KR20180127915A - Curable compositions, cured products and liquid crystal display elements - Google Patents

Abstract

The present invention relates to a curable composition comprising a copolymer (A) having fluorine and a carboxyl group; a multifunctional polymerizable compound (B); and a photopolymerization initiator (C). The curable composition of the present invention is capable of producing a cured product which can be patterned, has excellent anchoring ability, and can be applied to various electronic parts.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a cured product and a liquid crystal display element,

The present invention relates to an insulating material for electronic parts, 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 A protective film for a color filter, and the like, a cured product obtained therefrom, and a liquid crystal display element having the cured product.

BACKGROUND ART Liquid crystal display devices have characteristics such as thinness, light weight, and low power consumption, and therefore their use is expanding to a wide range of display devices such as cellular phones, computers, and televisions. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching) and FLC (Ferroelectric Liquid Crystal) have been proposed as the display principle of a liquid crystal display element. Most of them, however, You need to force it in advance.

As a method of forcing the alignment direction of the liquid crystal molecules, an orientation film produced by using a solution containing polyimide on a substrate is formed, and then a roller in which a cloth such as rayon or cotton is wound is rotated (Rubbing method) in which the surface of the alignment film is rubbed in one direction, and a method (optical alignment method) in which anisotropy is generated on the surface of the polyimide film by irradiation with polarized ultraviolet rays. By this treatment, the liquid crystal molecules are strongly bound to the surface of the substrate to which the alignment film is attached, and are oriented in a certain direction. Hereinafter, this liquid crystal molecule is confined to the surface of the substrate to which the alignment film is attached, and the direction of alignment is referred to as " alignment easy axis ".

Recently, a liquid crystal display element having a strong anchoring film on one side of the substrate and a weak anchoring film on the other side (see, for example, Patent Document 1) has been proposed as an improvement measure for improving the display responsiveness of the liquid crystal display element . In the present specification, a liquid layer and a film for weakening the alignment restraining force (anchoring) of the substrate surface are collectively referred to as " strong anchoring film ", and liquid films and films for forcing the alignment direction of liquid crystal molecules such as the above- Quot; weakly anchoring membrane ".

In the embodiment of Patent Document 1, a polyimide film subjected to a rubbing treatment is used as the steel anchoring film, and a method of forming a polymer brush on the substrate surface is adopted as the weak anchoring film. However, in order to form the polymer brush on the surface of the substrate, a substrate must be immersed in a polymerization solution containing a monomer, an initiator, a catalyst, and a solvent to polymerize the polymer on the substrate, It is necessary to protect the area not covered with the masking tape or to remove the formed polymer brush. In this method, there is a problem that the manufacturing process becomes complicated, and patterning of the weak anchoring film on the substrate is difficult.

Also, a display device has been proposed in which the alignment direction of the liquid crystal molecules is oriented in an arbitrary direction by an external field such as an electric field and a magnetic field, and the state is maintained (memorized) (see, for example, Patent Document 2). In order to realize such an operation, it is necessary to weaken the orientation forcing (anchoring) of the surface of the substrate, and in order to realize this, a method of constituting the liquid crystal device with a liquid-liquid crystal interface in a fully wetted state, A method has been proposed in which a liquid crystal composition to which a liquid (for example, polystyrene) is added is injected so as to fit on two substrates and a liquid-liquid crystal phase separation is generated in the liquid crystal composition to form a liquid layer on the substrate surface. However, with this method, both sides of the two substrates are weakly anchored.

Japanese Patent Application Laid-Open No. 2017-010030 Japanese Patent Application Laid-Open No. 2006-084536

The object of the present invention is to provide a curable composition capable of imparting a hardened body with excellent anchorability and capable of patterning, and a cured body formed from the curable composition, and to provide a liquid crystal display element having the cured body.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a cured product obtained by curing a composition comprising a copolymer having a fluorine and carboxyl group, a polyfunctional polymerizable compound and a photopolymerization initiator can achieve the above object And has completed the present invention.

The present invention includes the following configuration.

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

[2] The curable composition according to the above [1], wherein the copolymer (A) having a fluorine and carboxyl group is a copolymer from a raw material comprising a polymerizable compound (a1) having fluorine and a polymerizable compound (a2) Composition.

[3] The curable composition according to [2], wherein the fluorine-containing polymerizable compound (a1) is present in an amount of not less than 50% by weight and not more than 98% by weight, based on 100% by weight of the raw material of the copolymer (A) having the fluorine and carboxyl groups.

[4] The curable composition according to [2], wherein the fluorine-containing polymerizable compound (a1) 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 the fluorine and carboxyl groups.

[5] The curable composition according to [2], wherein the raw material of the copolymer (A) having fluorine and carboxyl groups is composed of the fluorine-containing polymerizable compound (a1) and the carboxyl group-containing polymerizable compound (a2) .

[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.

[7] The curable composition according to [6], wherein the fluorine-containing (meth) acrylate compound is a compound represented by the following formula (1).

(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, and n ² and n ⁴ Are independently an integer of 0 to 6, and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.

[8] A process for producing a photosensitive resin composition as described in [1], wherein the compound represented by the formula (1) is at least one selected from the group consisting of 2,2,2-trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) The curable composition according to [7], wherein the curable composition is at least one selected from ethyl (meth) acrylate, and 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate.

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

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

[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 multifunctional polymerizable compound (B) is a compound having three or more polymerizable double bonds per molecule.

[13] The positive photosensitive composition as described in any one of [1] to [12], wherein the compound having three or more polymerizable double bonds per molecule is selected from the group consisting of isocyanuric acid ethyleneoxide modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, The curable composition according to [12], wherein the curable composition is at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and 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 element having the weakened anchoring film as described in [15].

[17] a first substrate (LCP-1) having a weak anchoring film according to [15]

A second substrate (LCP-2) having a steel anchoring film disposed opposite to the weak anchoring film with a gap therebetween,

A liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film,

(LCP-1) and a second substrate (LCP-2) are provided on one of the first and second substrates (LCP-1 and LCP-2) And a driving electrode layer (LCP-4) for applying an electric field in a direction along the direction of the liquid crystal layer;

The liquid crystal molecules are driven by the electric field applied to the driving electrode layer (LCP-4), thereby changing the transmittance of light.

