained in the strong anchoring film forming material is applied to the weak anchoring film. (for example, N-methyl-2-pyrrolidone, hereinafter abbreviated as "NMP") needs weak anchoring properties (hereinafter referred to as "weak anchoring properties after contact with NMP").

However, the cured film provided by the curable composition described in Patent Document 4 has room for improvement in terms of weak anchoring properties after contact with NMP.

JP 2017-010030 JP 2017-214474 Japanese Patent Laid-Open No. 6-202086 JP 2013-141793 JP 2017-211566

An object of the present invention is to provide a curable composition which gives a cured film excellent in scratch resistance and weak anchoring property after contact with NMP, and which can be coated to form a film.

As a result of intensive studies to solve the above problems, the present inventors have found that a cured product obtained by curing a curable composition containing a copolymer having fluorine and a reactive group, a polyfunctional copolymer, and a polyfunctional epoxy compound The inventors have found that the above object can be achieved by the film, and have completed the present invention.

[1] A curable composition comprising a copolymer (A) having fluorine and a reactive group, a polyfunctional copolymer (B) and a polyfunctional epoxy compound (C);
The copolymer (A) having fluorine and a reactive group is a product from raw materials containing a polymerizable compound (m1) having fluorine and a polymerizable compound (m2) having a reactive group;
The polymerizable compound (m2) having a reactive group is at least one selected from a polymerizable compound (m21) having a carboxyl group and a polymerizable compound (m22) having an alkoxysilyl group;
The polyfunctional copolymer (B) is at least one selected from polyesteramic acid (B1), a copolymer having a carboxyl group (B2) and a copolymer having an acid anhydride group (B3) can be;
The copolymer (B2) having a carboxyl group includes the polymerizable compound (m21) having a carboxyl group, and a polymerizable compound having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group ( m4) is a copolymer;
In the raw materials of the copolymer having a carboxyl group (B2), the polymerizable compound having a carboxyl group (m21) and the polymerizable compound having none of the fluorine, the carboxyl group, the alkoxysilyl group, and the acid anhydride group The polymerizable compound (m21) having a carboxyl group is 5 to 30% by weight in 100% by weight of the total amount of the compound (m4);
Polymerization in which the copolymer (B3) having an acid anhydride group has neither the polymerizable compound (m3) having an acid anhydride group nor the fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group is a copolymer of a sexual compound (m4); and
A curable composition, wherein the polyfunctional epoxy compound (C) is a compound having 3 or more epoxy groups per molecule.

[2] In the total amount of 100% by weight of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B), 5 copolymers (A) having fluorine and a reactive group ~80% by weight;
[ 1] The curable composition according to the item.

[3] Item [1], wherein the fluorine-containing polymerizable compound (m1) is 40% by weight or more and 98% by weight or less in 100% by weight of the starting material of the copolymer (A) having fluorine and a reactive group. Or the curable composition according to item [2].

[4] Item [1], wherein the fluorine-containing polymerizable compound (m1) accounts for 50% by weight or more and 95% by weight or less in 100% by weight of the raw material of the copolymer (A) having fluorine and a reactive group. Or the curable composition according to item [2].

[5] The curable composition according to any one of [1] to [4], wherein the fluorine-containing polymerizable compound (m1) is a fluorine-containing (meth)acrylate compound.

式（１）中、Ｒ^１は水素又はメチル基であり；Ｒ^２～Ｒ^８はそれぞれ独立に水素又はフッ素であり；ｎ^１及びｎ^３はそれぞれ独立に０～３の整数であり；ｎ^２及びｎ^４はそれぞれ独立に０～６の整数であり；Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^８の内少なくとも１つはフッ素である。 [6] The curable composition according to item [5], wherein the fluorine-containing (meth)acrylate compound is a compound represented by the following formula (1);

In formula (1), R ¹ is hydrogen or a methyl group; R ² to R ⁸ are each independently hydrogen or fluorine; n ¹ and n ³ are each independently an integer of 0 to 3; n ² and n ⁴ are each independently an integer of 0 to 6; and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.

[7] The compound represented by formula (1) is 2,2,2-trifluoroethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl ( The curable composition according to item [6], which is at least one selected from meth)acrylate and 1,1,1,3,3,3-hexafluoroisopropyl(meth)acrylate.

[8] Any of [1] to [7], wherein the polymerizable compound (m21) having a carboxyl group is at least one selected from (meth)acrylic acid and a (meth)acrylate compound having a carboxyl group 1. The curable composition according to claim 1.

[9] The curable composition according to any one of [1] to [7], wherein the polymerizable compound (m21) having a carboxyl group is methacrylic acid.

[10] The polymerizable compound (m22) having an alkoxysilyl group is at least one selected from a (meth)acrylate compound having an alkoxysilyl group and a vinyl compound having an alkoxysilyl group, [1] to [ 9], the curable composition according to any one of the above items.

[11] The (meth)acrylate compound having an alkoxysilyl group is at least one selected from 3-trimethoxysilylpropyl (meth)acrylate and 3-triethoxysilylpropyl (meth)acrylate, and the alkoxysilyl group The curable composition according to item [10], wherein the vinyl compound having is at least one selected from vinyltrimethoxysilane and vinyltriethoxysilane.

[12] The copolymer (A) having fluorine and a reactive group has, in addition to the polymerizable compound (m1) having fluorine and the polymerizable compound (m2) having a reactive group, a polyethylene glycol chain ( The curable composition according to any one of [1] to [11], which is a product from raw materials further containing a meth)acrylate compound.

[13] The curable composition according to item [12], wherein the (meth)acrylate compound having a polyethylene glycol chain is methoxypolyethylene glycol (meth)acrylate.

[14] The polyfunctional epoxy compound (C) is at least one selected from compounds having 3 or more glycidyl ether groups, compounds having 3 or more glycidyl ester groups, and compounds having 3 or more oxiranyl groups. , The curable composition according to any one of [1] to [13].

[15] The curable composition according to any one of [1] to [14], for forming a weak anchoring film of a liquid crystal display device.

[16] A cured film obtained by curing the curable composition according to any one of [1] to [15].

[17] A liquid crystal display device comprising the cured film according to item [16] as a weak anchoring film.

[18] A first substrate (LCP-1) on which a weak anchoring film is formed,
a second substrate (LCP-2) on which a strong anchoring film is formed facing the weak anchoring film with a gap therebetween;
a liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film;
and provided on either one of the first substrate (LCP-1) and the second substrate (LCP-2), and the liquid crystal molecules in the liquid crystal layer are connected to the first substrate (LCP-1) and the second substrate A liquid crystal display device comprising a driving electrode layer (LCP-4) for applying an electric field in a direction along (LCP-2);
The liquid crystal display element according to item [17], wherein the liquid crystal molecules are driven by an electric field applied to the drive electrode layer (LCP-4), thereby changing light transmittance.

[19] The drive electrode layer (LCP-4) is composed of a plurality of electrode lines arranged on the substrate surface of the first substrate (LCP-1) or the second substrate (LCP-2), The liquid crystal display element according to item [15], wherein the orientation direction of the liquid crystal molecules on the second substrate (LCP-2) side is parallel or orthogonal to the direction in which the electrode lines are continuous during heating.

A curable composition according to a preferred embodiment of the present invention is a curable composition that provides a cured film having excellent scratch resistance and weak anchoring properties after contact with NMP, and is capable of forming a film by coating. The cured film can be used as a weak anchoring film for liquid crystal display elements. Since the weak anchoring film has high scratch resistance, it is difficult to be scratched during the production of the liquid crystal display element, and the weak anchoring property is high even after contact with NMP. It can also be used if both are formed. Moreover, since the cured film can be formed in the coating process, it has high productivity.

1 is a cross-sectional view showing a first embodiment of a liquid crystal display element 10 of the present invention, and a schematic configuration of a backlight unit 11 and polarizing plates 12A and 12B for display; FIG. 3 is a cross-sectional view showing the distribution of alignment directions of liquid crystal molecules in a state where a liquid crystal compound Lp having a positive dielectric anisotropy is used and an electric field E is applied in the first embodiment. FIG. In the first embodiment, a liquid crystal compound Lp having a positive dielectric anisotropy is used, and a plane showing the relationship between the wiring direction of the electrode lines and the alignment direction of the liquid crystal molecules near the weak anchoring film when no electric field is applied. It is a diagram. FIG. 2 is a plan view showing the relationship between the wiring direction of electrode lines and the orientation of liquid crystal molecules when a liquid crystal compound Lp having a positive dielectric anisotropy is used and an electric field E is applied in the first embodiment. FIG. 2 is a cross-sectional view showing a second embodiment of a liquid crystal display element 10 of the present invention, and a schematic configuration of a backlight unit 11 and polarizing plates 12A and 12B for display. FIG. 4 is a plan view showing the relationship between the wiring direction of the electrode wires 15A and the polarization direction of the polarizing plate 12A under the first condition in the method for determining the presence or absence of orientation when no voltage is applied in the example. FIG. 7 is a plan view showing the relationship between the wiring direction of the electrode wires 15A and the polarization direction of the polarizing plate 12A under the second condition in the method for determining the presence or absence of orientation when no voltage is applied in the example.

In this specification, "(meth)acryl" may be used to indicate one or both of "acryl" and "methacryl". Similarly, to indicate one or both of “acrylate” and “methacrylate”, it may be written as “(meth)acrylate”, and to indicate one or both of “acryloxy” and “methacryloxy”, It is sometimes written as "(meth)acryloxy".

<1. Curable composition of the present invention>
The curable composition of the present invention comprises a copolymer (A) having fluorine and a reactive group, a polyfunctional copolymer (B) and a polyfunctional epoxy compound (C). is.

In the curable composition of the present invention, the composition ratio of the copolymer (A) having fluorine and reactive groups, the polyfunctional copolymer (B) and the polyfunctional epoxy compound (C) is It is preferable that the copolymer (A) having fluorine and a reactive group is 5 to 80% by weight in the total amount of 100% by weight of the copolymer (A) and the polyfunctional copolymer (B) having The polyfunctional epoxy compound (C) is preferably 30 to 300 parts by weight with respect to a total of 100 parts by weight of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B).

In this specification, the copolymer (A) having fluorine and a reactive group, the polyfunctional copolymer (B) and the polyfunctional epoxy compound (C) may be collectively referred to as "main component". , the copolymer having fluorine and a reactive group (A), the polyfunctional copolymer (B) and the polyfunctional epoxy compound (C) may be referred to as the "major component amount".

<1-1. Copolymer (A) Having Fluorine and Reactive Group>
The copolymer (A) having fluorine and a reactive group used in the present invention is obtained from two or more raw materials including a polymerizable compound (m1) having fluorine and a polymerizable compound (m2) having a reactive group. is a product.

