JP2018197856A - Curable composition, cured product and liquid crystal display element - Google Patents

Abstract

To provide a curable composition which gives a cured product having excellent weak anchoring properties and can be patterned and to provide a cured product formed by the curable composition and an electronic component having the cured film.SOLUTION: There is provided a curable composition which comprises a copolymer (A) having fluorine and a carboxyl group, a polyfunctional polymerizable compound (B) and a photopolymerization initiator (C).SELECTED DRAWING: Figure 2

Description

  The present invention relates to an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, a weak anchoring film in a liquid crystal display element, and a protective film for a color filter The present invention relates to a curable composition that can be used for forming a liquid crystal display device, a cured product thereby, and a liquid crystal display device having the cured product.

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

  As a method of forcing the alignment direction of liquid crystal molecules, after forming an alignment film manufactured using a solution containing polyimide on a substrate, a roller wrapped with a cloth such as rayon or cotton is rotated and the distance between the roller and the substrate The method of rotating the surface of the alignment film and rubbing the surface of the alignment film in one direction (rubbing method), the method of generating anisotropy on the polyimide film surface by irradiating with polarized ultraviolet rays (photo alignment method), etc. It has been adopted. By these treatments, the liquid crystal molecules are strongly bound to the substrate surface with the alignment film and are aligned in a certain direction. Hereinafter, the direction in which the liquid crystal molecules are bound to the substrate surface with the alignment film and aligned is referred to as “orientation easy axis”.

  In recent years, a liquid crystal display element having a strong anchoring film on one side of the substrate and a weak anchoring film on the other side has been proposed as an improvement measure for improving the display responsiveness of the liquid crystal display element (for example, see Patent Document 1). Has been. In the present specification, the liquid phase and film forcing the alignment direction of liquid crystal molecules such as the alignment film described above are collectively referred to as “strong anchoring film”, and the alignment regulating force (anchoring) on the substrate surface is described. The liquid layer and the film that weaken the film are collectively referred to as “weak anchoring film”.

  In the example of Patent Document 1, a polyimide film subjected to rubbing treatment is used as the strong anchoring film, and a method of forming a polymer brush on the substrate surface is used as the weak anchoring film. However, in order to form a polymer brush on the substrate surface, the substrate must be immersed in a polymerization solution containing a monomer, an initiator, a catalyst, and a solvent and polymerized on the substrate. It is necessary to protect the area not forming the polymer brush with a masking tape or to remove the formed polymer brush. This method has a problem that the manufacturing process is complicated, and at the same time, it is difficult to pattern the weak anchoring film on the substrate.

  In addition, a display element has been proposed in which the alignment direction of liquid crystal molecules is directed in an arbitrary direction by an external field such as an electric field and a magnetic field, and the state is maintained (memory) (for example, see Patent Document 2). In order to realize such an operation, it is necessary to weaken the alignment forcing (anchoring) of the substrate surface, and for that purpose, a method of configuring a liquid crystal device with a completely wet liquid-liquid crystal interface, that is, Then, a liquid crystal composition added with a liquid insoluble in a liquid crystal material (for example, polystyrene) is injected so as to be sandwiched between two substrates, causing liquid-liquid crystal phase separation in the liquid crystal composition, and A method for forming a liquid layer has been proposed. However, in this method, both sides of the two substrates have weak anchoring properties.

JP2017-010030 JP 2006-084536 A

  An object of the present invention is to provide a curable composition capable of providing a cured product excellent in weak anchoring property and capable of patterning, and a cured product formed by the curable composition. It is providing the liquid crystal display element which has a body.

As a result of intensive studies to solve the above problems, the present inventors have obtained a cured product obtained by curing a composition comprising a copolymer having a fluorine and a carboxyl group, a polyfunctional polymerizable compound, and a photopolymerization initiator. Thus, the inventors have found that the above object can be achieved and have completed the present invention.
The present invention includes the following configurations.

[1] A curable composition comprising a copolymer (A) having fluorine and a carboxyl group, a polyfunctional polymerizable compound (B), and a photopolymerization initiator (C).

[2] The copolymer (A) having fluorine and a carboxyl group is a copolymer from a raw material containing a polymerizable compound (a1) having fluorine and a polymerizable compound (a2) having a carboxyl group, [1 ] The curable composition of a term.

[3] In item [2], the polymerizable compound (a1) having fluorine is 50% by weight to 98% by weight in 100% by weight of the raw material of the copolymer (A) having fluorine and carboxyl groups. The curable composition as described.

[4] In item [2], the polymerizable compound (a1) having fluorine is 80% by weight to 95% by weight in 100% by weight of the raw material of the copolymer (A) having fluorine and carboxyl groups. The curable composition as described.

[5] In the item [2], the raw material of the copolymer (A) having a fluorine and a carboxyl group comprises the polymerizable compound (a1) having the fluorine and the polymerizable compound (a2) having the carboxyl group. The curable composition as described.

[6] The curable composition according to any one of [2] to [5], wherein the fluorine-containing polymerizable compound (a1) 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の少なくとも１つはフッ素である。） [7] The curable composition according to item [6], 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; at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.)

[8] 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 [7], which is at least one selected from (meth) acrylate and 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate.

[9] The curable composition according to item [7], wherein the compound represented by the formula (1) is 2,2,2-trifluoroethyl methacrylate.

[10] Any of [2] to [9], wherein the polymerizable compound (a2) having a carboxyl group is at least one selected from (meth) acrylic acid and a (meth) acrylate compound having a carboxyl group. 2. The curable composition according to item 1.

[11] The curable composition according to any one of [2] to [9], wherein the polymerizable compound (a2) having a carboxyl group is methacrylic acid.

[12] The curable composition according to any one of [1] to [11], wherein the polyfunctional polymerizable compound (B) is a compound having three or more polymerizable double bonds per molecule.

[13] The compound having three or more polymerizable double bonds per molecule is an isocyanuric acid ethylene oxide-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di The curable composition according to item [12], which is at least one selected from pentaerythritol hexaacrylate and a carboxyl group-containing polyfunctional (meth) acrylate.

[14] The curable composition according to any one of [1] to [13] for forming a weak anchoring film of a liquid crystal display element.

[15] A cured product obtained by curing the curable composition according to any one of [1] to [14].

[16] A liquid crystal display device having the cured product according to the item [15] as a weak anchoring film.

[17] A first substrate (LCP-1) on which the weak anchoring film according to [16] is formed,
A second substrate (LCP-2) on which a strong anchoring film disposed opposite to the weak anchoring film with a space therebetween is formed;
A liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film;
The first substrate (LCP-1) and the second substrate (LCP-2) are provided on either one of the first substrate (LCP-1) and the second substrate (LCP-2). -2) a liquid crystal display device comprising a drive electrode layer (LCP-4) for applying an electric field in a direction along the line;
A liquid crystal display element in which light transmittance is changed by driving liquid crystal molecules by an electric field applied to the driving electrode layer (LCP-4).