The driving electrode layer LCP-4 is composed of a plurality of electrode lines arranged on a substrate surface of the first substrate LCP-1 or the second substrate LCP-2, The liquid crystal display element according to [17], wherein the alignment direction of the liquid crystal molecules on the side of the second substrate (LCP-2) is parallel or orthogonal to a direction in which the electrode lines continue.

The curable composition according to the preferred embodiment of the present invention is a curable composition which gives a cured product excellent in weak anchoring property and has good patterning property. When the cured product is used as a weakly anchoring film of a liquid crystal display device, display with higher transmittance can be performed in driving liquid crystal molecules at a low voltage, and a liquid crystal display device having a weak anchoring film attached thereto without a weak anchoring film removing step Can be manufactured. Particularly, it is useful as a liquid crystal display element in which one of two strong anchoring films of an IPS display mode liquid crystal display element is replaced with a weak anchoring film. It can also be used as a protective film for various optical materials and as a transparent insulating film.

1 is a sectional view showing a schematic configuration of a first embodiment of the liquid crystal display element 10 of the present invention and backlight unit 11 and polarizing plates 12A and 12B for display.
Fig. 2 is a cross-sectional view showing the distribution of the orientation directions of liquid crystal molecules in a state in which the electric field E is applied using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment. Fig.
Fig. 3 is a graph showing the relationship between the wiring direction of the electrode lines in the state in which no electric field is applied and the alignment direction of the liquid crystal molecules in the vicinity of the weak anchoring film, using the liquid crystal compound Lp having a positive dielectric anisotropy, Fig.
4 is a graph showing the relationship between the wiring direction of the electrode lines and the alignment direction of the liquid crystal molecules in a state in which the electric field E is applied using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment FIG.
5 is a sectional view showing a schematic configuration of a backlight unit 11 and polarizing plates 12A and 12B for the second embodiment of the liquid crystal display element 10 of the present invention and display.
6 is a plan view showing the relationship between the wiring direction of the electrode line 15A in the first condition and the polarization direction of the polarizing plate 12A in the method of determining the orientation in the voltage unapplied state in the embodiment.
Fig. 7 is a plan view showing the relationship between the wiring direction of the electrode line 15A in the second condition and the polarization direction of the polarizing plate 12A in the method of determining the orientation in the voltage unapplied state in the embodiment.

In the present specification, the term " cured product " is a generic term for a solid film type cured film, a concavo-convex film type cured film, a hole-formed film type cured film, a projected cured product, .

In the present specification, in order to express one or both of "acrylic" and "methacrylic", the term "(meth) acrylic" may be used. Likewise, in order to express either or both of "acrylate" and "methacrylate", there may be mentioned as "(meth) acrylate", and either "acryloxy" or "methacryloxy" Quot; (meth) acryloxy " for the sake of convenience.

<1. The curable composition of the present invention>

The curable composition of the present invention is a curable composition comprising a copolymer (A) having a fluorine and a carboxyl group, a multifunctional polymerizable compound (B), and a photopolymerization initiator (C).

<1-1. Copolymer (A) having fluorine and carboxyl groups>

The fluorine- and carboxyl-group-containing copolymer (A) used in the present invention is a copolymer of two or more kinds of raw materials and has fluorine and carboxyl groups. Is preferably a copolymer of two or more kinds of raw materials including a polymerizable compound (a1) having a fluorine and a polymerizable compound (a2) having a carboxyl group.

(Hereinafter referred to as &quot; other polymerizable compound (a3) &quot;) excluding a polymerizable compound (a1) having a fluorine and a polymerizable compound (a2) having a carboxyl group is added to the raw material of the fluorine- and carboxyl- Notation) may be included.

A preferable weight ratio of the polymerizable compound in the raw material is 50% by weight or more to 98% by weight or less of the polymerizable compound (a1) having fluorine, 2% by weight or more of the polymerizable compound (a2) By weight or less, and 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. More preferably, the weight ratio of the polymerizable compound having fluorine is 80% by weight or more and 95% by weight or less, the polymerizable compound (a2) having a carboxyl group is 5% by weight or more and 20% And the other polymerizable compound (a3) is 15% by weight or less in the case of containing the compound (a3).

<1-1-1. Polymerizable compound (a1) having fluorine>

In the present invention, a fluorine-containing polymerizable compound (a1) is used as a raw material for obtaining a copolymer (A) containing a fluorine and a carboxyl group.

In view of 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.

(Meth) acrylate compound having a fluorine atom is preferably a compound represented by the following formula (1).

(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, and n ² and n ⁴ Are independently an integer of 0 to 6, and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine.

In the above formula (1), n ¹ and n ³ are each independently preferably 0 to 2; n ² and n ⁴ are each independently preferably 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 (Perfluorohexyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2 , 3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro (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 may be used.

Trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate and the like are preferably used in consideration of the compatibility with the carboxyl group-containing polymerizable compound (a2) (Meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate are preferable, and 2,2,2- Trifluoroethyl (meth) acrylate is particularly preferred.

<1-1-2. Polymerizable compound (a2) having carboxyl group>

In the present invention, a polymerizable compound (a2) having a carboxyl group is used as a raw material for obtaining a 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; Styrene compounds having a carboxyl group such as 4-vinylbenzoic acid, dicarboxylic acid compounds such as itaconic acid, fumaric acid, maleic acid, and citraconic acid; And (meth) acrylic acid. One or more of these may be used.

(Meth) acrylic acid and a (meth) acrylate compound having a carboxyl group are preferable, and methacrylic acid is particularly preferable in view of the compatibility with the fluorine-containing polymerizable compound (a1) and the ease of obtaining the raw material.

<1-1-3. Other polymerizable compound (a3) &gt;

In the present invention, other polymerizable compound (a3) may be used as a raw material for obtaining the copolymer (A) containing fluorine and carboxyl groups.

Specific examples of the other polymerizable compound (a3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and dicyclopentanyl Alkyl (meth) acrylate compounds such as acrylate;

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 compound having a polydimethylsiloxane such as mono (meth) acryloxypropyl-modified polydimethylsiloxane;

(Meth) acrylate compound having a tertiary amino group such as 2- (dimethylamino) ethyl (meth) acrylate;

Diesters of dicarboxylic acid compounds having a double bond such as diethyl itaconate, diethyl fumarate, diethyl maleate, and diethyl itaconate; N-substituted maleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N- (4-hydroxyphenyl) maleimide;

Styrene, 4-hydroxystyrene, and (meth) acrylamide. One or more of these may be used.