Raw materials for the copolymer (A) having fluorine and a reactive group include, in addition to the polymerizable compound (m1) having fluorine and the polymerizable compound (m2) having a reactive group, fluorine, a carboxyl group, and an alkoxysilyl A polymerizable compound (m4) having neither a group nor an acid anhydride group may be included.

Desirable weight ratio of the polymerizable compound in the raw material is 40% by weight or more and 98% by weight or less of the polymerizable compound (m1) having fluorine and 2% by weight of the polymerizable compound (m2) having a reactive group in 100% by weight of the raw material. % by weight or more and 40% by weight or less and containing a polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group, fluorine, carboxyl group, alkoxysilyl group, and the polymerizable compound (m4) having neither an acid anhydride group is 58% by weight or less. This weight ratio gives a cured film with excellent weak anchoring properties. A more desirable weight ratio of the polymerizable compounds is as follows: the fluorine-containing polymerizable compound (m1) is 50% by weight or more and 95% by weight or less; the reactive group-containing polymerizable compound (m2) is 5% by weight or more and 20% by weight or less; And when it contains a polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group, fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group The polymerizable compound (m4) that does not have is 45% by weight or less.

<1-1-1. Polymerizable Compound (m1) Having Fluorine>
In the present invention, a polymerizable compound (m1) having fluorine is used as a raw material for obtaining a copolymer (A) having fluorine and a reactive group.

The fluorine-containing polymerizable compound (m1) is a compound having at least one fluorine and at least one polymerizable group in one molecule.

Considering the compatibility with the polymerizable compound (m2) having a reactive group during polymerization, the polymerizable compound (m1) having fluorine is preferably a (meth)acrylate compound having fluorine.

式（１）中、Ｒ^１は水素又はメチル基であり；Ｒ^２～Ｒ^８はそれぞれ独立に水素又はフッ素であり；ｎ^１及びｎ^３はそれぞれ独立に０～３の整数であり；ｎ^２及びｎ^４はそれぞれ独立に０～６の整数であり；Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^８の内少なくとも１つはフッ素である。 Considering the availability of the compound, a preferred fluorine-containing (meth)acrylate compound is the compound represented by the following formula (1).

In formula (1), R ¹ is hydrogen or a methyl group; R ² to R ⁸ are each independently hydrogen or fluorine; n ¹ and n ³ are each independently an integer of 0 to 3; n ² and n ⁴ are each independently an integer of 0 to 6; and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.

In the above formula (1), n ¹ and n ³ are each independently preferably an integer of 0 to 2; n ² and n ⁴ are each independently 0, 1, 2, 4, or 6. Preferably; 3 to 12 of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ are preferably fluorine.

Specific examples of the compound represented by formula (1) include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(per fluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2,2,3,3,4,4, 5,5-octafluoropentyl (meth)acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth)acrylate, 1,1,1, 3,3,3-hexafluoroisopropyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth)acrylate, and 1,2,2,2-tetrafluoro-1-(tri fluoromethyl)ethyl (meth)acrylate. These compounds may be used alone or in combination of two or more.

Considering the compatibility with the polymerizable compound (m2) having a reactive group and the availability of the compound, 2,2,2-trifluoroethyl (meth) acrylate, 2-(perfluorobutyl) ethyl (meth) acrylate , 2-(perfluorohexyl)ethyl (meth)acrylate and 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate are preferred, and 2,2,2-trifluoroethyl (meth)acrylate is preferred. Especially preferred.

<1-1-2. Polymerizable compound having a reactive group (m2)>
In the present invention, a polymerizable compound (m2) having a reactive group is used as a raw material for obtaining a copolymer (A) having fluorine and a reactive group. The polymerizable compound (m2) having a reactive group used in the present invention is at least one selected from a polymerizable compound (m21) having a carboxyl group and a polymerizable compound (m22) having an alkoxysilyl group.

<1-1-2-1. Polymerizable compound having a carboxyl group (m21)>
The carboxyl group-containing polymerizable compound (m21) is a compound having at least one carboxyl group and at least one polymerizable group in one molecule.

Specific examples of the polymerizable compound (m21) having a carboxyl group include (meth)acrylate compounds having a carboxyl group such as ethyl 2-phthalate (meth)acrylate and ethyl 2-hexahydrophthalate (meth)acrylate; styrene compounds having a carboxyl group such as vinyl benzoic acid; dicarboxylic acid compounds such as itaconic acid, fumaric acid, maleic acid and citraconic acid; and (meth)acrylic acid. These compounds may be used alone or in combination of two or more.

Considering the compatibility with the polymerizable compound (m1) having fluorine during polymerization and the availability of raw materials, (meth)acrylic acid and a (meth)acrylate compound having a carboxyl group are preferred, and methacrylic acid is particularly preferred.

<1-1-2-2. Polymerizable compound having alkoxysilyl group (m22)>
The alkoxysilyl group-containing polymerizable compound (m22) is a compound having at least one alkoxysilyl group and at least one polymerizable group in one molecule.

Specific examples of the polymerizable compound (m22) having an alkoxysilyl group include (meth)acrylate compounds having an alkoxysilyl group such as 3-trimethoxysilylpropyl (meth)acrylate and 3-triethoxysilylpropyl (meth)acrylate; and vinyl compounds having alkoxysilyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane. These compounds may be used alone or in combination of two or more.

3-trimethoxysilylpropyl methacrylate, 3-triethoxysilylpropyl methacrylate, vinyltrimethoxysilane, and vinyltriethoxysilane are particularly preferable in consideration of availability, and in consideration of transparency after additional heating of the cured film. , 3-trimethoxysilylpropyl methacrylate and 3-triethoxysilylpropyl methacrylate are particularly preferred.

<1-1-3. Polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group>
In the present invention, as a raw material for obtaining a copolymer (A) having fluorine and a reactive group, a polymerizable compound (m4) having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group can be used.

The polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group and acid anhydride group has none of fluorine, carboxyl group, alkoxysilyl group and acid anhydride group, It is a compound having at least one polymerizable group in one molecule.

Specific examples of the polymerizable compound (m4) having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, n - propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth)acrylate compounds having an aliphatic group such as (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate;
(meth)acrylate compounds having aromatic groups such as phenyl (meth)acrylate and benzyl (meth)acrylate;
(meth)acrylate compounds having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
(meth)acrylate compounds having a polyethylene glycol chain such as methoxypolyethylene glycol (meth)acrylate;
2-ethoxyethyl (meth) acrylate, and (meth) acrylate compounds having an ether bond such as dicyclopentenyloxyethyl (meth) acrylate;
(meth)acrylate compounds having a cyclic ether group such as glycidyl (meth)acrylate;
3-[Tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, and (meth) acrylate compounds having siloxane bonding sites such as mono (meth) acryloxypropyl-modified polydimethylsiloxane;
(meth)acrylate compounds having a tertiary amino group such as 2-(dimethylamino)ethyl (meth)acrylate;
Diesters of dicarboxylic acid compounds having double bonds such as diethyl itaconate, diethyl fumarate, diethyl maleate, and diethyl itaconate;
N-substituted maleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-(4-hydroxyphenyl)maleimide;
styrene, 4-hydroxystyrene, and (meth)acrylamide. These compounds may be used alone or in combination of two or more.

The polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group imparts the effect of improving the weak anchoring property and the properties of the cured film other than the weak anchoring property. have the effect of

An example of a compound that provides the effect of improving weak anchoring properties by using a polymerizable compound (m4) that does not have fluorine, a carboxyl group, an alkoxysilyl group, or an acid anhydride group has a polyethylene glycol chain ( It is a meth)acrylate compound. When the (meth)acrylate compound having a polyethylene glycol chain is 5% by weight or more in 100% by weight of the raw material of the copolymer (A) having fluorine and a reactive group, alignment can be achieved without annealing after liquid crystal injection. It is preferable because it becomes possible.

Among (meth)acrylate compounds having a polyethylene glycol chain, methoxypolyethylene glycol methacrylate is preferred from the standpoint of availability. Specific examples of commercially available methoxypolyethylene glycol methacrylates, compounds having a repeating number of polyethylene glycol chains of about 9, are Light Ester 130MA (trade name; Kyoeisha Chemical Co., Ltd.) and Funcryl FA-400M (100) (trade name; Hitachi Chemical Co., Ltd.), and a compound having a repeating number of polyethylene glycol chains of about 30 is Light Ester 041MA (trade name; Kyoeisha Chemical Co., Ltd.).

Examples of the effect of imparting properties of the cured film other than weak anchoring properties by using the polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group include aromatic The effect of adjusting the refractive index of the cured film by using a (meth) acrylate compound having a group, the effect of improving the chemical resistance of the cured film by using a (meth) acrylate compound having a cyclic ether group, and having a siloxane bonding site (meth ) The effect of improving the liquid repellency of the cured film by using the acrylate, and the effect of improving the heat resistance of the cured film by using the N-substituted maleimide compound.

<1-1-4. Polymerization method of copolymer>
The polymerization method of the copolymer (A) having fluorine and reactive groups is not particularly limited. An example of the polymerization method is radical polymerization in a solution using a polymerization solvent to obtain a solution containing fluorine and a copolymer (A) having reactive groups. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, but 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 of elevated pressure, reduced pressure or atmospheric pressure.

The polymerization solvent is preferably used in an amount of 100 parts by weight or more per 100 parts by weight of the total amount of raw materials for the copolymer (A) having fluorine and a reactive group, because the reaction proceeds smoothly.

A curable composition can be prepared by using a solution containing the copolymer (A) having fluorine and a reactive group. Examples of the method for preparing the curable composition include a method of preparing a curable composition by directly using a solution containing the copolymer (A) having fluorine and a reactive group in which the polymerization solvent is left as it is, and a method of preparing a curable composition, and fluorine and In this method, a liquid or gel curable composition is prepared by adding a diluting solvent after removing the polymerization solvent from the solution containing the copolymer (A) having a reactive group.

<1-1-5. Polymerization Solvent Used for Polymerization Reaction>
Specific examples of the polymerization solvent (hereinafter simply referred to as "polymerization solvent") used in the polymerization reaction for obtaining the copolymer (A) having fluorine and a reactive group include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, diethylene glycol, Diol compounds such as propylene glycol and triethylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, butylene glycol monomethyl ether, diethylene glycol Monoether forms of diol compounds such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and triethylene glycol monomethyl ether; ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Diether forms of diol compounds such as diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), monoether monoesters of diol compounds such as propylene glycol monoethyl ether acetate, butylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether acetate; Diesters of diol compounds such as ethylene glycol diacetate and propylene glycol diacetate; monoesters of monocarboxylic acid compounds such as butyl acetate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl butyrate; methyl methoxyacetate, ethyl methoxyacetate , methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 4-methoxybutyric acid monoether monoesters of monohydroxycarboxylic acid compounds such as methyl acid; diesters of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate; monocarboxylic acids such as N,N-dimethylacetamide and N,N-dimethylpropionamide Monoamides of acid compounds, dialkyl ketone compounds such as methyl isobutyl ketone, methyl normal butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl ketone, and di-normal butyl ketone; cyclic ether compounds such as hexamethylene oxide and 1,4-dioxane; cyclic ester compounds such as β-propiolactone, γ-butyrolactone and δ-valerolactone; cyclic amide compounds such as 2-pyrrolidone and NMP; and cyclic ketone compounds such as cyclopentanone, cyclohexanone and cycloheptanone. These compounds may be used alone or in combination of two or more.