[18] 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), and the electric field is not marked. The liquid crystal display element according to the item [17], 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.

  The curable composition which concerns on the preferable aspect of this invention is a curable composition which gives the hardening body excellent in weak anchoring property, and has favorable patterning property. When the cured product is used as a weak anchoring film of a liquid crystal display element, it is possible to perform a display with higher transmittance in driving a liquid crystal molecule at a low voltage, and the weak anchoring film is removed without removing the weak anchoring film in unnecessary portions. A liquid crystal display element with a ring film can be manufactured. In particular, it is useful as a liquid crystal display element in which one of the two strong anchoring films of the liquid crystal display element in the IPS display mode is replaced with a weak anchoring film. It can also be used as a protective film and a transparent insulating film for various optical materials.

It is sectional drawing which shows schematic structure of 1st Embodiment of the liquid crystal display element 10 of this invention, and the backlight unit 11 and polarizing plate 12A and 12B for a display. In the said 1st Embodiment, it is sectional drawing which shows distribution of the orientation direction of the liquid crystal molecule in the state which applied the electric field E using the liquid crystal compound Lp with positive dielectric anisotropy. In the first embodiment, the liquid crystal compound Lp having a positive dielectric anisotropy is used, and the plane showing the relationship between the wiring direction of the electrode lines and the alignment direction of the liquid crystal molecules in the vicinity of the weak anchoring film when no electric field is applied. FIG. In the said 1st Embodiment, it is a top view which shows the relationship between the wiring direction of the electrode wire | line in the state which applied the electric field E using the liquid crystal compound Lp with positive dielectric anisotropy, and the orientation direction of a liquid crystal molecule. It is sectional drawing which shows schematic structure of 2nd Embodiment of the liquid crystal display element 10 of this invention, and the backlight unit 11 and polarizing plates 12A and 12B for a display. FIG. 6 is a plan view showing the relationship between the wiring direction of an electrode line 15A and the polarization direction of a polarizing plate 12A in a first condition in the method for determining the presence or absence of orientation when no voltage is applied in an example. FIG. 10 is a plan view showing the relationship between the wiring direction of an electrode line 15A and the polarization direction of a polarizing plate 12A under a second condition in the method for determining the presence or absence of orientation when no voltage is applied according to an example.

  In this specification, “cured body” means a solid film-shaped cured film, an uneven film-shaped cured film, a perforated film-shaped cured film, a projection-shaped cured body, and a linear-shaped cured body. Etc. are used as a general term.

  In this specification, in order to show one or both of “acryl” and “methacryl”, it may be expressed as “(meth) acryl”. Similarly, in order to indicate one or both of “acrylate” and “methacrylate”, the term “(meth) acrylate” may be used, and to indicate one or both of “acryloxy” and “methacryloxy” Sometimes expressed as “(meth) acryloxy”.

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

<1-1. Copolymer having fluorine and carboxyl groups (A)>
The copolymer (A) having fluorine and carboxyl groups used in the present invention is a copolymer of two or more kinds of raw materials containing a polymerizable compound (a1) having fluorine and a polymerizable compound (a2) having a carboxyl group. It is.

  The raw material of the copolymer (A) having fluorine and carboxyl groups includes a polymerizable compound excluding the polymerizable compound (a1) having fluorine and the polymerizable compound (a2) having a carboxyl group (hereinafter referred to as “other polymerizable compounds”). (A3) ”).

  Desirable weight ratios of the polymerizable compound in the raw material are 50% by weight to 98% by weight of the polymerizable compound (a1) having fluorine and 2% by weight of the polymerizable compound (a2) having a carboxyl group in 100% by weight of the raw material. % Or more and 30% by weight or less, and when the other polymerizable compound (a3) is contained, the other polymerizable compound (a3) is 48% by weight or less. With this weight ratio, a cured film excellent in weak anchoring property is provided, and a curable material excellent in patterning property is obtained. A more desirable weight ratio of the polymerizable compound is that the polymerizable compound (a1) having fluorine is 80% by weight to 95% by weight, the polymerizable compound (a2) having a carboxyl group is 5% by weight to 20% by weight, and When the other polymerizable compound (a3) is contained, the other polymerizable compound (a3) is 15% by weight or less.

<1-1-1. Polymeric compound (a1) having fluorine>
In this invention, the polymeric compound (a1) which has a fluorine is used as a raw material for obtaining the copolymer (A) containing a fluorine and a carboxyl group.

  Considering the compatibility with the polymerizable compound (a2) having a carboxyl group at the time of polymerization, the preferred polymerizable compound (a1) having fluorine is 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 preferable fluorine-containing (meth) acrylate 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; 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 preferably each independently 0 to 2; n ² and n ⁴ are preferably each independently 0, ¹ , 2, ⁴ , or 6; It is preferable that 3 to 12 of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ are fluorine.

Specific examples of the compound represented by the formula (1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (par Fluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4,4 5,5-toctafluoropentyl (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 (Trifluoromethyl) ethyl (meth) acrylate. One or more of these can be used.

  In consideration of compatibility with the polymerizable compound (a2) having a carboxyl 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. Particularly preferred.

<1-1-2. Polymerizable compound having carboxyl group (a2)>
In this invention, the polymeric compound (a2) which has a carboxyl group is used as a raw material for obtaining the copolymer (A) containing a fluorine and a carboxyl group.

  Specific examples of the polymerizable compound (a2) 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; Styrenic 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. One or more of these can be used.

  In view of compatibility with the polymerizable compound (a1) having fluorine during polymerization and availability of raw materials, (meth) acrylic acid and (meth) acrylate compounds having a carboxyl group are preferred, and methacrylic acid is particularly preferred.

<1-1-3. Other polymerizable compounds (a3)>
In this invention, another polymeric compound (a3) can be used as a raw material for obtaining the copolymer (A) containing a fluorine and a carboxyl group.

Specific examples of the other polymerizable compound (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Alkyl (meth) acrylate compounds;
Aryl (meth) acrylate compounds 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 an ether bond such as 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate;
(Meth) acrylate compounds having a cyclic ether such as glycidyl (meth) acrylate;
(Meth) acrylate compounds having an alkoxysilyl group such as 3-trimethoxysilylpropyl (meth) acrylate; (meth) acrylate compounds having a polydimethylsiloxane 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-phenylmaleimide, N-cyclohexylmaleimide, and N- (4-hydroxyphenyl) maleimide N-substituted maleimide compounds such as
Styrene, 4-hydroxystyrene, and (meth) acrylamide. One or more of these can be used.

  The other polymerizable compound (a3) has an effect of imparting properties of the cured film other than the weak anchoring property and the patterning property. Examples of effects obtained by using other polymerizable compounds (a3) are the effects of adjusting the refractive index of a cured product by using an aryl (meth) acrylate compound, and the curing by using a (meth) acrylate compound having an alkoxysilyl group. The effect of improving adhesion to the substrate of the body, the effect of improving the chemical resistance of the cured product by using the (meth) acrylate compound having a cyclic ether, and the repelling property of the cured product by using the (meth) acrylate compound having polydimethylsiloxane. This is a liquid property improving effect and a heat resistance improving effect of the cured product by using an N-substituted maleimide compound.