The other polymerizable compound (a3) has an effect of imparting properties of a cured film other than weak anchoring property and patterning property. Examples of the effect of using the other polymerizable compound (a3) include the effect of adjusting the refractive index of the cured product by using an aryl (meth) acrylate compound, the effect of adjusting the refractive index of the cured product by using the (meth) acrylate compound having an alkoxysilyl group The effect of improving the chemical resistance of the cured product by using the (meth) acrylate compound having a cyclic ether, the effect of improving the lyophobicity of the cured product by using the (meth) acrylate compound having a polydimethylsiloxane, and Substituted maleimide compound is used to improve the heat resistance of the cured product.

<1-1-4. Method of Polymerization of Copolymer>

The polymerization method of the copolymer (A) having a fluorine and carboxyl group is not particularly limited. An example of the polymerization method is a radical polymerization in a solution using a polymerization solvent, and a solution containing the copolymer (A) having fluorine and carboxyl groups can be obtained. The polymerization temperature is not particularly limited as long as the radical generating from the polymerization initiator to be used is sufficiently generated, but is usually in the range of 50 to 150 占 폚. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. 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 materials of the copolymer (A) having fluorine and carboxyl groups, because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

By using the solution containing the copolymer (A) having the fluorine and carboxyl groups, the curable composition can be produced. Examples of the method for producing the curable composition include a method for producing a curable composition by directly using a solution containing the copolymer (A) having a fluorine and carboxyl group left behind as the polymerization solvent, and a method for producing a fluorine- and carboxyl- ), And then adding a diluting solvent to prepare a liquid or gel-like curable composition.

<1-1-5. Polymerization solvent used in polymerization reaction>

Specific examples of the polymerization solvent (hereinafter simply referred to as "polymerization solvent") used in the polymerization reaction for obtaining the fluorine- and carboxyl-group-containing copolymer (A) include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, Glycol, and diol compounds such as 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, Monoether compounds of diol compounds such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and triethylene glycol monomethyl ether; Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and triethylene glycol dimethyl Diether compounds of diol compounds such as ethers; Propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), propylene glycol monoethyl ether acetate, , Monoether monoester of diol compounds such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol monomethyl ether acetate; Diester compounds of diol compounds such as ethylene glycol diacetate and propylene glycol diacetate; Monoester compounds of monocarboxylic acid compounds such as butyl acetate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl butyrate; Monoethers of monohydroxycarboxylic acid compounds such as methyl methoxyacetate, ethyl methoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and methyl 4-methoxybutyrate Monoester; Diesters of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate; N, N-dimethylacetamide and N, N-dimethylpropionamide, monoamides of monoisocyanates such as methyl isobutyl ketone, methyl n-butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl Dialkyl ketone compounds such as ketone, and dinormal butyl ketone; Cyclic ether compounds such as hexamethylene oxide, and 1,4-dioxane; cyclic ester compounds such as? -propiolactone,? -butyrolactone, and? -valerolactone; Cyclic amide compounds such as 2-pyrrolidone, and 1-methyl-2-pyrrolidone; And cyclic ketone compounds such as cyclopentanone, cyclohexanone, and cycloheptanone. One or more of these may be used.

Among these specific examples of the polymerization solvent, 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 may be obtained by copolymerizing a copolymer (A) having a fluorine and a carboxyl group The solubility is high.

<1-1-6. Molecular Weight of Copolymer (A) Having Fluorine and Carboxyl Group>

The obtained fluorine- and carboxyl-group-containing copolymer (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50,000. Within this range, weak anchoring property and patterning property are improved.

The weight average molecular weight in the present specification is a value in terms of polystyrene determined by the GPC method (column temperature: 35 캜, flow rate: 1 mL / min). PLgel MIXED-D (trade name, Agilent Technologies Co., Ltd.) was used as a column, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies Co., It can be measured using hydrofuran. The weight average molecular weights of commercially available products in this specification are the catalog values.

<1-2. The multifunctional polymerizable compound (B)

Examples of the multifunctional 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 is excellent in the effect of giving a curable composition having patternability without deteriorating the weak anchoring property of the cured product and a compound having three or more polymerizable double bonds per molecule , Giving a curable composition that can be cured with a small amount of ultraviolet radiation.

With respect to a demand for improvement in productivity in the manufacturing process of a display device these days, since the curable composition is required to be cured by irradiation with a small amount of ultraviolet rays, a curable composition containing a compound having three or more polymerizable double bonds per molecule . It is preferable that a compound having three or more polymerizable double bonds per molecule in the 100 wt% of the multifunctional polymerizable compound (B) is contained in an amount of 50 wt% or more, more preferably 80 wt% or more.

<1-2-1. Compounds having two polymerizable double bonds per one molecule &gt;

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) Triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (Meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, and ethylene oxide modified Di (meth) acrylate product of a diol compound such as phenol's S di (meth) acrylate;

Di (meth) acrylate compounds of triol compounds such as glycerol acrylate methacrylate, glycerol di (meth) acrylate, and ethoxylated isocyanuric acid diacrylate;

Di (meth) acrylate compounds 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) (Meth) acrylate modified with epichlorohydrin, diethyleneglycol di (meth) acrylate modified with epichlorohydrin, hydroxypropylmethyl di (meth) acrylate modified with epichlorohydrin, (Meth) acrylate, epichlorohydrin modified dipropylene glycol di (meth) acrylate, epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di , Epichlorohydrin-modified polypropylene glycol di (meth) acrylate, bisphenol A type epoxy compound (Meth) acrylic acid adduct of a di (meth) acrylic acid adduct, a (meth) acrylic acid adduct of a bisphenol F type epoxy compound, and a (meth) acrylic acid adduct of a bisphenol S type epoxy compound. One or more of these may be used.

<1-2-2. Compounds having three or more polymerizable double bonds per molecule &gt;

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 tri (meth) acrylate, glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (meth) acrylate, pentaerythritol tri Trifunctional (meth) acrylate compounds such as ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate;

(Meth) acrylate such as ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra Tetrafunctional (meth) acrylate compounds;

Pentafunctional (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate;

Hexafunctional (meth) acrylate compounds such as dipentaerythritol hexaacrylate;

And a polyfunctional (meth) acrylate compound having a carboxyl group. One or more of these may be used.