Among specific examples of these polymerization solvents, a diether of a diol compound, a monoether monoester of a diol compound, and a monoether monoester of a monohydroxycarboxylic acid compound are copolymers ( A) is preferred because of its high solubility.

<1-1-6. Molecular Weight of Copolymer (A) Having Fluorine and Reactive Group>
The obtained copolymer (A) having fluorine and a reactive group preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50,000. Within these ranges, the weak anchoring property is good.

The weight-average molecular weight in this specification is a value in terms of polystyrene obtained by the GPC method (column temperature: 35° C., flow rate: 1 mL/min). Polystyrene with a molecular weight of 645 to 132,900 as standard polystyrene (for example, polystyrene calibration kit PL2010-0102 from Agilent Technologies Inc.), and PLgel MIXED-D (trade name, Agilent Technologies Inc.) for the column. can be measured using tetrahydrofuran as a mobile phase. The weight-average molecular weights of commercially available products in this specification are values listed in catalogues.

<1-2. Polyfunctional Copolymer (B)>
The polyfunctional copolymer (B) used in the present invention is selected from polyesteramic acid (B1), a copolymer having a carboxyl group (B2), and a copolymer having an acid anhydride group (B3). at least one

These polyfunctional copolymers (B) are easy to obtain raw materials and easy to produce compounds, and curable compositions containing the polyfunctional copolymers (B) contain fluorine and reactive groups. It has good compatibility with the copolymer (A) and the polyfunctional epoxy compound (C). Furthermore, since the polyester amic acid (B1) has a high ultraviolet absorption property, it has the effect of reducing ultraviolet damage to the substrate in the ultraviolet irradiation step after forming the cured film of the present invention, so the polyester amic acid (B1) is particularly preferable.

<1-2-1. Polyester amic acid (B1)>
The polyesteramic acid (B1) used in the present invention is a reaction product obtained by reacting a tetracarboxylic dianhydride (b11), a diamine (b12), and a polyhydric hydroxy compound (b13) as essential raw materials. be. Furthermore, in addition to these, one or more selected from monohydric alcohol (b14) and styrene-maleic anhydride copolymer (b15) may be added to the raw materials.

The method of adding the polyesteramic acid (B1) to the curable composition of the present invention may be the addition of the solution after the polymerization reaction as it is, or the solution may be concentrated to remove the solid content, and only the solid content may be added. .

<1-2-1-1. Tetracarboxylic dianhydride (b11)>
Examples of tetracarboxylic dianhydrides (b11) used in the present invention are aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.

Specific examples of the aromatic tetracarboxylic dianhydride include 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2 ,3,3′,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2′,3,3′-diphenylsulfonetetracarboxylic dianhydride acid dianhydride, 2,3,3′,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 2,2′,3,3 '-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride and ethylene glycol bis(anhydrotrimellitate); specific examples of alicyclic tetracarboxylic dianhydrides are cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride; specific examples of aliphatic tetracarboxylic dianhydrides are ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride.

Among these, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride, 2,2-[bis(3, 4-dicarboxyphenyl)]hexafluoropropane dianhydride, ethylene glycol bis(anhydrotrimellitate), and butanetetracarboxylic dianhydride are preferred, and 3,3′,4,4′-diphenylsulfonetetracarboxylic Acid dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride and butanetetracarboxylic dianhydride are particularly preferred. A cured film formed using a curable composition containing polyesteramic acid (B1) containing one or more selected from these as raw materials has high light transmittance.

As the tetracarboxylic dianhydride (b11), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-2. Diamine (b12)>
Examples of diamines (b12) 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′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, and 3,4′-diaminodiphenylsulfone; Specific examples include bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, [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'-diaminodiphenylsulfone is preferred. The polyesteramic acid (B1) containing this as a raw material has good solubility in solvents.

As the diamine (b12), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-3. Polyvalent hydroxy compound (b13)>
Specific examples of the polyhydric hydroxy compound (b13) used in the present invention include 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 and tripropylene. Glycol, tetrapropylene glycol, polypropylene glycol with 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-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanediol , 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 preferred. 4-Butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred. The polyesteramic acid (B1) containing one or more selected from these as raw materials has good solubility in solvents.

As the polyvalent hydroxy compound (b13), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-4. Monohydric alcohol (b14)>
In addition to the tetracarboxylic dianhydride (b11), the diamine (b12), and the polyhydric hydroxy compound (b13), a monohydric alcohol (b14) may be reacted to synthesize the polyester amic acid (B1). .

Specific examples of the monohydric alcohol (b14) include 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, dimethylbenzylcarbinol, 3-ethyl-3-hydroxymethyloxetane is.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are preferred, and benzyl alcohol is particularly preferred. The polyesteramic acid (B1) containing one or more selected from these as raw materials has good compatibility with the polyfunctional epoxy compound (C).

As the monohydric alcohol (b14), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-5. Styrene-maleic anhydride copolymer (b15)>
In the synthesis of polyester amic acid (B1), in addition to tetracarboxylic dianhydride (b11), diamine (b12), and polyhydroxy compound (b13), a styrene-maleic anhydride copolymer (b15) is added. may be reacted.

By adding the styrene-maleic anhydride copolymer (b15), the compatibility of the polyesteramic acid (B1) with the polyfunctional epoxy compound (C) can be improved. The molar ratio of styrene/maleic anhydride is 0.5 to 4, preferably 1 to 3, specifically about 1, about 2 or about 3 is more preferable, and about 1 or about 2 is more preferable, About 1 is particularly preferred.

Specific examples of commercial products of the styrene-maleic anhydride copolymer (b15) are SMA1000, SMA2000, and SMA3000 (all trade names, Kawakuro Kagaku Co., Ltd.). Among these, SMA1000 is particularly preferred because of its good solubility in solvents.

As the styrene-maleic anhydride copolymer (b15), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-6. Method for producing polyesteramic acid (B1)>
The polyesteramic acid (B1) 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 (hereinafter referred to as "polymerization solvent") used for the polymerization reaction.

<1-2-2. Carboxyl Group-Containing Copolymer (B2)>
The copolymer having a carboxyl group (B2) used in the present invention is a polymerizable compound having a carboxyl group (m21) and a polymerizable compound having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group. It is a copolymer of compound (m4).

<1-2-2-1. Preferred examples of the polymerizable compound (m21) having a carboxyl group>
Preferred examples of the polymerizable compound (m21) having a carboxyl group used as a raw material for the copolymer (B2) having an acid anhydride group are (meth)acrylic acid and a (meth)acrylate compound having a carboxyl group, A particularly preferred example is methacrylic acid. These compounds have high compatibility with the copolymer (A) having fluorine and a reactive group, and raw materials are readily available.

<1-2-2-2. Preferred example of polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group>
Preferred examples of the polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group used as a raw material for the copolymer (B2) having an acid anhydride group are aliphatic a (meth)acrylate compound having a group, a (meth)acrylate compound having an aromatic group, a (meth)acrylate compound having a cyclic ether group, and an N-substituted maleimide compound, particularly preferred examples having an aliphatic group (meth)acrylate compounds and N-substituted maleimide compounds. These compounds have high compatibility with the copolymer (A) having fluorine and a reactive group, and raw materials are readily available.

<1-2-2-3. Method for Producing Copolymer (B2) Having Carboxyl Group>
The carboxyl group-containing copolymer (B2) used in the present invention is produced by a known production method. A preferred production method is a radical polymerization method in a solution using a solvent. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, but 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 of elevated pressure, reduced pressure or atmospheric pressure. The manufacturing method is solution polymerization using a polymerization solvent.

<1-2-3. Copolymer (B3) Having Acid Anhydride Group>
The copolymer (B3) having an acid anhydride group used in the present invention includes both the polymerizable compound (m3) having an acid anhydride group and fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group. It is a copolymer of a polymerizable compound (m4) that does not

<1-2-3-1. Polymerizable compound (m3) having an acid anhydride group>
The acid anhydride group-containing polymerizable (m3) is a compound having at least one acid anhydride group and at least one polymerizable group in one molecule.

Specific examples of the polymerizable compound (m3) having an acid anhydride group used in the present invention are maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride and itaconic anhydride.

Among these, maleic anhydride and itaconic anhydride are preferred, and maleic anhydride is particularly preferred. A curable composition containing a polymer (B2) having an acid anhydride group obtained by polymerizing a mixture containing one or more selected from these has good curability.

<1-2-3-2. Preferred example of polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group>
Preferred examples of the polymerizable compound (m4) having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group used as a raw material for the copolymer (B3) having an acid anhydride group are aromatic group-containing (meth)acrylate compounds, cyclic ether group-containing (meth)acrylate compounds, N-substituted maleimide compounds, and styrene, with styrene being particularly preferred. These compounds have high compatibility with the copolymer (A) having fluorine and a reactive group, and raw materials are readily available.

<1-2-3-3. Method for Producing Copolymer (B3) Having Acid Anhydride Group>
The copolymer (B3) having an acid anhydride group used in the present invention is produced by a known production method. A preferred production method is a radical polymerization method in a solution using a solvent. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, but 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 of elevated pressure, reduced pressure or atmospheric pressure. The manufacturing method is solution polymerization using a polymerization solvent.

<1-2-3-4. Specific Examples of Commercially Available Copolymers (B3) Having Acid Anhydride Groups>
Specific examples of commercial products of the copolymer (B3) having an acid anhydride group used in the present invention include styrene-maleic anhydride copolymer (polymerizable compound (m3) having an acid anhydride group is maleic acid SMA1000, SMA2000, and SMA3000 (any is also a product name, Kawakuro Kagaku Co., Ltd.).

<1-3. Polyfunctional epoxy compound (C)>
The polyfunctional epoxy compound (C) used in the present invention is a compound having 3 or more epoxy groups per molecule.

Examples of the polyfunctional epoxy compound (C) used in the present invention are
Phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds, biphenyl type polyfunctional epoxy compounds, polyfunctional epoxy compounds having siloxane bonding sites, 2-[4-(2,3-epoxypropoxy)phenyl ]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, 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 α-2, Compounds having 3 or more glycidyl ether groups such as 3-epoxypropoxyphenyl-ω-hydropoly[2-(2,3-epoxypropoxy)benzylidene-2,3-epoxypropoxyphenylene];
Compounds having 3 or more glycidyl ester groups, such as homopolymers of glycidyl methacrylate, copolymers of glycidyl methacrylate and polymerizable compounds other than glycidyl methacrylate; and
Compounds having 3 or more oxiranyl groups such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol.