<1-1-4. Copolymer polymerization method>
The polymerization method of the copolymer (A) having fluorine and carboxyl groups is not particularly limited. An example of the polymerization method is radical polymerization in a solution using a polymerization solvent, and a solution containing a copolymer (A) having fluorine and a carboxyl group can be obtained. 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 not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

  The polymerization solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of the raw material for the copolymer (A) having fluorine and carboxyl groups, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours.

  A curable composition can be produced by using a solution containing the copolymer (A) having fluorine and carboxyl groups. Examples of the method for producing a curable composition include a method for producing a curable composition by directly using a solution containing a copolymer (A) having fluorine and a carboxyl group in which the polymerization solvent is left as it is, and fluorine and carboxyl. In this method, the polymerization solvent in the solution containing the copolymer (A) having a group is removed, and then a dilution solvent is added to produce a liquid or gel curable composition.

<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 carboxyl groups are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene. Diol compounds such as 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 monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Monoethers of diol compounds such as 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, diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, diethylene glycol Diethers of diol compounds such as propylene glycol dimethyl ether and 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, methoxy Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropio Monoether monoesters of monohydroxycarboxylic acid compounds such as ethyl acetate and methyl 4-methoxybutyrate; diesters of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate; N, N-dimethylacetamide, and N Monoamides of monocarboxylic acid compounds such as, N-dimethylpropionamide, dialkyl ketone compounds such as methyl isobutyl ketone, methyl normal butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl ketone, and dinormal butyl ketone; hexamethylene oxide; And cyclic ether compounds such as 1,4-dioxane; cyclic ester compounds such as β-propiolactone, γ-butyrolactone, and δ-valerolactone; cyclic amides such as 2-pyrrolidone and 1-methyl-2-pyrrolidone Compound; and cyclopentanone, cyclohexanone, and cyclic ketone compounds such cycloheptanone. One or more of these can be used.

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

<1-1-6. Molecular Weight of Copolymer (A) Having Fluorine and Carboxyl Group>
The weight average molecular weight of the obtained copolymer (A) having fluorine and carboxyl groups is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in these ranges, weak anchoring property and patterning property will become favorable.

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

<1-2. Polyfunctional polymerizable compound (B)>
Examples of the polyfunctional polymerizable compound (B) used in the present invention are a compound having two polymerizable double bonds per molecule and a compound having three or more polymerizable double bonds per molecule.

  A compound having two polymerizable double bonds per molecule has an excellent effect of giving a curable composition having patternability without impairing the weak anchoring property of the cured product, and 3 polymerizable double bonds per molecule. A compound having one or more compounds provides a curable composition that can be cured with a small amount of ultraviolet irradiation.

  With respect to the demands for improving productivity in the manufacturing process of display devices in recent years, the curable composition is required to be cured by a small amount of ultraviolet irradiation, and therefore, at least 3 polymerizable double bonds per molecule in the curable composition. It is desirable to contain the compound which has. Further, in 100% by weight of the polyfunctional polymerizable compound (B), a compound having 3 or more polymerizable double bonds per molecule is preferably contained in an amount of 50% by weight or more, more preferably 80% by weight or more.

<1-2-1. Compound having two polymerizable double bonds per molecule>
Specific examples of the compound having two polymerizable double bonds 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 A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, and ethylene oxide-modified bisphenol S di (meth) di (meth) acrylate of diol compounds such as 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, 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 Tetrapropylene 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 epoxy compound ( It is a (meth) acrylic acid adduct of a diepoxy compound such as a (meth) acrylic acid adduct. One or more of these can be used.

<1-2-2. Compound having 3 or more polymerizable double bonds per molecule>
Specific examples of the compound having three or more polymerizable double bonds 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- Trifunctional (meth) acrylate compounds such as (2- (meth) acryloxyethyl) isocyanurate;
Tetrafunctional (meta) such as ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, and diglycerin EO modified tetraacrylate ) 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. One or more of these can be used.

  The following commercially available products can be used as the compound having 3 or more polymerizable double bonds per molecule.

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

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

  Specific examples of commercially available dipentaerythritol hexaacrylate, which is a hexafunctional acrylate compound, are NK ester A-DPH (trade name, Shin-Nakamura Kogyo Co., Ltd.) and DPHA (trade name, Daicel Ornex Co., Ltd.). is there.

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

  Specific examples of commercial products of a mixture of ethoxylated isocyanuric acid triacrylate, which is a trifunctional acrylate compound, and ethoxylated isocyanuric acid diacrylate, which is a bifunctional acrylate compound, are Aronics M-313 (30-40 wt%) and M -315 (3 to 13% by weight) (all are trade names, Toagosei Co., Ltd., and the content in parentheses is the catalog value of the content of ethoxylated isocyanuric diacrylate in the mixture).

  Specific examples of commercial products of a mixture of pentaerythritol triacrylate, which is a trifunctional acrylate compound, and pentaerythritol tetraacrylate, which is a tetrafunctional acrylate compound, are PETIA, PETRA, and PETA (all trade names, Daicel Ornex Corporation) Company), Aronix M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 (30-60 wt%), M-452 (25-40 wt%), and M -450 (less than 10% by weight) (both are trade names, Toagosei Co., Ltd., and the content in parentheses is the value listed in the catalog of the content of pentaerythritol triacrylate in the mixture).

Specific examples of commercial products of a mixture of dipentaerythritol pentaacrylate, which is a pentafunctional acrylate compound, and dipentaerythritol hexaacrylate, which is a hexafunctional acrylate compound, are Aronics M-403 (50 to 60% by weight), M- 400 (40-50 wt%), M-402 (30-40 wt%), M-404 (30-40 wt%), M-406 (25-35 wt%), and M-405 (10-20 % By weight) (trade name, Toagosei Co., Ltd., the content in parentheses is the value listed in the catalog of the content of pentaerythritol pentaacrylate in the mixture).
<1-3. Photoinitiator (C)>
The photopolymerization initiator (C) used in the present invention is a compound capable of initiating polymerization of the polyfunctional polymerizable compound (B).

  Specific examples of the photopolymerization initiator (C) 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-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACUR) 907; trade name, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE 369; trade name, BASF Japan Ltd.), 4-dimethylaminobenzo Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRGACURE OXE01; trade name, BASF Japan Ltd.), Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -1- (O-acetyloxime (IRGACURE OXE02; trade name, BASF Japan Ltd.), IRGACURE OXE03 (trade name, BASF Japan Ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) (Adeka Arcles NCI-930; trade name, ADEKA Corporation), Adeka Arcles NCI-831 (trade name, ADEKA Corporation), Adekaoptomer N-1919 (trade name, ADEKA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4' -Dimethoxystyryl) -4,6-bis (trichloromethyl)- -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′-methoxy) Phenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothia Sol, 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) carbazo 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. One or more of these can be used.