As the compound having three or more polymerizable double bonds per one molecule, commercially available products as described below can be used.

Specific examples of commercially available products of trimethylolpropane triacrylate which is a trifunctional acrylate compound include NK ester A-TMPT (trade name, Shin Nakamura Chemical Co., Ltd.), TMPTA (trade name, Daicel Allyn Co., Ltd.) Knix M-309 (trade name, Toagosei Co., Ltd.);

Specific examples of commercially available products of trimethylolpropane EO-modified triacrylate are TMPEOTA (trade name, Daicel Allyn Co., Ltd.), Aronix M-350 and M-360 (all trade names, Toagosei Co., Ltd.);

Specific examples of commercially available products of trimethylolpropane PO-modified triacrylate are EBECRYL 135 (trade name, Daicel Olenex Co., Ltd.), Aronix M-310 and M-321 (all trade names, Toagosei Co., Ltd.);

A specific example of a commercially available product of glycerol PO-modified triacrylate is OTA 480 (trade name, Daicel Olenex Co., Ltd.);

A specific example of a commercially available product of ethoxylated isocyanuric acid triacrylate is NK Ester A-9300 (trade name, Shin Nakamura Chemical Co., Ltd.);

A specific example of a commercially available product of ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate is NK ester A-9300-1CL (trade name, Shin Nakamura Chemical Co., Ltd.).

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

Specific examples of commercially available products of ditrimethylolpropane tetraacrylate which is a tetrafunctional acrylate compound include NK ester AD-TMP (trade name, Shin Nakamura Chemical Industry Co., Ltd.), EBECRYL 140 and 1142 (all trade names, Aronix M-408 (trade name, Toagosei Co., Ltd.);

A specific example of a commercial product of ethoxylated pentaerythritol tetraacrylate is NK ester ATM-35E (trade name, Shin Nakamura Chemical Co., Ltd.);

A specific example of a commercially available product of pentaerythritol tetraacrylate is NK ester A-TMMT (trade name, Shin Nakamura Chemical Co., Ltd.);

A specific example of a commercially available product of pentaerythritol alkoxytetraacrylate is EBECRYL 40 (trade name, Daicel Olenex Co., Ltd.);

A specific example of a commercially available product of diglycerol EO-modified tetraacrylate is Aronix M-460 (trade name, Toagosei Co., Ltd.).

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

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

Specific examples of commercially available products of a mixture of ethoxylated isocyanuric acid triacrylate as a trifunctional acrylate compound and ethoxylated isocyanuric acid diacrylate as a bifunctional acrylate compound include ARONIX M-313 40% by weight) and M-315 (3 to 13% by weight) (all trade names, Toa Synthetic Chemical Co., Ltd., content values in parentheses are catalog values of content of ethoxylated isocyanuric acid diacrylate in the mixture).

Specific examples of commercially available products of a mixture of pentaerythritol triacrylate, which is a trifunctional acrylate compound, and pentaerythritol tetraacrylate, which is a tetrafunctional acrylate compound, include PETIA, PETRA, and PETA (all trade names, M-305 (55 to 63% by weight), M-303 (30 to 60% by weight), M-452 (25 to 40% by weight), and Aronix M- M-450 (less than 10% by weight) (all trade names, Toa Synthetic Industries Co., Ltd., content values in parentheses are catalog values of the content of pentaerythritol triacrylate in the mixture).

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

<1-3. Photopolymerization initiator (C)

The photopolymerization initiator (C) used in the present invention is a compound capable of initiating polymerization of the multifunctional polymerizable compound (B).

Specific examples of the photopolymerization initiator (C) include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone , Isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butyl) -2-morpholinopropane-1-one (Irgacure 907; trade name, BASF Japan KK) (4-dimethylaminobenzoyl) benzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4 , 4'-tri (t-butylperoxycarbonyl) benzophenone Ethanone, 1- [9-ethyl (2-ethylhexyloxy)], 2- , Irgacure OXE02 (trade name, BASF Japan Co., Ltd.), Irgacure OXE03 (trade name, BASF Japan Co., Ltd.), and 1- (ADEKA) (trade name: ADEKA, NCI-930, trade name; manufactured by Nippon Polyurethane Industry Co., Ltd.) (ADEKA), Adeka Optomer N-1919 (trade name, ADEKA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'- (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) Triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, Bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxy) (Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - 2,6- (Trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) - (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis Diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- ) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4- 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3'- - (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2- 2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (eta 5-2,4-cyclopentadien- 6-difluoro-3- (lH-pyrrol-l-yl) -phenyl) titanium. One or more of these may be used.

Among the specific examples of the above-mentioned photopolymerization initiator, preferred are 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime), ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- acetyloxime), and 1,2-propanedione, 1- [4- [4- ) Phenylthio] phenyl] -2- (O-acetyloxime), the curable composition is cured to a lower exposure dose. It is preferable that at least one selected from them is at least 20% by weight based on the total weight of the photopolymerization initiator, and more preferably at least 50% by weight.

<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 is added from the viewpoint of improving the properties of the curable composition of the present invention such as coating uniformity, adhesion, stability, chemical resistance, and resolution. Examples of the additive (D) include anionic surfactants, cationic surfactants, nonionic surfactants, and fluorine surfactants; A silicone resin-based coating property improving agent; Adhesiveness improvers such as silane coupling agents; An anti-aggregation agent such as sodium polyacrylate; Polymer dispersants such as acrylic type, styrene type, polyethylene imine type, and urethane type; Antioxidants such as hindered phenols; A crosslinking agent such as an epoxy compound, a melamine compound, and a bisazide compound; And photoacid generators.