A curable composition containing a compound having 3 or more glycidyl ether groups gives a cured film having good heat resistance, and a curable composition containing a compound having 3 or more glycidyl ester groups can be used even when the baking temperature is low. A cured film with good chemical resistance is provided, and a curable composition containing a compound having 3 or more oxiranyl groups gives a cured film with good UV resistance.

Among compounds having 3 or more glycidyl ether groups, a bisphenol A novolac type epoxy compound, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-, which gives a cured film with particularly good heat resistance, [1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, 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 α-2,3-epoxypropoxyphenyl-ω -hydropoly[2-(2,3-epoxypropoxy)benzylidene-2,3-epoxypropoxyphenylene] is particularly preferred.

Specific examples of commercial products of phenol novolac type epoxy compounds are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.) and jER 152 and 154 (both trade names, Mitsubishi Chemical Co., Ltd.); Cresol novolac type epoxy Specific examples of commercially available compounds are EOCN-102S, 103S, 104S, and 1020 (all trade names, Nippon Kayaku Co., Ltd.); Specific examples of commercially available bisphenol A novolac epoxy compounds are jER 157S65, 157S70 (both trade names, Mitsubishi Chemical Corporation); specific examples of commercially available biphenyl-type polyfunctional epoxy compounds include NC-3000, NC-3000-L, NC-3000-H, and NC-3100 (each (trade name, Nippon Kayaku Co., Ltd.); specific examples of commercially available polyfunctional epoxy compounds having a siloxane bond site include COATOSIL MP200 (trade name, Momentive Performance Materials Japan LLC) and Compoceran SQ506. (trade name, Arakawa Chemical Co., Ltd.), ES-1023 (trade name, Shin-Etsu Chemical Co., Ltd.); 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- A specific example of a commercial product containing [4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol is TECHMORE VG3101L (trade name, Printec Co., Ltd.); specific examples of commercial products of α-2,3-epoxypropoxyphenyl-ω-hydropoly[2-(2,3-epoxypropoxy)benzylidene-2,3-epoxypropoxyphenylene] include: EPPN-501H and 502H (both trade names, Nippon Kayaku Co., Ltd.); a specific example of the homopolymer of glycidyl methacrylate is Marproof G-01100 (trade name, NOF Corporation); A specific example of a commercially available 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol is EHPE3150 (trade name, Daicel Corporation).

<1-4. Additive (D)>
The curable composition of the present invention may further contain an additive (D). The additive (D) optionally added to the curable composition of the present invention enhances the properties of the curable composition of the present invention, such as coating uniformity, adhesion, stability, chemical resistance, and low-temperature curability. It is added from the viewpoint of improvement.

Examples of the additive (D) include anionic, cationic, nonionic, and fluorine-based surfactants; silicone resin coating improvers; adhesion improvers such as silane coupling agents; sodium polyacrylate, etc. Anti-agglomeration agents; polymer dispersants such as acrylic, styrene, polyethyleneimine, and urethane; antioxidants such as hindered phenol; epoxy compounds other than polyfunctional epoxy compounds (C), melamine compounds, and cross-linking agents such as bisazide compounds; photoacid generators; polyfunctional (meth)acrylate compounds; and photopolymerization initiators.

<1-4-1. Surfactant, coatability improver>
The curable composition of the present invention may further contain a surfactant from the viewpoint of further improving coating uniformity. Specific examples of surfactants include Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (all trade names, Kyoeisha Chemical Co., Ltd.), DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK-181, DISPERBYK-182, BYK -300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all product names, BYK-Chemie Japan Co., Ltd.) , KP-341, KP-368, KF-96-50CS, KF-50-100CS (both trade names, Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade name, AGC Seimi Chemical Co., Ltd.), lid FTERGENT 222F, FTERGENT 208G, FTERGENT 251, FTERGENT 710FL, FTERGENT 710FM, FTERGENT 710FS, FTERGENT 601AD, FTERGENT 650A, FTX-218 (all trade names, Neos Co., Ltd.), MEGAFACE F-171 , Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-472SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Mega Fac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS -72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, (both trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate , diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), Luoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylenetri Decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate , sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl It is a diphenyl ether disulfonate. These compounds may be used alone or in combination of two or more.

Among specific examples of these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Futergent 710FL, Futergent 710FM, Futergent 710FS, Futergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoro At least one selected from alkylsulfonates, fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates is preferable because it has a large effect of improving the coating uniformity of the curable composition.

The amount of surfactant added to the curable composition of the present invention is preferably 0.01 to 20 parts by weight per 100 parts by weight of the main components.

<1-4-2. Adhesion improver>
The curable composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion of the formed cured film to the substrate. Specific examples of adhesion improvers that can be used include silane-based, aluminum-based, and titanate-based coupling agents. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (eg, Sila Ace S510; trade name, JNC Corporation), 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane (eg, Sila Ace S530; trade name, JNC Corporation), 3-trimethoxysilylpropyl methacrylate (eg, Sila Ace S710; trade name, JNC Corporation), 3-mercaptopropyltri Silane-based coupling agents such as methoxysilane (e.g., Sila Ace S810; trade name, JNC Corporation), aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate, and titanates such as tetraisopropylbis(dioctylphosphite) titanate is a system coupling agent. These compounds may be used alone or in combination of two or more.

Among specific examples of these adhesion improvers, 3-glycidyloxypropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate are preferred because they are highly effective in improving the adhesion of the cured film to the substrate.

The amount of the adhesion improver added to the curable composition of the present invention is preferably 0.1 to 20 parts by weight per 100 parts by weight of the main component.

<1-4-3. Aggregation inhibitor>
The curable composition of the present invention may further contain an anti-aggregation agent from the viewpoint of blending with the solvent and preventing aggregation. An anti-agglomeration agent is used for compatibility with a solvent to prevent aggregation. Specific examples of the anti-agglomeration agent optionally added to the curable composition of the present invention are DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-182, DISPERBYK-184, DISPERBYK -185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DISPERBYK-199, DISPERBYK-2015 (all trade names, BYK-Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent 710FS (both trade names, Neos Co., Ltd.), Floren G-600, and Floren G-700 (both trade names, Kyoeisha Chemical Industry Co., Ltd.). These compounds may be used alone or in combination of two or more.

<1-4-4. Antioxidant>
The curable composition of the present invention may further contain an antioxidant from the viewpoint of preventing yellowing when the cured film is exposed to high temperatures.酸化防止剤の具体例は、Ｉｒｇａｎｏｘ１０１０、ＩｒｇａｎｏｘＦＦ、Ｉｒｇａｎｏｘ１０３５、Ｉｒｇａｎｏｘ１０３５ＦＦ、Ｉｒｇａｎｏｘ１０７６、Ｉｒｇａｎｏｘ１０７６ＦＤ、Ｉｒｇａｎｏｘ１０９８、Ｉｒｇａｎｏｘ１１３５、Ｉｒｇａｎｏｘ１３３０、Ｉｒｇａｎｏｘ１７２６、Ｉｒｇａｎｏｘ１４２５ＷＬ、Ｉｒｇａｎｏｘ１５２０Ｌ、Ｉｒｇａｎｏｘ２４５、Ｉｒｇａｎｏｘ２４５ＦＦ、Ｉｒｇａｎｏｘ２５９、Ｉｒｇａｎｏｘ３１１４、Ｉｒｇａｎｏｘ５６５、Ｉｒｇａｎｏｘ５６５ＤＤ、（いずれも商品名、 BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, and ADK STAB AO-80 (all trade names, ADEKA Corporation). These compounds may be used alone or in combination of two or more.

Among specific examples of these antioxidants, Irganox 1010 and ADK STAB AO-60 are more preferred.

The amount of the antioxidant added to the curable composition of the present invention is preferably 0.01 to 5 parts by weight per 100 parts by weight of the main components.

<1-4-5. Crosslinking agent>
From the viewpoint of improving heat resistance, chemical resistance, in-plane uniformity, flexibility, softness and elasticity, the curable composition of the present invention contains an epoxy compound other than the polyfunctional epoxy compound (C), and a melamine compound. , and a cross-linking agent such as a bisazide compound.

Examples of epoxy compounds other than the polyfunctional epoxy compound (C) include glycidyl ether groups such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenyl type bifunctional epoxy compounds, and bifunctional epoxy compounds having a siloxane bonding site. compounds having two; compounds having two glycidyl ester groups such as diglycidyl terephthalate, diglycidyl phthalate, and diglycidyl 1,2-cyclohexanedicarboxylate; and 3′,4′-epoxycyclohexylmethyl-3, It is a compound having two alicyclic epoxy groups such as 4-epoxycyclohexanecarboxylate. These compounds may be used alone or in combination of two or more.

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004 and 1009 (all trade names, Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F type epoxy compounds are jER 806 and 4005P. (all trade names, Mitsubishi Chemical Corporation); specific examples of commercially available biphenyl-type bifunctional epoxy compounds are jER YX4000, YX4000H, and YL6121H (all trade names, Mitsubishi Chemical Corporation); siloxane bonds A specific example of a commercially available bifunctional epoxy compound having a site is TSL9906 (trade name, Momentive Performance Materials Japan LLC); a specific example of a commercially available diglycidyl terephthalic acid ester is Denacol EX- 711 (trade name, Nagase ChemteX Corporation); a specific example of a commercially available diglycidyl phthalate is Denacol EX-721 (trade name, Nagase ChemteX Corporation); A specific example of a commercial product of epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is Celoxide 2021P (trade name, Daicel Corporation).

The amount of the epoxy compound other than the polyfunctional epoxy compound (C) added to the curable composition of the present invention is preferably 1 to 20 parts by weight per 100 parts by weight of the main component.

<1-4-6. Photoacid Generator>
The curable composition of the present invention may further contain a photoacid generator from the viewpoint of improving resolution. Examples of photoacid generators are 1,2-quinonediazide compounds.

Specific examples of 1,2-quinonediazide compounds include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide. -5-sulfonic acid ester (for example, product name, NT-200, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6 -trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,2′,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′, 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,3',4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2, 3,3′,4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis(p- hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonic acid ester; tri(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri(p-hydroxyphenyl)methane-1 ,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri(p- hydroxyphenyl)ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester; bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis(2,3 , 4-tri hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 ,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)- 3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester , 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester; bis(2, 5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1 ,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3′,3′-tetramethyl-1,1′-spirobiindene-5,6,7,5′,6′,7′-hexanol -1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3′,3′-tetramethyl-1,1′-spirobiindene-5,6,7,5′,6′,7′ -hexanol-1,2-naphthoquinonediazide-5-sulfonate; 2,2,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate, and 2,2,4-trimethyl-7,2′,4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester. These compounds may be used alone or in combination of two or more.