  Among the specific examples of the photopolymerization initiator described above, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl When one or more selected from 2- (O-acetyloxime) is used, the curable composition is cured with a smaller exposure amount. One or more selected from them is preferably 20% by weight or more, and more preferably 50% by weight or more, based on the total weight of the photopolymerization initiator.

<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 has the characteristics of the curable composition of the present invention such as coating uniformity, adhesion, stability, chemical resistance, and resolution. It is added from the viewpoint of improving. Examples of additives include anionic, cationic, nonionic, and fluorine surfactants; silicone resin coating improvers; adhesion improvers such as silane coupling agents; and aggregation prevention such as sodium polyacrylate Agents; polymer dispersants such as acrylic, styrene, polyethyleneimine, and urethane; antioxidants such as hindered phenols; crosslinking agents such as epoxy compounds, melamine compounds, and bisazide compounds; and photoacid generators It is.

<1-4-1. Surfactant, coatability improver>
The curable composition of the present invention may further contain a surfactant from the viewpoint of further improving the coating uniformity. Specific examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, Kyoeisha Chemical Co., Ltd.), Disperbak 161, Dispersake 162, Dispersake 163, Dispersake 164, Dispersake 166, Dispersake 170, Dispersake 180, Dispersake 181, Dispers Bake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all are trade names, Shin-Etsu Chemical Co., Ltd.), Surflon SC-10 , Surflon KH-40, Surflon S611 (all are trade names, AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 602A, Aftergent 650A, FTX-218 (all are trade names, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (and above) All are trade names, Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Gafuck F-472SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F -558, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 (and above) All are trade names, DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxy) Ethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, poly Oxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxy Ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Ethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. One or more of these can be used.

  Among specific examples of these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surflon S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Footage 650A, Megafuck F-477, Megafuck F-556, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxy When at least one selected from ethylene ether, fluoroalkyl sulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonate, the coating uniformity of the curable composition is improved. This is preferable because of its great effect.

  The addition amount of the surfactant in the curable composition of the present invention is 100 weight total of the copolymer (A) having a fluorine and a carboxyl group, the polyfunctional polymerizable compound (B), and the photopolymerization initiator (C). It is preferable that it is 0.01-5 weight part with respect to a part.

<1-4-2. Adhesion improver>
The curable composition of this invention may further contain the adhesive improvement agent from a viewpoint of further improving the adhesiveness with respect to the base material of the hardening body formed. As a specific example of the adhesion improver, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; trade name, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (e.g., Silaace S530; trade name, JNC Corporation), 3-trimethoxysilylpropyl methacrylate (e.g., Silaace S710; trade name, JNC Corporation), 3-mercaptopropyltri Silane coupling agents such as methoxysilane (eg, Silaace S810; trade name, JNC Corporation), aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and tetraisopropyl It is a titanate coupling agent such as pyrbis (dioctyl phosphite) titanate. One or more of these can be used.

  Among the specific examples of these adhesion improvers, 3-glycidyloxypropyltrimethoxysilane and 3-trimethoxysilylpropyl methacrylate are preferable because they have a large effect of improving the adhesion of the cured product to the substrate.

  The addition amount of the adhesion improver in the curable composition of the present invention is 100 in total of the copolymer (A) having a fluorine and a carboxyl group, the polyfunctional polymerizable compound (B), and the photopolymerization initiator (C). It is preferable that it is 0.1-20 weight part with respect to a weight part.

<1-4-3. Anti-agglomeration agent>
The curable composition of the present invention may further contain an agglomeration inhibitor from the viewpoint of becoming familiar with the solvent and preventing agglomeration. The agglomeration inhibitor is used to blend with the solvent and prevent agglomeration. Specific examples of the aggregation inhibitor optionally added to the curable composition of the present invention include 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 are trade names, BIC Chemie Japan Co., Ltd.), FTX-218, aftergent 710FM, aftergent 710FS (All are trade names, Neos Co., Ltd.), Floren G-600, and Floren G-700 (all trade names, It is a company Chemical Industry Co., Ltd.). One or more of these can be used.

<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 product is exposed to a high temperature. Specific examples of the antioxidant include, Irganox1010, IrganoxFF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 ( All are trade names, BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50 ADK STAB AO-60, ADK STAB AO-70, and ADK STAB AO-80 (trade names, Ltd. ADEKA) is. One or more of these can be used.

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

  The addition amount of the antioxidant in the curable composition of the present invention is 100 weight total of the copolymer (A) having a fluorine and a carboxyl group, the polyfunctional polymerizable compound (B), and the photopolymerization initiator (C). It is preferable that it is 0.01-5 weight part with respect to a part.

<1-4-5. Cross-linking agent>
The curable composition of the present invention includes a crosslinking agent such as an epoxy compound, a melamine compound, and a bisazide compound from the viewpoint of improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity. Furthermore, you may contain.

  Examples of epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolacs. Type epoxy compound, aliphatic polyglycidyl ether compound, cycloaliphatic epoxy compound, polymer of polymerizable compound having epoxy group, copolymer of polymerizable compound having epoxy group and other polymerizable compound, and siloxane bond An epoxy compound having a moiety.

  Specific examples of commercial products of bisphenol A type epoxy compounds are jER 828, 1004, and 1009 (all trade names are Mitsubishi Chemical Corporation); specific examples of commercial products of bisphenol F type epoxy compounds are jER 806 and 4005P. Specific examples of commercially available glycidyl ether type epoxy compounds are TECHMORE VG3101L (trade name, Printec Co., Ltd.), EHPE-3150 (trade name, Daicel Corporation). EPPN-501H, 502H (all trade names, Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name, Mitsubishi Chemical Corporation); specific examples of commercially available glycidyl ester type epoxy compounds include Denacol EX- 721 (trade name, Nagase ChemteX Corporation), and Diglycidyl 1,2-cyclohexanedicarboxylate (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available biphenyl type epoxy compounds are jER YX4000, YX4000H, YL6121H (all trade names, Mitsubishi Chemical Corporation). ), And NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names, Nippon Kayaku Co., Ltd.); specific examples of commercially available phenol novolac epoxy compounds are: EPPN-201 (trade name, Nippon Kayaku Co., Ltd.) and jER 152, 154 (both trade names, Mitsubishi Chemical Co., Ltd.), etc .; specific examples of commercially available cresol novolac epoxy compounds are EOCN-102S , 103S, 104S, 1020 (all trade names, Nippon Kayaku Co., Ltd.), etc .; Specific examples of commercial products of Sphenol A novolac type epoxy compounds are jER 157S65 and 157S70 (both trade names, Mitsubishi Chemical Corporation); specific examples of commercial products of cycloaliphatic epoxy compounds include Celoxide 2021P, 3000 (all are trade names, Daicel Corporation); a specific example of a commercially available epoxy compound having a siloxane bonding site is 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldi Siloxane (trade name, Gelest Incorporated), TSL 9906 (trade name; Momentive Performance Material Co., Ltd.), CoatOsil MP200 (trade name, Momentive Performance Material Co., Ltd.), Composeran SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES- 10 3 (trade name, Shin-Etsu Chemical Co., Ltd.) is. One or more of these can be used.