<1-4-1. Surfactant, coating property improving agent>

The curable composition of the present invention may further contain a surfactant in order to further improve coating uniformity. DISPERBYK-162, DISPERBYK-163, DISPERBYK-164 (all trade names, manufactured by Kyowa Chemical Industry Co., Ltd.), DISPERBYK-161, DISPERBYK- , DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK-181, DISPERBYK-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK- KP-361N, BYK-UV3500, and BYK-UV3570 (trade names, all of which are trademarks of Shin-Etsu Chemical Co., Ltd.); KP-341; KP-368; KF- , Surflon S611 (trade name, manufactured by AGC Seiyaku Chemical Co., Ltd.), PtGent 222F, PtGent 208G, PtGent 251, PtGent 710FL, PtGent 710FM, PtGent 710FS, PtGent 601AD, PtGent 650A, FTX Megaface F-477, Megafac F-477, Megafac F-478, Megafac F-472, Megafac F-472, Megafac F- 552, Mega Pack F-553, Mega Pack F-554, Mega Pack F-555, Mega Pack Megapack RS-72-K, Megapack RS-76-NS, Megapack DS-21 (available from MEGAPAK F-556, Megapack F-558, Megapack F-559, Megapack R-94, Megapack RS- TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names, Ebonic Japan Co., Ltd.), fluoroalkylbenzenesulfonates, fluoroalkyl (Fluoroalkylpolyoxyethylene ether), a fluoroalkyltrimethylammonium salt (fluoroalkylpolyoxyethylene ether), a fluoroalkylpolyoxyethylene ether, a fluoroalkylammonium iodide, a fluoroalkylbetaine, a fluoroalkylsulfonate salt, a diglycerin tetrakis , Fluoroalkylaminosulfonates, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, poly Oxyethylene cetyl ether, Polyoxyethylene stearate, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, , And alkyl diphenyl ether disulfonates. One or more of these may be used.

Among these specific examples of surfactants, mention may be made of BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surplon S611, Pptant 710FL, Pptant 710FM, Pptantent 710FS, PtGent 650A, F-477, Megapack F-556, Megapack RS-72-K, Megapack DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, At least one kind selected from a fluoroalkylsulfonic acid salt, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonic acid salt is preferable because it has a large effect of enhancing the uniformity of application of the curable composition.

The amount of the surfactant added to the curable composition of the present invention is preferably 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the copolymer (A) having a fluorine and carboxyl group, the multifunctional polymerizable compound (B), and the photopolymerization initiator (C) By weight.

<1-4-2. Adhesion improving agent>

The curable composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion of the formed cured product to the substrate. As specific examples of the adhesion improver, silane-based, aluminum-based or titanate-based coupling agents can be used. Specific examples thereof include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, Sara Ace S510 , JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sara Ace S530 (trade name, JNC Co., Ltd.), 3-trimethoxysilylpropyl methacrylate Silane-based coupling agents such as 3-mercaptopropyltrimethoxysilane (e.g., Sara Ace S810 (trade name, JNC Co., Ltd.)), acetoxyalkoxy diisopropyl An aluminate-based coupling agent such as tetrakis (triphenylphosphine) palladium, and a titanate-based coupling agent such as tetraisopropylbis (dioctylphosphite) titanate. One or more of these may be used.

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

The amount of the adhesion improver to be added in the curable composition of the present invention is preferably 0.1 to 100 parts by weight based on 100 parts by weight of the total amount of the copolymer (A) having a fluorine and carboxyl group, the multifunctional polymerizable compound (B), and the photopolymerization initiator (C) 20 parts by weight.

<1-4-3. Anti-aggregation agent>

The curable composition of the present invention may further contain an anti-aggregation agent from the viewpoint of affinity with a solvent and prevention of agglomeration. The anti-aggregation agent is used to make it compatible with a solvent and prevent aggregation. Specific examples of the coagulation 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- 2100, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DISPERBYK-199 and DISPERBYK-2015 (all trade names, Big Chem Japan Co., Ltd.), FTX- , FLOWREN G-600, and FLOWREN G-700 (both trade names, manufactured by Kyowa Chemical Industry Co., Ltd.). One or more of these may be used.

<1-4-4. Antioxidants>

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 high temperatures. Specific examples of the antioxidant include Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD , ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, and ADK STAB AO-80 (all trade names, ADEKA Corporation). One or more of these may be used.

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

The amount of the antioxidant to be added in the curable composition of the present invention is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the copolymer (A) having a fluorine and carboxyl group, the multifunctional polymerizable compound (B), and the photopolymerization initiator (C) 5 parts by weight.

<1-4-5. Cross-linking agent>

The curable composition of the present invention may further contain 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.

Examples of the epoxy compound include epoxy compounds such as 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 novolak type epoxy compounds, Type epoxy compound, a bisphenol A novolak type epoxy compound, an aliphatic polyglycidyl ether compound, a cyclic aliphatic epoxy compound, a polymerizable compound aggregate having an epoxy group, a polymerizable compound having an epoxy group and a copolymer of other polymerizable compound, and Is an epoxy compound having a siloxane bonding site.

Specific examples of commercially available products of the bisphenol A type epoxy compound are jER 828, 1004 and 1009 (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available bisphenol F type epoxy compounds are jER 806 and 4005P (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available glycidyl ether type epoxy compounds include commercially available products such as TECHMORE VG3101L (trade name, manufactured by PRINTEC), EHPE3150 (trade name, Daicel), EPPN-501H and 502H (all trade names, Nippon Yakusho Co., Ltd.), and jER 1032H60 Trade name, Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available products of glycidyl ester type epoxy compounds include DENARCOL EX-721 (trade name, manufactured by Nagase Chemtex Co., Ltd.) and diglycidyl 1,2-cyclohexanedicarboxylic acid (trade name, manufactured by Tokyo Chemical Industry Co., Lt; / RTI &gt; Specific examples of commercial products of biphenyl type epoxy compounds are jER YX4000, YX4000H, YL6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), and NC-3000, NC-3000-L, NC-3000- , &Lt; / RTI &gt; Nippon Yakusho Co., Ltd.); Specific examples of commercially available phenol novolak epoxy compounds include EPPN-201 (trade name, manufactured by Nippon Yakushin Co., Ltd.) and jER 152 and 154 (all trade names, Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available products of cresol novolak-type epoxy compounds are EOCN-102S, 103S, 104S and 1020 (all trade names, Nippon Yakusho Co., Ltd.); Specific examples of commercially available bisphenol A novolak epoxy compounds include jER 157S65 and 157S70 (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available products of the cyclic aliphatic epoxy compound are Celloxide 2021P, 3000 (all trade names, Daicel Co., Ltd.); Specific examples of commercially available epoxy compounds having a siloxane bonding site include 1,3-bis [2- (3,4-epoxycyclohexyl) ethyl] tetramethyldisiloxane (trade name, manufactured by Zerrest Inc.), TSL9906 (Japan), COATOSIL MP200 (product name, Momentive Performance Materials Japan Co., Ltd.)), Conforcer SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES- 1023 (trade name, Shin-Etsu Chemical Co., Ltd.). One or more of these may be used.