The amount of the photoacid generator added to the curable composition of the present invention is preferably 1 to 20 parts by weight per 100 parts by weight of the main components.

<1-4-7. Polyfunctional (meth)acrylate compound>
The curable composition of the present invention may further contain a polyfunctional (meth)acrylate compound from the viewpoint of improving scratch resistance.

Examples of polyfunctional (meth)acrylates are compounds having two (meth)acryloyl groups per molecule and compounds having three or more (meth)acryloyl groups per molecule.

Specific examples of compounds having two (meth)acryloyl groups per molecule include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di( meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide-modified bisphenol Di(meth)acrylates of diol compounds such as A di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, and ethylene oxide-modified bisphenol S di(meth)acrylate;
Di(meth)acrylates of triol compounds such as glycerol acrylate methacrylate, glycerol di(meth)acrylate, and ethoxylated isocyanuric acid diacrylate;
Di(meth)acrylates of bisphenol compounds such as bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, and bisphenol S di(meth)acrylate; and
Epichlorohydrin-modified ethylene glycol di(meth)acrylate, epichlorohydrin-modified 1,6-hexanediol di(meth)acrylate, epichlorohydrin-modified diethylene glycol di(meth)acrylate, epichlorohydrin-modified triethylene glycol di(meth)acrylate, epichlorohydrin-modified tetraethylene glycol di(meth)acrylate (Meth)acrylate, epichlorohydrin-modified polyethylene glycol di(meth)acrylate, epichlorohydrin-modified propylene glycol di(meth)acrylate, epichlorohydrin-modified dipropylene glycol di(meth)acrylate, epichlorohydrin-modified tripropylene glycol di(meth)acrylate, epichlorohydrin-modified tetra Propylene glycol di(meth)acrylate, epichlorohydrin-modified polypropylene glycol di(meth)acrylate, (meth)acrylic acid adduct of bisphenol A type epoxy compound, (meth)acrylic acid adduct of bisphenol F type epoxy compound, and bisphenol S type It is a (meth)acrylic acid addition of a diepoxy compound such as a (meth)acrylic acid adduct of an epoxy compound. These compounds may be used alone or in combination of two or more.

Specific examples of compounds having 3 or more (meth)acryloyl groups per molecule 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 isocyanuric acid tri(meth)acrylate, and ε-caprolactone-modified tris- (2-(meth)acryloxyethyl) trifunctional (meth)acrylate compounds such as isocyanurate;
Ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate, and diglycerin EO modified tetra acrylate such as tetrafunctional (meth) ) acrylate compounds;
Pentafunctional (meth)acrylate compounds such as dipentaerythritol penta(meth)acrylate;
Hexafunctional (meth)acrylate compounds such as dipentaerythritol hexaacrylate;
and a polyfunctional (meth)acrylate compound having a carboxyl group. These compounds may be used alone or in combination of two or more.

Specific examples of commercial products of trimethylolpropane triacrylate, which is a trifunctional acrylate compound, include NK Ester TMPT (trade name, Shin-Nakamura Chemical Industry Co., Ltd.), TMPTA (trade name, Daicel Allnex Co., Ltd.), and Aronix. M-309 (trade name h Toagosei Co., Ltd.);
Specific examples of commercial products of trimethylolpropane EO-modified triacrylate are TMPEOTA (trade name, Daicel Allnex Co., Ltd.), Aronix M-350, M-360 (both trade names, Toagosei Co., Ltd.);
Specific examples of commercial products of trimethylolpropane PO-modified triacrylate are EBECRYL 135 (trade name, Daicel-Ornex Co., Ltd.), Aronix M-310, M-321 (both trade names, Toagosei Co., Ltd.);
A specific example of a commercially available product of glycerol PO-modified triacrylate is OTA 480 (trade name, Daicel Allnex Co., Ltd.);
A specific example of a commercially available product of ethoxylated isocyanuric acid triacrylate is NK Ester A-9300 (trade name, Shin-Nakamura Chemical Co., Ltd.);
A specific example of a commercially available ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate is NK Ester A-9300-1CL (trade name, Shin-Nakamura Chemical Co., Ltd.).

A specific example of a commercial product of trimethylolpropane trimethacrylate, which is a trifunctional methacrylate compound, is NK Ester TMPT (trade name, Shin-Nakamura Chemical Co., Ltd.).

Specific examples of commercial products of ditrimethylolpropane tetraacrylate, which is a tetrafunctional acrylate compound, include NK Ester AD-TMP (trade name, Shin-Nakamura Chemical Co., Ltd.), EBECRYL 140, and 1142 (both trade names, Daicel Allnex Co., Ltd., Aronix M-408 (trade name, Toagosei Co., Ltd.);
A specific example of a commercially available ethoxylated pentaerythritol tetraacrylate is NK Ester ATM-35E (trade name, Shin-Nakamura Chemical Co., Ltd.);
A specific example of a commercial product of pentaerythritol tetraacrylate is NK Ester A-TMMT (trade name, Shin-Nakamura Chemical Co., Ltd.);
A specific example of a commercial product of pentaerythritol alkoxytetraacrylate is EBECRYL 40 (trade name, Daicel Allnex Co., Ltd.);
A specific example of a commercial product of diglycerin EO-modified tetraacrylate is Aronix M-460 (trade name, Toagosei Co., Ltd.).

Specific examples of commercial products of dipentaerythritol hexaacrylate, which is a hexafunctional acrylate compound, include NK Ester A-DPH (trade name, Shin-Nakamura Chemical Co., Ltd.) and DPHA (trade name, Daicel Allnex Co., Ltd.). is.

Specific examples of commercially available polyfunctional acrylate compounds having carboxyl groups are Aronix M-510 and M-520 (both trade names, Toagosei Co., Ltd.).

A specific example of a commercially available mixture of ethoxylated isocyanuric acid triacrylate, which is a trifunctional acrylate compound, and ethoxylated isocyanuric acid diacrylate, which is a bifunctional acrylate compound, is Aronix M-315 (3 to 13% by weight) (product Name, Toagosei Co., Ltd., the content in parentheses is the catalog published value of the content of ethoxylated isocyanuric acid diacrylate in the mixture).

Specific examples of commercially available mixtures of pentaerythritol triacrylate, which is a trifunctional acrylate compound, and pentaerythritol tetraacrylate, which is a tetrafunctional acrylate compound, include PETIA, PETRA, and PETA (all trade names, Daicel Allnex Co., Ltd. company), Aronix M-306 (65-70% by weight), M-305 (55-63% by weight), and M-450 (less than 10% by weight) (all are trade names, Toagosei Co., Ltd., parentheses The content is the value listed in the catalog for the content of pentaerythritol triacrylate in the mixture).

Specific examples of commercially available mixtures of dipentaerythritol pentaacrylate, which is a pentafunctional acrylate, and dipentaerythritol hexaacrylate, which is a hexafunctional acrylate, include Aronix M-403 (50 to 60% by weight), M-400 ( 40-50% by weight), M-402 (30-40% by weight), M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight) ) (trade name, Toagosei Co., Ltd., the content in parentheses is the catalog published value of the content of pentaerythritol pentaacrylate in the mixture).

The amount of the polyfunctional (meth)acrylate compound added to the curable composition of the present invention is preferably 10 to 50 parts by weight per 100 parts by weight of the main components.

<1-4-8. Photoinitiator>
The curable composition of the present invention may further contain a photopolymerization initiator from the viewpoint of improving low-temperature curability. When adding a photopolymerization initiator, it is possible to lower the baking temperature by using it together with a polyfunctional (meth)acrylate compound and performing an ultraviolet irradiation step.

Specific examples of photoinitiators include benzophenone, Michler's ketone, 4,4′-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2 -methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (for example, trade name; Irgacure 907, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (eg, trade name; Irgacure 369, BASF Japan Ltd.), ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 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-carbazole-3- yl]-,1-(O-acetyloxime) (for example, trade name; Irgacure OXE02, BASF Japan Ltd.), Irgacure OXE03 (trade name, BASF Japan Ltd.), 1,2-propanedione, 1-[4 -[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-acetyloxime) (for example, trade name; Adeka Arkles NCI-930, ADEKA Corporation), Adeka Arkles NCI-831 (trade name) , ADEKA Corporation), ADEKA OPTOMER N-1919 (trade name, ADEKA Corporation), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4′-methoxystyryl)-4,6-bis( trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyst lyl)-4,6-bis(trichloromethyl)-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-[pN, 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-mercaptobenzothiazole , 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-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, and bis(η ⁵ -2,4-cyclopentadiene- 1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. These compounds may be used alone or in combination of two or more.

Among specific examples of these photoinitiators, 1,2-octanedione, 1-[4-(phenylthio)phenyl],-2-(O-benzoyloxime) and 1,2-propanedione, 1-[ When one or more selected from 4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-acetyloxime) is used, the effect of improving the low-temperature curability of the curable composition is less. It is expressed in light exposure. A suitable addition amount of the photopolymerization initiator for expressing this effect is 0.1 to 10 parts by weight with respect to 100 parts by weight of the main component.

<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 "dilution solvent (E)") is a copolymer (A) having fluorine and a reactive group, a polyfunctional copolymer ( Solvents capable of dissolving B) and the polyfunctional epoxy compound (C) are preferred. When the curable composition contains the additive (D) described above, the solvent for dilution (E) is preferably a solvent capable of dissolving the additive (D).

Specific examples of the diluent solvent (E) are the same as the solvents described above as specific examples of the polymerization solvent. These compounds may be used alone or in combination of two or more.

<1-6. Storage of Curable Composition>
It is preferable that the curable composition of the present invention is stored in the range of -30°C to 25°C in the absence of light, because the composition has good stability over time. Storage at -10°C to 20°C is more preferred.

<2. Cured Film Obtained from Curable Composition>
The curable composition of the present invention is a mixture of a copolymer (A) having fluorine and a reactive group, a polyfunctional copolymer (B) and a polyfunctional epoxy compound (C), and depending on the desired properties, Furthermore, the additive (D) and diluent solvent (E) are selected and added as necessary, and they are uniformly mixed and dissolved.

By applying the curable composition obtained as described above to the substrate surface, when the curable composition contains a composition solvent, the composition solvent is further subjected to steps such as a heating step and a pressure reduction step. By removing, a coating film can be formed. Specific examples of the method of applying the curable composition to the substrate surface are spin coating, roll coating, dipping, and slit coating. This coating film is then pre-baked with a hot plate, an oven, or the like. The pre-baking conditions vary depending on the type and blending ratio of each component, but are usually 70 to 150° C. for 1 to 5 minutes in a hot plate and 5 to 15 minutes in an oven.