  TECHMORE VG3101L (trade name, Printec Co., Ltd.) is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- ( 2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; EHPE-3150 (trade name, Daicel Corporation) is 2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct; Celoxide 2021P (trade name, Daicel Corporation) is ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Celoxide 3000 (trade name, Daicel Corporation) is 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] Heptane; CoatOsil MP200 (trade name, Momentive Performance Material Co., Ltd.) is a polymer containing 3-glycidoxypropyltrimethoxysilane as a raw material 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. An example of a photoacid generator is a 1,2-quinonediazide compound.

  Specific examples of 1,2-quinonediazide compounds include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide. -5-sulfonic acid ester (for example, trade name, NT-200, Toyo Gosei 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-naphtho Quinonediazide-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) meta -1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester; tri (p-hydroxyphenyl) methane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphtho Quinonediazide-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] fur Nyl] 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′-spirobi Indene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-s Phosphonate ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide— 5-sulfonic acid ester; 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, and 2,2,4-trimethyl-7, 2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester. One or more of these can be used.

<1-5. Solvent optionally added to the curable composition>
In addition to the polymerization solvent, a solvent may be added to the curable composition of the present invention. The solvent optionally added to the curable composition of the present invention (hereinafter referred to as “dilution solvent (E)”) is a copolymer having a fluorine and a carboxyl group (A), a compound having a polymerizable double bond. A solvent capable of dissolving (B) and the photopolymerization initiator (C) is preferred. When the curable composition contains the above-mentioned additive (D), the solvent for dilution (E) is preferably a solvent that can dissolve the additive (D).

  The specific example of the said solvent for dilution (E) is the same as the solvent described as a specific example of the above-mentioned polymerization solvent. One or more of these can be used.

<1-6. Storage of Curable Composition>
The curable composition of the present invention is preferably stored in the range of −30 ° C. to 25 ° C. in a light-shielded state because the composition has good stability over time. It is more preferable to store at −10 ° C. to 20 ° C.

<2. Cured product obtained from curable composition>
The curable composition of the present invention is a mixture of a copolymer having fluorine and carboxyl groups (A), a polyfunctional polymerizable compound (B), and a photopolymerization initiator (C). Further, the additive (D) and the diluting solvent (E) can be selected and added as necessary, and they can be obtained by uniformly mixing and dissolving them.

  When the curable composition obtained as described above is applied to the substrate surface, and the curable composition contains a solvent, the solvent is further removed by a heating step, a decompression step, etc. A film can be formed. Specific examples of the method for applying the curable composition to the substrate surface include a spin coating method, a roll coating method, a dipping method, and a slit coating method. Next, this coating film is temporarily baked by a hot plate, an oven or the like. Temporary baking conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 1 to 5 minutes for a hot plate, and 5 to 15 minutes for an oven.

Thereafter, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet irradiation is suitably 5 to 1,000 mJ / cm ^{2 for} i-line. The coating film irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of the polyfunctional polymerizable compound, and is insolubilized in the alkali developer.

  Next, the substrate is immersed in an alkaline developer by shower development, spray development, paddle development, dip development, or the like, and unnecessary portions of the coating film are dissolved and removed. Specific examples of the alkali developer are aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, surfactant or the like can be added to the alkaline developer.

  Finally, in order to completely cure the coating film, a cured product can be obtained by heat treatment at 100 to 250 ° C., preferably 120 to 230 ° C., for 5 to 60 minutes for a hot plate, and 30 to 90 minutes for an oven. it can.

  The cured product obtained in this way has weak alignment regulation (anchoring) due to the surface free energy lowering ability unique to fluorine. Therefore, the cured product of the present invention is effective when used as a weak anchoring film, and a liquid crystal display element and a solid-state imaging device using the weak anchoring film can be manufactured. Furthermore, the curable composition of the present invention can form a pattern-shaped cured body by irradiating ultraviolet rays through a pattern-shaped mask. Therefore, it is possible to selectively form a necessary portion of the liquid crystal display element or the like instead of the entire surface and form a cured body having weak anchoring properties.

<3. Liquid crystal display element having cured body having weak anchoring property>
Liquid crystal compounds include a positive type having a positive dielectric anisotropy and a negative type having a negative dielectric anisotropy. The positive type liquid crystal compound has a large dielectric property in the major axis direction of the liquid crystal molecules and is small in a direction perpendicular to the major axis direction. The negative type liquid crystal compound has a small dielectric property in the major axis direction of the liquid crystal molecules and is large in the direction perpendicular to the major axis 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 above-described strong anchoring film and weak anchoring film as alignment films for controlling the alignment direction of liquid crystal molecules. In the liquid crystal display element of the present invention, one of the two alignment films facing each other is a strong anchoring film, and the other is a weak anchoring film.

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

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

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

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

  The polarizing plates 12A and 12B are arranged so that their polarization directions are orthogonal to each other. For example, the polarization direction of the polarizing plate 12A is the direction Y, and the polarization direction of the polarizing plate 12B is the direction X.

  The drive electrode layer (LCP-4) is provided on one of the first substrate (LCP-1) and the second substrate (LCP-2). As shown in FIG. 1, in the first embodiment, the drive electrode layer (LCP-4) is provided on the first substrate (LCP-1). The drive electrode layer (LCP-4) is formed by arranging a plurality of electrode lines 15A in parallel along the surface of the first substrate (LCP-1). In FIG. 1, each electrode line 15 </ b> A is formed in a linear shape so that the major 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 in a plane parallel to the surface of the first substrate (LCP-1).

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

  Next, the present invention will be specifically described with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples.

  The compound used for the synthesis example, the comparative synthesis example, the Example, and the comparative example is described for every component.