In addition, TECHMORE VG3101L (trade name, manufactured by PRINTEC Co., Ltd.) is commercially available under the trade name of 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- -Epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; EHPE3150 (trade name, Daicel Corporation) is a 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol; Celllock 2021P (trade name, Daicel Corporation) is 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; Celllock 3000 (trade name, Daicel Corporation) is 1-methyl-4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane; COATOSIL MP200 (trade name, Momentive Performance Materials Japan Joint-Stock Company) is an aggregate containing 3-glycidoxypropyltrimethoxysilane as a raw material component.

<1-4-6. Photo acid generator>

The curable composition of the present invention may further contain a photoacid generator from the viewpoint of improving the resolution. An example of the photoacid generator is a 1,2-quinonediazide compound.

Specific examples of the 1,2-quinonediazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester (for example, trade name, NT-200, manufactured by Toyo Synthetic Chemical Industry Co., Ltd.), 2,4,6-trihydroxybenzophenone- -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- 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 Sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonedi (P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphtho Quinonediazide-5-sulfonic acid ester; (P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane- Ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1- 1,2-naphthoquinonediazide-5-sulfonic acid ester; Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester; (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- [ Methylphenyl] 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- Phenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene- 6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl- Spirobindene 5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflagane-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,2,4-trimethyl- ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester. One or more of these may be used.

<1-5. Solvent optionally added to the curable composition &gt;

In addition to the polymerization solvent, a solvent may be added to the curable composition of the present invention. (A), a multifunctional polymerizable compound (B), and a photopolymerization initiator (C), which are optionally added to the curable composition of the present invention ) Is preferably used. When the curable composition contains the above-mentioned additive (D), the diluting solvent (E) is preferably a solvent capable of dissolving the additive (D).

Specific examples of the diluting solvent (E) are the same as the solvent described as specific examples of the above-mentioned polymerization solvent. One or more of these may be used.

<1-6. Preservation of the curable composition &gt;

When the curable composition of the present invention is stored in the range of -30 ° C to 25 ° C by shielding it from light, the stability with time of the composition becomes favorable, which is preferable. It is more preferable to store at -10 ° C to 20 ° C.

<2. Cured product obtained from the curable composition &gt;

The curable composition of the present invention is obtained by mixing a fluoropolymer and a carboxyl group-containing copolymer (A), a multifunctional polymerizable compound (B) and a photopolymerization initiator (C) Adding a diluting solvent (E), if necessary, and adding them uniformly and dissolving them uniformly.

When the curable composition thus obtained is applied to the surface of the substrate, when the curable composition contains a solvent, the solvent can be removed by a heating process, a depressurization process, or the like to form a coating film. Specific examples of the application method of the curable composition on the substrate surface are the spin coating method, the roll coating method, the dipping method, and the slit coat method. Next, this coating film is fired by a hot plate, an oven, or the like. The firing conditions vary depending on the kind of each component and the blending ratio, but are usually from 70 to 150 ° C for 1 to 5 minutes for a hot plate and 5 to 15 minutes for an oven.

Then, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet radiation is suitably 5 to 1,000 mJ / cm ² by i-line. The coating film irradiated with ultraviolet rays becomes a three-dimensionally crosslinked product by polymerization of a polyfunctional polymerizable compound, and is insoluble in an alkali developing solution.

Subsequently, the substrate is immersed in an alkaline developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon or the like to dissolve and remove an unnecessary portion of the coating film. Specific examples of the alkali developing solution include 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. In addition, an appropriate amount of methanol, ethanol, and a surfactant may be added to the alkali developing solution.

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

In the cured product thus obtained, the orientation regulation (anchoring) is weakened by the surface free energy lowering ability peculiar 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 or a solid-state imaging element using the weakened anchoring film can be produced. The curable composition of the present invention can form a patterned cured product by irradiating ultraviolet rays through a patterned mask. For this reason, it is possible to form a cured body having weak anchoring property selectively at a necessary portion other than the entire surface of a liquid crystal display element or the like.

<3. Liquid crystal display element having cured body having weak anchoring property>

The liquid crystal compound has 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 genetic property in the long axis direction of the liquid crystal molecule and a small direction in the direction orthogonal to the long axis direction. The negative type liquid crystal compound has a small genetic property in the long axis direction of the liquid crystal molecule and a large direction perpendicular to the long axis direction. In the following description of the liquid crystal display element, a case of using a positive liquid crystal compound will be described.

As the alignment film for controlling the alignment direction of the liquid crystal molecules, the above-described strong anchoring film and weak anchoring film exist in the liquid crystal display element. In the liquid crystal display element of the present invention, one of the two orientation 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 above weak anchoring film.

<3-1. First Embodiment>

1 is a sectional view showing a schematic configuration of a first embodiment of the liquid crystal display element 10 of the present invention and a backlight unit 11 and polarizing plates 12A and 12B for display. 2 is a diagram showing the distribution of the alignment direction of the liquid crystal molecules in a state in which the electric field E is applied using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment. Fig. 3 is a graph showing the relationship between the wiring direction of the electrode lines in the state in which no electric field is applied and the alignment direction of the liquid crystal molecules in the vicinity of the weak anchoring film, using the liquid crystal compound Lp having a positive dielectric anisotropy, Fig. 4 is a graph showing the relationship between the wiring direction of the electrode lines and the alignment direction of the liquid crystal molecules in a state where the electric field E is applied using the liquid crystal compound Lp having a positive dielectric anisotropy in the first embodiment Fig.

1, the liquid crystal display element of the present invention comprises a first substrate LCP-1 having a weak anchoring film 13 formed thereon, a steel anchoring film A liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film and configured to transmit or block the light by driving liquid crystal molecules, and a second substrate (LCP- And a driving 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 molecules.

The first substrate LCP-1 and the second substrate LCP-2 are each made of a glass substrate or the like, and are arranged parallel to each other with a predetermined gap therebetween.