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

The cured film thus obtained has weaker orientation regulation (anchoring) due to the surface free energy lowering ability peculiar to fluorine. Therefore, the cured film of the present invention is effective when used as a weak anchoring film, and a liquid crystal display device using this weak anchoring film can be produced. Furthermore, the obtained cured film is a three-dimensional crosslinked by the reaction of the carboxyl group of the polyfunctional copolymer (B) and the epoxy group of the polyfunctional epoxy compound (C), fluorine and a copolymer having a reactive group ( When A) has a carboxyl group, three-dimensional cross-linking by reaction of the carboxyl group of the copolymer (A) having fluorine and a reactive group and the epoxy group of the polyfunctional epoxy compound (C), fluorine and the reactive group When the copolymer (A) has alkoxysilyl groups, three-dimensional cross-linking occurs due to condensation of the alkoxysilyl groups. In addition, regarding the condensation of the alkoxysilyl groups of the copolymer (A) having fluorine and a reactive group, the carboxyl groups of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B ) acts as a catalyst to improve the condensation reaction rate. These three-dimensional crosslinks can improve scratch resistance and prevent deterioration of weak anchoring properties due to contact with NMP.

<3. Liquid crystal display element having cured film having weak anchoring property>
Liquid crystal compounds include a positive type with positive dielectric anisotropy and a negative type with negative dielectric anisotropy. A positive liquid crystal compound has a large dielectric property in the long axis direction of liquid crystal molecules and a small dielectric property in a direction orthogonal to the long axis direction. A negative-type liquid crystal compound has a dielectric property that is small in the longitudinal direction of liquid crystal molecules and large in a direction orthogonal to the longitudinal direction. In the following description of the liquid crystal display element, an example using a positive liquid crystal compound will be described.

The liquid crystal display element includes the strong anchoring film and the weak anchoring film as alignment films for controlling the alignment direction of the 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 a weak anchoring film.

A cured film obtained from the curable composition of the present invention can be used as the above weak anchoring film.

<3-1. First Embodiment>
FIG. 1 is a cross-sectional view showing 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. FIG. 2 is a diagram showing the distribution of orientation directions of liquid crystal molecules in a state where a liquid crystal compound Lp with positive dielectric anisotropy is used and an electric field E is applied in the first embodiment. FIG. 3 shows the wiring direction of the electrode lines and the orientation direction of the liquid crystal molecules near the weak anchoring film when the liquid crystal compound Lp with positive dielectric anisotropy is used and no electric field is applied in the first embodiment. FIG. 4 is a diagram showing relationships; FIG. 4 is a diagram showing the relationship between the wiring direction of the electrode lines and the orientation of the liquid crystal molecules when the liquid crystal compound Lp having the positive dielectric anisotropy is used and the electric field E is applied in the first embodiment. .

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

The first substrate (LCP-1) and the second substrate (LCP-2) are made of substrates such as glass, respectively, and are arranged parallel to each other with a predetermined space therebetween.

The polarizing plate 12A and the polarizing plate 12B are arranged in crossed Nicols. For example, the polarizing direction of the polarizing plate 12A is the Y direction, and the polarizing direction of the polarizing plate 12B is the X direction.

A drive electrode layer (LCP-4) is provided on either one of the first substrate (LCP-1) and the second substrate (LCP-2). As shown in FIG. 1, in the first embodiment, the drive electrode layer (LCP-4) is provided on the first substrate (LCP-1). The driving electrode layer (LCP-4) is formed by arranging a plurality of electrode lines 15A in parallel along the surface of the first substrate (LCP-1). In FIG. 1, each electrode line 15A is formed linearly so that its long axis direction extends along 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 within a plane parallel to the surface of the first substrate (LCP-1).

<3-2. Second Embodiment>
In the second embodiment, as shown in FIG. 5, a drive electrode layer (LCP-4) is provided on the second substrate (LCP-2). Other configurations are the same as those of the first embodiment.

EXAMPLES Next, the present invention will be specifically described by synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited by these examples.

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

Polymerizable compound having fluorine (m1):
m1-1: 2,2,2-trifluoroethyl methacrylate m1-2: 2-(perfluorohexyl)ethyl methacrylate m1-3: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate

Polymerizable compound having a carboxyl group (m21):
m21-1: methacrylic acid m21-2: 2-ethyl phthalate methacrylate polymerizable compound having an alkoxysilyl group (m22):
m22-1: 3-trimethoxysilylpropyl methacrylate m22-2: vinyltriethoxysilane

Polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group:
m4-1: methoxy polyethylene glycol methacrylate (Funkryl FA-400M (100), Hitachi Chemical Co., Ltd.)
m4-2: methoxy polyethylene glycol methacrylate (light ester 041MA, Kyoeisha Chemical Co., Ltd.)
m4-3: mono (meth) acryloxypropyl-modified polydimethylsiloxane (Silaplane FM0711 (number average molecular weight catalog value: 1,000), JNC Corporation)
m4-4: N-cyclohexylmaleimide m4-5: n-hexyl methacrylate

Polymerization initiator:
2,2'-Azobis(2-methylpropionate) dimethyl (V-601; trade name, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "V-601")

Polymerization solvent:
PGMEA

Tetracarboxylic dianhydride (b11):
b11-1: Butanetetracarboxylic dianhydride (trade name; Rikacid BT-100, Shin Nippon Rika Co., Ltd., hereinafter abbreviated as “BT-100”)
b11-2: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA")
Diamine (b12):
b12-1: 3,3′-diaminodiphenylsulfone (hereinafter referred to as “DDS”)
Polyvalent hydroxy compound (b13):
b13-1: 1,4-butanediol
Monohydric alcohol (b14):
b14-1: benzyl alcohol
Styrene-maleic anhydride copolymer (b15):
b15-1: SMA1000 (Kawa Petrochemical Co., Ltd.)
Polymerization solvent used for reaction of polyesteramic acid (B1):
PGMEA

Copolymer (B3) having an acid anhydride group:
B3-1: SMA1000 (Kawa Petrochemical Co., Ltd.)

Polyfunctional epoxy compound (C):
C-1: TECHMORE VG3101L (trade name, Printec Co., Ltd., hereinafter abbreviated as “VG3101L”), which is a compound having 3 or more glycidyl ether groups
C-2: EPPN-501H (trade name, Nippon Kayaku Co., Ltd.), which is a compound having 3 or more glycidyl ether groups
C-3: Marproof G-01100 (trade name, NOF Corporation, hereinafter abbreviated as "G-01100"), which is a compound having 3 or more glycidyl ester groups
C-4: EHPE3150 (trade name, Daicel Corporation), which is a compound having 3 or more oxiranyl groups

Additive (D):
D-1: COATOSIL MP200 (trade name, Momentive Performance Materials Japan LLC, hereinafter abbreviated as “MP200”), which is an epoxy compound
D-2: 3-glycidyloxypropyltrimethoxysilane (Sila Ace S510; trade name, JNC Corporation, hereinafter abbreviated as "S510"), which is a silane coupling agent
D-3: ADK STAB AO-60 (trade name; ADEKA Corporation, hereinafter abbreviated as "AO-60"), which is a hindered phenolic antioxidant
D-4: Megafac RS-72-K (trade name, DIC Corporation, hereinafter abbreviated as "RS-72-K"), which is a surfactant
D-5: TEGO Rad 2200N, a surfactant (trade name, Evonik Degussa Japan Co., Ltd., hereinafter abbreviated as "2200N")

First, a solution containing a copolymer having fluorine and a reactive group and a solution containing a polymer having no fluorine were synthesized as shown below (Synthesis Examples 1-14 and Comparative Synthesis Examples 1-2). .

[Synthesis Example 1] Synthesis of copolymer solution (A-1) having fluorine and reactive groups Fluorine was added to a 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet. 2,2,2-trifluoroethyl methacrylate (m1-1) as a polymerizable compound having (m1), methacrylic acid (m21-1) as a polymerizable compound having a carboxyl group (m21), V- as a polymerization initiator 601 and PGMEA as a polymerization solvent were added in the following weights, and polymerization was carried out by heating at a polymerization temperature of 90° C. for 4 hours.
2,2,2-trifluoroethyl methacrylate 96.00 g
24.00 g of methacrylic acid
V-601 4.80g
PGMEA 280.00g
The reaction solution was cooled to room temperature to obtain a 30% by weight solution (A-1) of a copolymer having fluorine and a reactive group. A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis. As a result, the weight average molecular weight was 14,000.

[Synthesis Examples 2-14 and Comparative Synthesis Examples 1-2]
According to the method of Synthesis Example 1, the raw material polymerizable compound, polymerization initiator, and polymerization solvent are charged in the proportions (unit: g) shown in Tables 1-1 and 1-2, and the polymerization reaction is carried out. Copolymer solutions (A-2) to (A-12) having fluorine and reactive groups, copolymer solutions (B2-1) and (B2-1) having no fluorine and having carboxyl groups, and (B'-1) and a reactive copolymer solution (B'-2) having no fluorine and having an alkoxysilyl group were obtained. In addition, the ratio of the polymerizable compound (m1) having fluorine in 100% by weight of the raw material (unit:% by weight; )]”), the ratio of the polymerizable compound (m21) having a carboxyl group in 100% by weight of the raw material (unit: wt%, the table shows “100 × (m2) / [(m1) + (m21) + (m22) + (m4)]”), and the weight average molecular weight of the solids contained in the obtained solution are also shown in Tables 1-1 and 1-2.

Using raw materials containing tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound, a polyesteramic acid solution was synthesized as shown below (Synthesis Examples 15 and 16).

[Synthesis Example 15] Synthesis of polyesteramic acid solution (B1-1) In a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, PGMEA as a solvent used in the synthesis reaction was added. 604.80 g of BT-100 as a tetracarboxylic dianhydride, 164.11 g of SMA-1000 as a styrene-maleic anhydride copolymer, 50.17 g of benzyl alcohol as a monohydroxy compound, 10.45 g of 1,4-butanediol was charged as a hydroxyl compound and stirred at 130° C. for 3 hours under a stream of dry nitrogen. After that, the solution after the reaction is cooled to 25°C, and 10.80 g of DDS and 25.20 g of PGMEA are added as diamines, stirred at 20 to 30°C for 2 hours, and then stirred at 115°C for 1 hour to 30°C or less. A pale yellow transparent polyesteramic acid solution (B1-1) having a solid content concentration of 30% by weight was obtained. The weight average molecular weight measured by GPC was 10,000.

[Synthesis Example 16] Synthesis of polyesteramic acid solution (B1-2) In a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, MMP was added as a solvent for the synthesis reaction. 446.96 g of , 31.93 g of 1,4-butanediol as a polyhydric hydroxy compound, 25.54 g of benzyl alcohol as a monohydroxy compound, and 183.20 g of ODPA as a tetracarboxylic dianhydride were charged, and dried under a stream of nitrogen. Stirred at 130° C. for 3 hours. After that, the solution after the reaction is cooled to 25° C., 29.33 g of DDS and 183.04 g of MMP are added as diamines, stirred at 20 to 30° C. for 2 hours, and then stirred at 115° C. for 1 hour, 30° C. or lower. A pale yellow transparent polyesteramic acid solution (B1-2) having a solid content concentration of 30% by weight was obtained. Also, the weight average molecular weight measured by GPC was 4,200.