Polymeric compound (a1) having fluorine:
a1-1: 2,2,2-trifluoroethyl methacrylate a1-2: 2- (perfluorohexyl) ethyl methacrylate a1-3: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate

Polymerizable compound (a2) having a carboxyl group:
a2-1: Methacrylic acid a2-2: 2-Phthalic acid ethyl methacrylate

Other polymerizable compound (a3):
a3-1: benzyl methacrylate a3-2: glycidyl methacrylate a3-3: 3-trimethoxysilylpropyl methacrylate (Silaace S710; trade name, JNC Corporation, hereinafter abbreviated as “S710”)
a3-4: Mono (meth) acryloxypropyl-modified polydimethylsiloxane (Silaplane FM0711 (number average molecular weight catalog listed value: 1,000), JNC Corporation, hereinafter abbreviated as “FM0711”)
a3-5: N-cyclohexylmaleimide

Polymerization initiator:
2,2′-azobis (2-methylpropionic acid) dimethyl (V-601; trade name, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “V-601”)

Polymerization solvent:
PGMEA

Compound having two polymerizable double bonds per molecule:
B1: Diethylene glycol dimethacrylate (NK ester 2G; trade name, Shin-Nakamura Chemical Co., Ltd., hereinafter abbreviated as “2G”)

Compounds having 3 or more polymerizable double bonds per molecule:
B2: Mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate (Aronix M-315; trade name, Toagosei Co., Ltd., hereinafter abbreviated as “M-315”)
B3: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-402; trade name, Toagosei Co., Ltd., hereinafter abbreviated as “M-402”)
B4: Polyfunctional acrylate having a carboxyl group (Aronix M-520; trade name, Toagosei Co., Ltd., hereinafter abbreviated as “M-520”)

Photopolymerization initiator (C):
C1: 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRGACURE OXE01; trade name, BASF Japan Ltd., hereinafter abbreviated as “OXE01”)
C2: 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) (Adeka Arcles NCI-930; trade name, ADEKA Corporation Hereafter abbreviated as “NCI-930”)

Additive (D):
D1: TECHMORE VG3101L which is an epoxy compound (trade name, Printec Co., Ltd., hereinafter abbreviated as “VG3101L”)
D2: CoatOsil MP200 which is an epoxy compound (trade name, Momentive Performance Material Co., Ltd., hereinafter abbreviated as “MP200”)
D3: 3-glycidyloxypropyltrimethoxysilane which is a silane coupling agent (Silaace S510; trade name, JNC Corporation, hereinafter abbreviated as “S510”)
D4: S710 which is a silane coupling agent
D5: ADKSTAB AO-60 which is a hindered phenol-based antioxidant (trade name; ADEKA Co., Ltd., hereinafter abbreviated as “AO-60”)
D6: Megafac RS-72-K, which is a fluorosurfactant (trade name, DIC Corporation, hereinafter abbreviated as “RS-72-K”)

  First, a solution containing a copolymer having fluorine and a carboxyl group, a solution containing a copolymer having a carboxyl group, and a solution containing a homopolymer having fluorine were synthesized as shown below (Synthesis Example). 1-8 and Comparative Synthesis Examples 1-2).

[Synthesis Example 1] Synthesis of copolymer solution (A1) having fluorine and carboxyl groups Polymerization having fluorine in a 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet 2,2,2-trifluoroethyl methacrylate (a1-1) as the compound (a1), methacrylic acid (a2-1) as the polymerizable compound (a2) having a carboxyl group, V-601 as the polymerization initiator, and PGMEA was charged in the following weight as a polymerization solvent, 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
Methacrylic acid 24.00 g
V-601 4.80g
PGMEA 280.00g
The reaction solution was cooled to room temperature to obtain a 30 wt% solution (A1) of a copolymer having fluorine and carboxyl groups. 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 2-8 and Comparative Synthesis Examples 1-2]
In accordance with the method of Synthesis Example 1, a raw material polymerizable compound, a polymerization initiator, and a polymerization solvent are charged at a ratio (unit: g) shown in Table 1 and a polymerization reaction is performed to have a fluorine and a carboxyl group. Copolymer solutions (A2) to (A8), a copolymer solution (A′1) having a carboxyl group, and a homopolymer solution (A′2) having fluorine were obtained. Further, Table 1 also shows the weight average molecular weight of the solid content contained in the obtained solution.

[Example 1]
The copolymer solution (A1), M-402, OXE01, and PGMEA having the fluorine and carboxyl groups obtained in Synthesis Example 1 were mixed and dissolved in the proportions (unit: g) described in Table 2-1, and a membrane filter was obtained. (0.2 μm) to obtain a curable composition.

  In addition, the total amount of the solvent contained in this curable composition is the total amount of PGMEA which is a polymerization solvent contained in the copolymer solution (A1) having fluorine and carboxyl groups, and PGMEA of the dilution solvent (E). In this step, the solid content concentration was adjusted to about 2% by weight. The same applies to Examples 2 and below and the comparative example.

[Method for Producing Substrate 1 for Weak Anchoring Evaluation]
The above curable composition is spin-coated on a substrate with SiNx / ITO comb electrodes for IPS cells at 3,000 rpm for 10 seconds, and prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a substrate with a coating film. It was. Next, the entire surface was exposed using a proximity exposure machine TME-150PRC (trade name, Topcon Co., Ltd.) in nitrogen. The exposure dose was 50 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name, Ushio Electric Co., Ltd.) and a photoreceiver UVD-365PD (trade name, Ushio Electric Co., Ltd.). The exposed substrate with the coating film was subjected to paddle development for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and then the coated substrate was washed with pure water for 20 seconds and then on a hot plate at 100 ° C. for 2 minutes. Dried. Furthermore, it post-baked for 30 minutes on a 150 degreeC hotplate, and obtained the board | substrate with a hardening body whose film thickness is about 30 nm. Hereinafter, this obtained board | substrate with a hardening body is called the board | substrate 1 for weak anchoring evaluation.

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

  In a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging charge port, and a nitrogen gas inlet port, 1.9123 g of 1,4-bis (4-aminophenyl) piperazine, 4,4′-diaminodiphenyl ether; 8561 g, 1,4-phenylenediamine 0.3082 g, and dehydrated NMP 44.0 g were added and dissolved under stirring in 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 stirring was continued 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 content concentration of 6% by weight. This polyamic acid solution is designated as (PB-1). The weight average molecular weight of the polyamic acid contained in (PB-1) was 50,000.

A polyamide acid solution polyamide for weak anchoring evaluation having a polymer solid content concentration of 4% by weight is prepared by mixing the polyamic acid solution (PA-1), the polyamic acid solution (PB-1), and NMP in the following weights and mixing and dissolving them. The acid (PI-1) was made.

9.00 g of polyamic acid solution (PA-1) having a solid content concentration of 6% by weight
21.00 g of polyamic acid solution (PB-1) having a solid content concentration of 6% by weight
NMP 15.00g

[Production Method of Weak Anchoring Evaluation Substrate 2]
A substrate with a coating film was obtained by spin-coating a polyamic acid solution (PI-1) for weak anchoring evaluation on a glass substrate at 2,000 rpm for 10 seconds and pre-baking on a 70 ° C. hot plate for 80 seconds. . Next, using Multilight ML-501C / B (trade name, Ushio Electric Co., Ltd.), the substrate with the coating film was irradiated with ultraviolet linearly polarized light from the vertical direction through the polarizing plate. The amount of exposure was 50 mJ / cm ^{2 as} measured by an ultraviolet integrated light meter UIT-150 (trade name, USHIO INC.) And a photoreceiver UVD-S365 (trade name, USHIO INC.). Further, the substrate was post-baked in an oven at 230 ° C. for 20 minutes to obtain a substrate with a strong anchoring film having a thickness of about 100 nm. Hereinafter, the obtained substrate with a strong anchoring film is referred to as “weak anchoring evaluation substrate 2”.