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

The driving electrode layer LCP-4 is provided on either the first substrate LCP-1 or the second substrate LCP-2. As shown in Fig. 1, in the first embodiment, the driving electrode layer LCP-4 is provided on the first substrate LCP-1. The driving electrode layer LCP-4 is formed by arranging a plurality of electrode lines 15A side by side along the surface of the first substrate LCP-1. In Fig. 1, each of the electrode lines 15A is formed in a straight line so that its major axis direction extends along the direction Y in a plane parallel to the surface of the first substrate LCP-1. The electrode lines 15A of the driving electrode layer LCP-4 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, a driving electrode layer LCP-4 is provided on the second substrate LCP-2. The other configuration is the same as that of the first embodiment.

[Example]

EXAMPLES Next, the present invention will be described concretely with Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited by these Examples.

Compounds used in Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples are listed for each component.

Polymerizable 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 carboxyl group:

a2-1: Methacrylic acid

a2-2: 2-phthalic acid ethyl methacrylate

Other polymerizable compounds (a3):

a3-1: benzyl methacrylate

a3-2: glycidyl methacrylate

a3-3: 3-trimethoxysilylpropyl methacrylate (Sara Ace S710 (trade name, JNC Co., Ltd., hereinafter abbreviated as "S710"))

a3-4: mono (meth) acryloxypropyl modified polydimethylsiloxane (Sara Plain FM0711 (number average molecular weight catalog value: 1,000), JNC Co., Ltd., hereinafter abbreviated as "FM0711"

a3-5: N-Cyclohexylmaleimide

Polymerization initiator:

V-601 (trade name, abbreviated as "V-601" by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (2-methylpropionic acid)

Polymerization solvent:

PGMEA

A compound having two polymerizable double bonds per one molecule:

B1: Diethylene glycol dimethacrylate (NK ester 2G; trade name, Shin Nakamura Chemical Co., hereinafter abbreviated as "2G")

A compound having three or more polymerizable double bonds per molecule:

B2: a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate (Aronix M-315 (trade name, hereinafter abbreviated as "M-315"

B3: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-402 (trade name, hereinafter abbreviated as &quot; M-402 &quot;

B4: polyfunctional acrylate having a carboxyl group (ARONIX M-520 (trade name, hereinafter abbreviated as "M-520"

Photopolymerization initiator (C):

(Hereinafter abbreviated as &quot; OXE01 &quot;, trade name, BASF Japan Co., Ltd.), 1- [4- (phenylthio) phenyl]

C2: 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O- acetyloxime) (Adekaacruus NCI- ADEKA, abbreviated as "NCI-930" hereinafter)

Additive (D):

D1: TECHMORE VG3101L (trade name: PRINTEC, hereinafter abbreviated as "VG3101L"), which is an epoxy compound,

D2: COATOSIL MP200 (trade name, Momentive Performance Materials Co., Ltd., hereinafter abbreviated as "MP200"), which is an epoxy compound,

D3: 3-glycidyloxypropyltrimethoxysilane (Sara Ace S510 (trade name, JNC Corporation, hereinafter abbreviated as "S510"), which is a silane coupling agent,

D4: Silane coupling agent, S710

D5: ADK STAB AO-60 (trade name: ADEKA, hereinafter abbreviated as "AO-60"), which is a hindered phenol antioxidant,

D6: Megapac RS-72-K (trade name, DIC Co., hereinafter abbreviated as "RS-72-K") which is a fluorochemical surfactant

First, a solution containing a copolymer containing 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 Examples 1 to 8 and Comparative Synthesis Examples 1 to 2).

[Synthesis Example 1] Synthesis of copolymer solution (A1) having fluorine and carboxyl groups

To a 500 mL four-necked flask equipped with a thermometer, a stirrer, a feedstock inlet, and a nitrogen gas inlet were added 2,2,2-trifluoroethyl methacrylate (a1-1) as the polymerizable compound (a1) Methacrylic acid (a2-1) as a polymerizable compound (a2) having a carboxyl group, V-601 as a polymerization initiator and PGMEA as a polymerization solvent were charged at the following weights and heated at a polymerization temperature of 90 DEG C for 4 hours And polymerization was carried out.

2,2,2-trifluoroethyl methacrylate 96.00 g

Methacrylic acid 24.00 g

V-601 4.80g

PGMEA 280.00 g

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 to 8 and Comparative Synthesis Examples 1 to 2]

A polymerizable compound as a starting material, a polymerization initiator and a polymerization solvent were charged in the ratio (unit: g) shown in Table 1 in accordance with the method of Synthesis Example 1, and a polymerization reaction was carried out to obtain a copolymer solution having a fluorine- and carboxyl- ) To (A8), a solution of a copolymer (A'1) having a carboxyl group, and a homopolymer solution (A'2) having fluorine. Table 1 also shows the weight average molecular weight of the solid content contained in the obtained solution.

[Example 1]

(A1), M-402, OXE01 and PGMEA obtained in Synthesis Example 1 were mixed and dissolved in the ratio (unit: g) shown in Table 2-1, and the solution was mixed with a membrane filter Followed by filtration to obtain a curable composition.

The total amount of the solvent contained in the curing composition is the total amount of PGMEA of the polymerization solvent PGMEA contained in the fluorine- and carboxyl-group-containing copolymer solution (A1) and PGMEA of the diluting solvent (E) To about 2% by weight. Example 2 The same applies to the following and comparative examples.

[Production method of substrate 1 for evaluation of weak anchoring property]

The above-mentioned curable composition was spin-coated on a substrate with a Cr comb electrode for IPS cell at 3,000 rpm for 10 seconds, and pre-baked on a hot plate at 100 캜 for 2 minutes to obtain a substrate having a coated film. Next, the entire surface was exposed in a nitrogen atmosphere using a proximity phototray TME-150PRC (trade name, Topcon Co., Ltd.). The amount of exposure was determined to be 50 mJ / cm ² by measuring with a cumulative photometer UIT-102 (trade name, manufactured by Ushio Inc.) and a photoreceptor UVD-365PD (trade name, manufactured by Ushio Inc.). The substrate having the coated film after exposure was paddled with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then the substrate with the coated film was washed with pure water for 20 seconds and then dried with a hot plate at 100 DEG C for 2 minutes. Post-baking was carried out on a hot plate at 150 占 폚 for 30 minutes to obtain a substrate with a cured body having a film thickness of approximately 30 nm. Hereinafter, the obtained substrate on which the cured body is attached is referred to as &quot; weakly anchoring property evaluation substrate 1 &quot;.