[Example 1]
The copolymer solution (A-1) having fluorine and a reactive group obtained in Synthesis Example 1, SMA1000, VG3101L, RS-72-K, and PGMEA were mixed in the proportions shown in Table 2-1 (unit: g). and filtered through a membrane filter (0.2 μm) to obtain a curable composition.

Proportion of the copolymer (A) having fluorine and a reactive group in the total amount of 100% by weight of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B) (unit: weight %, described as “100×(A)/[(A)+(B)]” in the table) are shown in Table 2-1.

The amount of the polyfunctional epoxy compound (C) added to 100 parts by weight of the total amount of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B) (unit: parts by weight, the table shows " 100×(C)/[(A)+(B)]”) is shown in Table 2-1.

The total amount of the solvent contained in this curable composition is the total amount of PGMEA, which is the polymerization solvent contained in the copolymer solution (A-1) having fluorine and a reactive group, and PGMEA, which is the diluent solvent (E). It is the total amount, and it was prepared so that the solid content concentration was about 2.5% by weight in this step. The same applies to Example 2 and the following and Comparative Examples.

[Evaluation of scratch resistance]
The resulting curable composition was spin-coated on a glass substrate at 1,000 rpm for 10 seconds, and prebaked on a hot plate at 100° C. for 2 minutes to obtain a substrate with a coating film. Further, by post-baking in an oven at 230° C. for 30 minutes, a substrate with a cured film having a film thickness of approximately 100 nm was obtained. Hereinafter, the obtained cured film-coated substrate is referred to as "cured film-coated glass substrate".

The obtained glass substrate with a cured film was subjected to JIS K-5400-1990 8.4.1 pencil scratch test to measure the pencil hardness of the cured film. When the pencil hardness was H or more, the scratch resistance was evaluated as “◯”, and when the pencil hardness was F or less, the scratch resistance was evaluated as “×”. Table 2-1 shows the pencil hardness measurement results and scratch resistance evaluation results. However, in the pencil scratch test, if scratches were found even in the test using a pencil with a hardness of 2B, the pencil hardness measurement result was expressed as "<2B".

[Preparation of Comb-shaped Electrode Substrate 1 with Cured Film]
The resulting curable composition was spin-coated at 1,000 rpm for 10 seconds on a substrate with a Cr comb tooth electrode for IPS cells, and prebaked on a hot plate at 100° C. for 2 minutes to obtain a substrate with a coating film. . Further, by post-baking in an oven at 230° C. for 30 minutes, a substrate with a cured film having a film thickness of approximately 100 nm was obtained. Hereinafter, the obtained cured film-coated substrate is referred to as "cured film-coated comb electrode substrate 1".

[Preparation of strong anchoring film forming material (S-1)]
1.4184 g of 4,4'-diaminoazobenzene, 0.4184 g of 1,4-bis(4-aminophenyl)butane were placed in a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet. 5736 g, 0.1281 g of 1,4-bis(4-aminophenyl)piperazine, and 44.0 g of dehydrated NMP were charged and dissolved with stirring under a dry nitrogen stream. Then, 3.8799 g of 1,8-bis(3,4-dicarboxylic acid)octane dianhydride and 20.0 g of dehydrated NMP were added and stirred at room temperature for 24 hours to obtain a reaction solution. 20.0 g of ethylene glycol monobutyl ether was added to this reaction solution to obtain a polyamic acid solution having a solid concentration of 6% by weight. This polyamic acid solution is designated as (PA-1). The polyamic acid contained in (PA-1) had a weight average molecular weight of 10,000.

1.9123 g of 1,4-bis(4-aminophenyl)piperazine, 0.9123 g of 4,4′-diaminodiphenyl ether were placed in a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet. 8561 g, 0.3082 g of 1,4-phenylenediamine, and 44.0 g of dehydrated NMP were added and dissolved with stirring under a dry nitrogen stream. 1.8354 g of 1,2,3,4-butanetetracarboxylic dianhydride, 1.0880 g of pyromellitic dianhydride and 20.0 g of dehydrated NMP were added and stirred at room temperature for 24 hours. 30.0 g of ethylene glycol monobutyl ether was added to this reaction solution to obtain a polyamic acid solution having a polymer solid concentration of 6% by weight. This polyamic acid solution is designated as (PB-1). The polyamic acid contained in (PB-1) had a weight average molecular weight of 50,000.

A strong anchoring film forming material (S- 1) was prepared.
9.00 g of polyamic acid solution (PA-1) with a solid concentration of 6% by weight
21.00 g of polyamic acid solution (PB-1) with a solid concentration of 6% by weight
NMP 15.00g

[Fabrication of substrate with strong anchoring film]
The material for forming a strong anchoring film (S-1) was spin-coated on a glass substrate at 2,000 rpm for 10 seconds and prebaked on a hot plate at 70° C. for 80 seconds to obtain a glass substrate with a coating film. Next, using Multilight ML-501C/B (trade name, Ushio Inc.) equipped with an ultra-high pressure mercury lamp and a polarizing plate, the coated glass substrate was irradiated with linearly polarized ultraviolet light in the vertical direction. The amount of exposure was measured with a UV integrated light meter UIT-150 (trade name, Ushio Inc.) and a photodetector UVD-S365 (trade name, Ushio Inc.), and was converted to 2 J/cm ² at a wavelength of 365 nm. . Further, by post-baking in an oven at 230° C. for 20 minutes, a substrate with a strong anchoring film having a thickness of about 100 nm was obtained.

[Preparation of positive liquid crystal composition (LC-1)]
A positive liquid crystal composition (LC-1) was prepared by mixing and dissolving the compounds represented by the following general formulas (2-1) to (2-9) at the indicated weight ratios.

[Production of liquid crystal display element 1]
The two substrates, the comb electrode substrate with the cured film and the substrate with the strong anchoring film, were placed facing each other with the cured film side and the strong anchoring film side, respectively. The wiring direction of the comb-teeth electrode and the easy orientation axis of the strong anchoring film of the substrate with the strong anchoring film were arranged so as to be parallel to each other. Further, a gap for injecting the positive liquid crystal composition (LC-1) was formed between the cured film and the strong anchoring film, and the films were laminated to prepare an empty evaluation cell having a cell thickness of 4 μm. A positive liquid crystal composition (LC-1) was vacuum injected into the prepared empty cell for evaluation, and then annealed in an oven at 120° C. for 30 minutes to prepare a liquid crystal display device. Hereinafter, this obtained liquid crystal display element is referred to as "liquid crystal display element 1". 1, the wiring direction of the electrode lines 15A and the orientation easy axis of the strong anchoring film 14 are the direction Y. As shown in FIG.

[Determination of the presence or absence of orientation when no voltage is applied]
The prepared liquid crystal display element was sandwiched between two polarizing plates arranged in crossed Nicols on a light viewer 7000PRO (trade name, Hakuba Photo Sangyo Co., Ltd., hereinafter referred to as "backlight device"). Subsequently, the backlight device was turned on, and the light passing through the two polarizing plates and the liquid crystal display element thus produced was visually observed under two conditions. The first condition is that the wiring direction of the comb-tooth electrodes of the liquid crystal display element thus produced, that is, the easy alignment axis of the strong anchoring film of the substrate with the strong anchoring film is parallel to the polarization direction of the polarizer. If this condition corresponds to FIG. 1, the polarizing direction of the polarizing plate 12A on the backlight device side is the Y direction, and the polarizing direction of the other polarizing plate 12B is the X direction. FIG. 6 shows the relationship between the wiring direction of the electrode wires 15A and the polarization direction of the polarizing plate 12A. The second condition is a condition in which the two polarizing plates 12A and 12B of the first condition are rotated counterclockwise by 45° within the XY plane. That is, under the second condition, the angle formed by the wiring direction of the comb-teeth electrode and the polarization direction of the polarizing plate on the backlight device side is 45°. FIG. 7 shows the relationship between the wiring direction of the electrode wires 15A and the polarization direction of the polarizing plate 12A. A case where there was no light leakage under the first condition and light transmission was observed under the second condition was judged to be "existing" orientation when no voltage was applied. In the case of one or more of the case where there was light leakage under the first condition and the case where light transmission was not observed under the second condition, it was determined that the alignment was "absent" when no voltage was applied. Table 2-1 shows the result of determining the presence or absence of orientation when no voltage was applied.

[Determination of whether to drive when voltage is applied]
The alignment easy axis of the strong anchoring film of the liquid crystal display element obtained in the determination of the presence or absence of alignment when no voltage is applied is parallel to the polarization direction of the polarizing plate of the backlight device, and the comb-teeth electrode A voltage was applied to both electrodes so as to form a rectangular wave with a potential difference of 5 V and 60 Hz. When the light transmittance increased when voltage was applied compared to when no voltage was applied, it was determined that the light transmittance was "yes" when voltage was applied. . Table 2-1 shows the determination result of whether or not to drive when voltage is applied.

[Evaluation of weak anchoring property]
If the surface of the cured film is not given anisotropy by the rubbing method and the photo-alignment method described above, if the anchoring of the cured film is strong, the liquid crystal molecules in the vicinity of the cured film are random. , and in the process of judging the presence or absence of orientation when no voltage is applied, light leakage is observed. Therefore, the weak anchoring property was judged to be “good” when the above orientation was judged to be “yes” when the voltage was applied and the driving was “yes” when no voltage was applied. In other cases, the weak anchoring property was evaluated as “×”.

[Preparation of Comb-tooth Electrode Substrate 2 with Cured Film]
The resulting curable composition was spin-coated at 1,000 rpm for 10 seconds on a substrate with a Cr comb tooth electrode for IPS cells, and prebaked on a hot plate at 100° C. for 2 minutes to obtain a substrate with a coating film. . Further, by post-baking in an oven at 230° C. for 30 minutes, a substrate with a cured film having a film thickness of approximately 100 nm was obtained. Subsequently, NMP was spin-coated on the obtained substrate with the cured film, dried on a hot plate at 100° C. for 2 minutes, and then dried in an oven at 230° C. for 10 minutes. Hereinafter, the obtained cured film-coated substrate is referred to as "cured film-coated comb electrode substrate 2".

[Production of liquid crystal display element 2]
A liquid crystal display element 2 was produced in the same manner as the liquid crystal display element 1 except that the comb electrode substrate 1 with a cured film was changed to the comb electrode substrate 2 with a cured film.

[Evaluation of weak anchoring property after contact with NMP]
The liquid crystal display element 2 was used to determine the presence or absence of alignment when no voltage was applied in the same manner as the determination of the presence or absence of alignment when no voltage was applied using the liquid crystal display element 1 . Subsequently, the liquid crystal display element 2 was used to determine whether or not it was driven when a voltage was applied, in the same manner as the determination of whether or not it was driven when a voltage was applied using the liquid crystal display element 1 . The weak anchoring property after contact with NMP was judged to be “good” when the orientation was “present” when voltage was applied and the drive was “present” when no voltage was applied. In other cases, the weak anchoring property after contact with NMP was evaluated as "x".