[Method for producing positive-type liquid crystal composition (LC-1) for weak anchoring evaluation]
A positive liquid crystal composition (LC-1) was produced by mixing and dissolving the compounds described in the following general formulas (2-1) to (2-9) at the described weight ratio.

[Method for producing liquid crystal display element for weak anchoring evaluation]
The two substrates of the weak anchoring evaluation substrate 1 and the weak anchoring evaluation substrate 2 face the cured body side and the strong anchoring film side, respectively, and the SiNx / ITO comb of the weak anchoring evaluation substrate 1 is faced. The wiring direction of the tooth electrode and the strong anchoring film of the weak anchoring evaluation substrate 2 were arranged so that the easy axis of alignment was parallel. Further, a void for injecting the positive type liquid crystal composition (LC-1) was formed between the cured body and the strong anchoring film and bonded together to produce 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 evaluation cell to prepare an evaluation liquid crystal display element. When this evaluation liquid crystal display element is made to correspond to FIG. 1, the wiring direction of the electrode line 15A and the easy axis of orientation of the strong anchoring film 14 are the direction Y.

[Method for judging the presence or absence of orientation when no voltage is applied]
Two polarizing plates having polarization directions orthogonal to each other were arranged on a right viewer 7000PRO (trade name, Hakuba Photo Industry Co., Ltd., hereinafter referred to as “backlight device”) in parallel with the substrate, and produced between them. It installed so that the liquid crystal display element for evaluation might be inserted. Subsequently, the backlight device was turned on, and light passing through the two polarizing plates and the prepared liquid crystal display element for evaluation was visually observed under two conditions. The first condition is a condition in which the wiring direction of the comb electrodes of the manufactured evaluation liquid crystal display element is parallel to the polarization direction of the polarizing plate on the backlight device side. When this condition corresponds to FIG. 1, the polarization direction of the polarizing plate 12A on the backlight device side is the direction Y, and the polarization direction of the other polarizing plate 12B is the direction X. FIG. 6 shows the relationship between the wiring direction of the electrode wire 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 45 ° counterclockwise in the XY plane. In other words, under the second condition, the angle formed by the wiring direction of the comb 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 wire 15A and the polarization direction of the polarizing plate 12A. The case where there was no light leakage under the first condition and light transmission was observed under the second condition was judged as “present” when no voltage was applied. In the case where there was light leakage under the first condition and in one or more cases where no light transmission was observed under the second condition, it was determined that the orientation was “no” when no voltage was applied.

[Method of judging the presence or absence of drive during voltage application]
As the state where the orientation easy axis of the strong anchoring film of the evaluation liquid crystal display element produced in the method for judging the presence or absence of orientation when no voltage is applied is parallel to the polarization direction of the polarizing plate on the backlight device side, A voltage was applied to both electrodes of the comb electrode so that a rectangular wave with a potential difference of 5 V and 60 Hz was obtained. Compared to when no voltage is applied, when the light transmittance is increased when voltage is applied, it is determined that the drive is applied when the voltage is applied, and when the voltage is not changed, it is determined that the drive is when the voltage is applied. .

[Method for evaluating weak anchoring]
If the cured body is not given anisotropy on the surface of the cured body by the above-described rubbing method, photo-alignment method, or the like, assuming that the cured body has strong anchoring, liquid crystal molecules near the cured body are randomly In the process of determining the presence / absence of orientation when no voltage is applied, light leakage is observed. For this reason, the case where it was determined that the orientation when the voltage was applied was “present” and the drive was “present” when no voltage was applied was determined as weak anchoring property “◯”. The other cases were evaluated as weak anchoring ability “x”.

[Method for producing substrate for patterning evaluation]
The curable composition was spin-coated on a glass substrate at 3,000 rpm for 10 seconds, and pre-baked on a hot plate at 100 ° C. for 2 minutes to obtain a substrate with a coating film. Next, through a mask having a line pattern of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 50 μm in nitrogen, a proximity exposure machine TME-150PRC (trade name, Exposure was performed using Topcon Corporation. The exposure dose was 50 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name, Ushio Electric Co., Ltd.) and a photoreceiver UVD-365PD (trade name, Ushio Electric Co., Ltd.). The exposed substrate with the coating film was subjected to paddle development for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, then the coated substrate was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. did. Furthermore, it post-baked for 30 minutes with a 150 degreeC hotplate, and obtained the board | substrate with the hardening body for patterning evaluation which is a film thickness of about 30 nm.

[Observation method of minimum resolution line width]
The obtained substrate with a cured body for patterning evaluation was observed using an optical microscope, and the minimum resolution line width was observed.

[Patternability evaluation method]
When the observed minimum resolution line width is 10 μm or less, the patterning property ○, when the minimum resolution line width is larger than 10 μm, or when the line pattern of all widths cannot be resolved (denoted as “unresolved”) The patterning property x was evaluated.

[Examples 2 to 11 and Comparative Examples 1 to 3]
According to the method of Example 1, each component was mixed and dissolved at the ratios (unit: g) described in Table 2-1 and Table 2-2 to obtain a curable composition. According to the method of Example 1, the presence / absence of orientation when no voltage is applied and the presence / absence of driving when a voltage is applied are determined, and by observing the minimum resolution line width, weak anchoring and patterning properties are evaluated. The results are shown in Table 2-1 and Table 2-2. However, in the method for preparing the weak anchoring evaluation substrate 1 and the method for preparing the patterning evaluation substrate, “post baking for 30 minutes on a 150 ° C. hot plate” was changed to “post baking for 30 minutes in an oven at 230 ° C.”. In some cases, Table 2-1 and Table 2-2 list the post-baking apparatus and post-baking temperature. In addition, the post-baking apparatus of Table 2-1 and Table 2-2 described the case of a hot plate as "H", and the case of the oven as "O".

[Refractive index controllability test (Examples 1 and 7)]
A curable composition described in Example 1 and Example 7 was formed on a glass substrate in the same manner as in the method for preparing weak anchoring evaluation substrate 1 to obtain a substrate with a cured body. Using a reflection spectral film thickness meter FE-3000 (Otsuka Electronics Co., Ltd.), the reflectance of the cured body on the substrate with the cured body obtained in each case was measured. The measurement wavelength range was 400 to 780 nm, and the refractive index value was obtained by fitting to the theoretical formula of nk-Couchy from the interference spectrum of reflectance. When the refractive index of wavelength 589nm of a hardening body was confirmed, the refractive index of the hardening body of Example 1 was 1.49, and the refractive index of the hardening body of Example 7 was 1.54. From this, it was judged that the refractive index could be controlled by adjusting the addition amount of benzyl alcohol, which is aryl methacrylate, in the raw material of the copolymer (A) having fluorine and carboxyl groups.

[Chemical resistance test (Examples 2, 4, 6, 8, and 11)]
A curable composition described in Examples 2, 4, 6, 8, and 11 was formed on a glass substrate in the same manner as in the method for preparing weak anchoring evaluation substrate 1, whereby a substrate with a cured body was obtained. . 0.1 mL of PGMEA was hung on each of the obtained substrates with a cured body, left at 23 ° C. for 1 minute, and then dried by air blow. Thereafter, it was visually observed under a fluorescent lamp, and since no trace remained on any of the substrates with the cured body, it was judged that the chemical resistance of the cured body obtained from the curable composition was good.

[Adhesion test (Examples 2, 6, 8, and 9)]
A curable composition described in Examples 2, 6, 8, and 9 was formed on a glass substrate in the same manner as in the method for preparing weak anchoring evaluation substrate 1, whereby a substrate with a cured body was obtained. A cross-cut test (JIS-K5600, ISO 2409) by tape peeling of the cured body was performed on each of the obtained substrates with the cured body, and the remaining number was counted. Since any test result was classification 0, it was judged that the adhesiveness to the base material of the hardening body obtained from this curable composition was favorable.

[Liquid Repellency Test (Example 10)]
A curable composition described in Example 10 was formed on a glass substrate in the same manner as in the method for preparing substrate 1 for weak anchoring evaluation, and a substrate with a cured body was obtained. Using the portable contact angle meter PCA-1 (Kyowa Interface Science Co., Ltd.), 5 μL of water was dropped on the cured body of the obtained substrate with a cured body, and the contact angle of water was measured. Since the contact angle of water was 95 °, it was judged that the liquid repellency of the cured product obtained from the curable composition was good.

[Heat resistance test (Example 11)]
The curable composition described in Example 11 was formed on a glass substrate in the same manner as in the method for preparing weak anchoring evaluation substrate 1, and a substrate with a cured body was obtained. The obtained board | substrate with a hardening body was reheated for 60 minutes in 230 degreeC oven, and the board | substrate with a hardening body was obtained after reheating. A liquid crystal display element is prepared in the same manner as the weak anchoring evaluation liquid crystal display element manufacturing method except that a substrate with a cured body after reheating is used in place of the weak anchoring evaluation substrate 1. When the weak anchoring property was evaluated by judging the presence / absence of orientation when no voltage was applied and the presence / absence of driving when a voltage was applied, a cured product obtained from the cured composition was evaluated as weak anchoring property ○ Was judged to have good heat resistance.

  As is clear from the results shown in Tables 2-1 and 2-2, the curable compositions of Examples 1 to 11 have excellent patterning properties, and the cured products obtained from the curable compositions have weak anchoring properties. It turns out that is excellent. On the other hand, it can be seen that the cured product obtained in Comparative Example 1 which is a curable composition not containing a polymerizable compound (a1) having fluorine as a raw material compound has poor weak anchoring properties. Moreover, the comparative example 2 which is a curable composition which does not contain the polymeric compound (a2) which has a carboxyl group in a raw material, and the curable composition which does not contain a polyfunctional polymerizable compound (B) and a photoinitiator (C). It can be seen that Comparative Example 3, which is a product, has poor patterning properties.

  The cured product obtained from the curable composition of the present invention is excellent in weak anchoring properties, and therefore can be used as a weak anchoring film used in liquid crystal display elements. Furthermore, since the curable composition of the present invention has high patternability, a cured product having a pattern shape corresponding to the mask pattern shape can be formed, and a cured product is not formed in unnecessary portions such as the outer peripheral portion of the substrate. A liquid crystal display element can be manufactured without a step of removing an unnecessary portion of the cured body.

DESCRIPTION OF SYMBOLS 10 Liquid crystal display element 11 Backlight unit 12A, 12B Polarizing plate LCP-1 1st board | substrate LCP-2 2nd board | 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 and 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 carboxyl group, a polyfunctional polymerizable compound (B), and a photopolymerization initiator (C).   The copolymer (A) having fluorine and a carboxyl group is a copolymer from a raw material containing a polymerizable compound (a1) having fluorine and a polymerizable compound (a2) having a carboxyl group. Curable composition.   The curability according to claim 2, wherein the polymerizable compound (a1) having fluorine is 50 wt% or more and 98 wt% or less in 100 wt% of the raw material of the copolymer (A) having fluorine and carboxyl groups. Composition.   The curability according to claim 2, wherein the polymerizable compound (a1) having fluorine is 80% 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 carboxyl group. Composition.   The curability according to claim 2, wherein the raw material of the copolymer (A) having a fluorine and a carboxyl group comprises the polymerizable compound (a1) having the fluorine and the polymerizable compound (a2) having the carboxyl group. Composition.   The curable composition according to any one of claims 2 to 5, wherein the fluorine-containing polymerizable compound (a1) is a fluorine-containing (meth) acrylate compound. The curable composition according to claim 6, 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; at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.)   The compound represented by the formula (1) is 2,2,2-trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate. The curable composition according to claim 7, wherein the curable composition is at least one selected from 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate.   The curable composition of Claim 7 whose compound represented by Formula (1) is 2,2,2- trifluoroethyl methacrylate.   The polymerizable compound (a2) having a carboxyl group is at least one selected from (meth) acrylic acid and a (meth) acrylate compound having a carboxyl group. Curable composition.   The curable composition according to any one of claims 2 to 9, wherein the polymerizable compound (a2) having a carboxyl group is methacrylic acid.   The curable composition according to any one of claims 1 to 11, wherein the polyfunctional polymerizable compound (B) is a compound having three or more polymerizable double bonds per molecule.   The compound having three or more polymerizable double bonds per molecule is an isocyanuric acid ethylene oxide-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa. The curable composition according to claim 12, which is at least one selected from an acrylate and a carboxyl group-containing polyfunctional (meth) acrylate.   The curable composition of any one of Claims 1-13 for forming the weak anchoring film | membrane of a liquid crystal display element.   The hardening body obtained by hardening the curable composition of any one of Claims 1-14.   The liquid crystal display element which has the hardening body of Claim 15 as a weak anchoring film. A first substrate (LCP-1) on which the weak anchoring film according to claim 16 is formed,
A second substrate (LCP-2) on which a strong anchoring film disposed opposite to the weak anchoring film with a space therebetween is formed;
A liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film;
The first substrate (LCP-1) and the second substrate (LCP-2) are provided on either one of the first substrate (LCP-1) and the second substrate (LCP-2). -2) a liquid crystal display device comprising a drive electrode layer (LCP-4) for applying an electric field in a direction along the line;
A liquid crystal display element in which light transmittance is changed by driving liquid crystal molecules by an electric field applied to the driving electrode layer (LCP-4).   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), and when no electric field is applied The liquid crystal display element according to claim 17, wherein an alignment direction of the liquid crystal molecules on the second substrate (LCP-2) side is parallel or orthogonal to a direction in which the electrode lines are continuous.

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