[Examples 2 to 21 and Comparative Examples 1 to 3]
According to the method of Example 1, each component was mixed and dissolved in proportions (unit: g) shown in Tables 2-1, 2-2 and 2-3 to obtain a curable composition. According to the method of Example 1, the scratch resistance was evaluated from the results of measuring the pencil hardness, and the presence or absence of orientation when no voltage was applied and the presence or absence of driving when voltage was applied were determined, thereby weak anchoring property and NMP contact. The subsequent weak anchoring property was evaluated. The results are shown in Tables 2-1, 2-2 and 2-3. However, in the determination of the presence or absence of alignment when no voltage is applied using the liquid crystal display element 2, if it is determined that the alignment is "no" when voltage is applied, the determination of whether or not to drive when voltage is applied is not performed. 1, Tables 2-2 and 2-3 are marked with "-".

[Evaluation of weak anchoring property when annealing treatment is omitted]
The same as the liquid crystal display element 1 except that the curable compositions described in Examples 9, 11, 12, 16, 17, 18 and 19 were used and the annealing treatment step for 30 minutes in an oven at 120 ° C. was omitted. Then, a liquid crystal display element 3 was produced. The liquid crystal display element 3 was used to determine the presence or absence of alignment when no voltage was applied in the same manner as the determination of the presence or absence of alignment when no voltage was applied using the liquid crystal display element 1 . Subsequently, the liquid crystal display element 3 was used to determine whether or not it was driven when a voltage was applied, in the same manner as the determination of whether or not it was driven when a voltage was applied using the liquid crystal display element 1 . In both cases, it was determined that the alignment was "yes" when voltage was applied and the driving was "yes" when no voltage was applied.

[Adhesion test (Examples 4 and 6)]
Using the curable compositions described in Examples 4 and 6, glass substrates with cured films were obtained in the same manner as in the scratch resistance evaluation. A cross-cut test (JIS-K5600, ISO2409) by tape peeling of the cured film was performed on each of the obtained glass substrates with the cured film, and the remaining number was counted. Since all test results were classified as 0, it was judged that the adhesion of the cured film obtained from the curable composition to the substrate was good.

[Liquid repellency test (Example 20)]
An electrode substrate with a cured film was obtained in the same manner as in Example 1 using the curable composition described in Example 20. Using a portable contact angle meter PCA-1 (Kyowa Interface Science Co., Ltd.), 2 μL of water was dropped onto the obtained glass substrate with the cured film, and the contact angle of water was measured. Since the contact angle of water was 96°, it was judged that the liquid repellency of the cured film obtained from the curable composition was good.

[Heat resistance test (Example 21)]
Liquid crystal was prepared in the same manner as in Example 1, except that the curable composition described in Example 21 was used and the post-baking time in producing the cured film-coated comb electrode substrate 1 was changed from 30 minutes to 120 minutes. A display element 1 was obtained. Using the obtained liquid crystal display element, the weak anchoring property was evaluated in the same manner as in Example 1. As a result, the weak anchoring property was evaluated as ○, so the heat resistance of the cured film obtained from the cured composition. was judged to be good.

As is clear from the results shown in Tables 2-1, 2-2 and 2-3, the curable compositions of Examples 1 to 21 had scratch resistance and NMP Excellent weak anchoring property after contact. On the other hand, the curable composition of Comparative Example 1, which contains a polymer using the same raw material as the polymer brush, has good weak anchoring properties after the cured film comes into contact with NMP, but has poor scratch resistance. In addition, the curable composition of Comparative Example 2, which does not contain the polyfunctional copolymer (B), has poor scratch resistance and weak anchoring properties after contact with NMP in the cured film obtained from the curable composition. . The curable composition of Comparative Example 3, which is a curable composition containing a polyfunctional copolymer (B) but has a small proportion of the compound (m21) having a carboxyl group in the raw material of the polyfunctional copolymer (B) However, the resulting cured film has poor scratch resistance and weak anchoring properties after contact with NMP.

A cured film obtained from the curable composition of the present invention is excellent in weak anchoring properties, and thus can be used as a weak anchoring film for liquid crystal display devices. Furthermore, since it is also excellent in weak anchoring properties after contact with NMP, it can be used when both a weak anchoring film and a strong anchoring film are formed. In addition, since the cured film of the curable composition of the present invention has high scratch resistance, it is less likely to be scratched during the production of the liquid crystal display device. Therefore, the productivity of the liquid crystal display device can be improved.

10 liquid crystal display element 11 backlight unit 12A, 12B polarizing plate LCP-1 first substrate LCP-2 second substrate LCP-3 liquid crystal layer LCP-4 drive electrode layer 13 weak anchoring film 14 strong anchoring film 15A electrode line Lp Liquid crystal compounds X, Y Coordinate axes imaginary on a plane parallel to the first substrate and the second substrate

Claims (18)

A curable composition comprising a copolymer (A) having fluorine and a reactive group, a polyfunctional copolymer (B) and a polyfunctional epoxy compound (C);
The copolymer (A) having fluorine and a reactive group comprises a polymerizable compound (m1) having fluorine, a polymerizable compound (m2) having a reactive group, fluorine, a carboxyl group, an alkoxysilyl group, and an acid a product from a feed comprising a polymerizable compound (m4) having none of the anhydride groups;
The polymerizable compound (m2) having a reactive group is at least one selected from a polymerizable compound (m21) having a carboxyl group and a polymerizable compound (m22) having an alkoxysilyl group;
The polymerizable compound (m4) having none of fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group contains at least one (meth)acrylate compound having a polyethylene glycol chain;
The polyfunctional copolymer (B) is at least one selected from polyesteramic acid (B1), a copolymer having a carboxyl group (B2) and a copolymer having an acid anhydride group (B3) can be;
The copolymer (B2) having a carboxyl group includes the polymerizable compound (m21) having a carboxyl group, and a polymerizable compound having none of fluorine, a carboxyl group, an alkoxysilyl group, and an acid anhydride group ( m4) is a copolymer;
In the raw materials of the copolymer having a carboxyl group (B2), the polymerizable compound having a carboxyl group (m21) and the polymerizable compound having none of the fluorine, the carboxyl group, the alkoxysilyl group, and the acid anhydride group The polymerizable compound (m21) having a carboxyl group is 5 to 30% by weight in 100% by weight of the total amount of the compound (m4);
The copolymer (B3) having an acid anhydride group is a polymerizable compound (m3) having an acid anhydride group
and a copolymer of the polymerizable compound (m4) having none of the fluorine, carboxyl group, alkoxysilyl group, and acid anhydride group; and
A curable composition, wherein the polyfunctional epoxy compound (C) is a compound having 3 or more epoxy groups per molecule. 5 to 80 weight percent of the copolymer (A) having fluorine and a reactive group in the total amount of 100% by weight of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B) %;
Claim that the polyfunctional epoxy compound (C) is 30 to 300 parts by weight with respect to the total amount of 100 parts by weight of the copolymer (A) having fluorine and a reactive group and the polyfunctional copolymer (B). Item 1. The curable composition according to item 1. 3. The polymerizable compound (m1) having fluorine is 40% by weight or more and 98% by weight or less in 100% by weight of the raw material of the copolymer (A) having fluorine and a reactive group, according to claim 1 or 2. curable composition. 3. The polymerizable compound (m1) having fluorine is 50% by weight or more and 95% by weight or less in 100% by weight of the raw material of the copolymer (A) having fluorine and a reactive group, according to claim 1 or 2. curable composition. 5. The curable composition according to any one of claims 1 to 4, wherein the fluorine-containing polymerizable compound (m1) is a fluorine-containing (meth)acrylate compound. The curable composition according to claim 5, wherein the fluorine-containing (meth)acrylate compound is a compound represented by the following formula (1);

In formula (1), R ¹ is hydrogen or a methyl group; R ² to R ⁸ are each independently hydrogen or fluorine; n ¹ and n ³ are each independently an integer of 0 to 3; n ² and n ⁴ are each independently an integer of 0 to 6; and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine. The compound represented by formula (1) is 2,2,2-trifluoroethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate. , and 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate. The polymerizable compound having a carboxyl group (m21) is at least one selected from (meth)acrylic acid and a (meth)acrylate compound having a carboxyl group, according to any one of claims 1 to 7. curable composition. The curable composition according to any one of claims 1 to 7, wherein the polymerizable compound (m21) having a carboxyl group is methacrylic acid. Any one of claims 1 to 9, wherein the polymerizable compound having an alkoxysilyl group (m22) is at least one selected from a (meth)acrylate compound having an alkoxysilyl group and a vinyl compound having an alkoxysilyl group. 2. The curable composition according to item 1. The (meth)acrylate compound having an alkoxysilyl group is at least one selected from 3-trimethoxysilylpropyl (meth)acrylate and 3-triethoxysilylpropyl (meth)acrylate, and the vinyl having the alkoxysilyl group 11. The curable composition according to claim 10, wherein the compound is at least one selected from vinyltrimethoxysilane. The curable composition according to any one of claims 1 to 11, wherein the (meth)acrylate compound having a polyethylene glycol chain is methoxypolyethylene glycol (meth)acrylate. The polyfunctional epoxy compound (C) is at least one selected from a compound having 3 or more glycidyl ether groups, a compound having 3 or more glycidyl ester groups, and a compound having 3 or more oxiranyl groups. 13. The curable composition according to any one of 1 to 12. 14. The curable composition according to any one of claims 1 to 13, for forming a weak anchoring film of a liquid crystal display device. A cured film obtained by curing the curable composition according to any one of claims 1 to 14. A liquid crystal display device comprising the cured film according to claim 15 as a weak anchoring film. a first substrate (LCP-1) on which a weak anchoring film is formed;
a second substrate (LCP-2) on which a strong anchoring film is formed facing the weak anchoring film with a gap therebetween;
a liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film;
and provided on either one of the first substrate (LCP-1) and the second substrate (LCP-2), and the liquid crystal molecules in the liquid crystal layer are connected to the first substrate (LCP-1) and the second substrate A liquid crystal display device comprising a driving electrode layer (LCP-4) for applying an electric field in a direction along (LCP-2);
17. The liquid crystal display device according to claim 16, wherein the liquid crystal molecules are driven by an electric field applied to the driving electrode layer (LCP-4) to change the light transmittance. The drive electrode layer (LCP-4) is composed of a plurality of electrode wires arranged on the substrate surface of the first substrate (LCP-1) or the second substrate (LCP-2), and when the electric field is not applied, 18. The liquid crystal display element according to claim 17, wherein the alignment direction of the liquid crystal molecules on the second substrate (LCP-2) side is parallel or perpendicular to the direction in which the electrode lines continue.

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