[Method for preparing polyamic acid solution (PI-1) for evaluation of weak anchoring property]

To a 200 mL four-necked flask equipped with a thermometer, a stirrer, a feed inlet for a raw material, and a nitrogen gas inlet were added 1.4184 g of 4,4'-diaminoazobenzene, 0.5736 g of 1,4-bis (4-aminophenyl) 0.1281 g of 4-bis (4-aminophenyl) piperazine, and 44.0 g of dehydrated N-methylpyrrolidone (hereinafter abbreviated as "NMP") were poured in and dissolved in a dry nitrogen stream. Then, 3.8799 g of 1,8-bis (3,4-dicarboxylic acid) octane dianhydride and 20.0 g of dehydrated NMP were 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 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.

To a 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material feed inlet and a nitrogen gas inlet were added 1.9123 g of 1,4-bis (4-aminophenyl) piperazine, 0.8561 g of 4,4'-diaminodiphenyl ether , 0.3082 g of 1,4-phenylenediamine and 44.0 g of dehydrated NMP were placed and dissolved by stirring in a dry nitrogen stream. 1.8354 g of 1,2,3,4-butanetetracarboxylic acid 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 referred to as (PB-1). The weight average molecular weight of the polyamic acid contained in the polyimide resin (PB-1) was 50,000.

Polyamic acid solution (PA-1), polyamic acid solution (PB-1) and NMP were poured in the following weights and mixed and dissolved to obtain a polyamic acid solution for weakly anchoring property PI-1).

A polyamic acid solution (PA-1) having a solid concentration of 6 wt% 9.00 g

A polyamic acid solution (PB-1) having a solid concentration of 6 wt% 21.00 g

NMP 15.00 g

[Production method of substrate 2 for weak anchoring property evaluation]

The polyamic acid solution (PI-1) for weak anchoring property evaluation was spin-coated on a glass substrate at 2,000 rpm for 10 seconds, and prebaked on a hot plate at 70 占 폚 for 80 seconds to obtain a substrate having a coated film. Next, using a multi-light ML-501C / B (trade name, manufactured by Ushio Inc.), linearly polarized light of ultraviolet rays was irradiated from a vertical direction through a polarizing plate to a substrate having a coated film. The exposure dose was determined to be 50 mJ / cm ² by ultraviolet light intensity meter UIT-150 (trade name, manufactured by Ushio Inc.) and UV detector UVD-S365 (trade name, manufactured by Ushio Inc.). Post baking was carried out in an oven at 230 deg. C for 20 minutes to obtain a substrate having a steel anchoring film with a thickness of approximately 100 nm attached thereto. Hereinafter, the obtained substrate having the steel anchoring film attached thereto is referred to as &quot; weak anchoring property evaluation substrate 2 &quot;.

[Production method of positive liquid crystal composition (LC-1) for weak anchoring property evaluation]

(LC-1) was prepared by mixing and dissolving the compounds described in the following general formulas (2-1) to (2-9) at the stated weight ratios.

[Method of producing liquid crystal display element for weak anchoring property evaluation]

The two substrates of the weak anchoring property evaluation substrate 1 and the weak anchoring property evaluation substrate 2 were placed so as to face each other on the side of the hardened body and the steel anchoring film side so that the wiring direction of the Cr comb electrodes of the weak anchoring property evaluation substrate 1 and the weak anchoring And the easy axis of the steel anchoring film of the evaluation substrate 2 was parallel. Further, voids for injecting the positive-type liquid crystal composition (LC-1) were formed between the cured body and the steel anchoring film and adhered to each other to prepare an empty evaluation cell having a cell thickness of 4 탆. The positive type liquid crystal composition (LC-1) was vacuum-injected into the fabricated blank evaluation cell to prepare a liquid crystal display device for evaluation. 1, the wiring direction of the electrode line 15A and the easy axis of easy orientation of the steel anchoring film 14 are the direction Y. In addition,

[Method for judging whether or not the alignment is carried out when voltage is not applied]

Two polarizing plates orthogonal to the polarizing direction were placed on a light viewer 7000PRO (product name, Hakuba Photo Industrial Co., Ltd., hereinafter referred to as "backlight device") in parallel with the substrate, and the produced liquid crystal display device for evaluation Respectively. Subsequently, the backlight device was turned on, and light passing through the above-described two polarizing plates and the evaluation liquid crystal display device produced was visually observed under two conditions. The first condition is a condition in which the wiring direction of the interdigital electrodes of the manufactured evaluation liquid crystal display element is parallel to the polarization direction of the polarizing plate on the backlight device side. 1, the polarizing direction of the polarizing plate 12A on the backlight device side is the direction Y and the polarizing direction of the other polarizing plate 12B is the direction X. In this case, 6 shows the relationship between the wiring direction of the electrode line 15A and the polarization direction of the polarizing plate 12A. The second condition is that the two polarizers 12A and 12B under the first condition are rotated in the counterclockwise direction by 45 DEG in the X-Y plane. That is, 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 °. The relationship between the wiring direction of the electrode line 15A and the polarization direction of the polarizing plate 12A is shown in Fig. The case where there was no light leakage under the first condition and the case where the light transmission was observed under the second condition was determined to be the orientation "good" when the voltage was not applied. In the case where at least one of the cases where light is missing in the first condition and the case where the light transmission is not observed in the second condition is determined as "no" at the time of no voltage application.

[Method for judging whether or not driving is performed at the time of voltage application]

The easy axis of the strong anchoring film of the evaluation liquid crystal display element manufactured in the method for determining the orientation at the time of voltage unapplication is in a state of being parallel to the polarization direction of the polarizing plate on the backlight device side, A voltage was applied to the anode so as to have a square wave of 5 V and 60 Hz in potential difference. The case where the light transmittance was high at the time of applying the voltage was judged to be the drive "at the time of voltage application", and the case where it was not changed was judged to be the drive at the time of voltage application.

[Method for evaluating weak anchoring property]

If the anisotropy is not imparted to the cured product by the rubbing method or the photo alignment method described above, if the anchoring of the cured product is strong, the liquid crystal molecules in the vicinity of the cured product are randomly oriented, In the process of determining the orientation at the unattended state, light is missing. Therefore, the case where the orientation "oil" at the time of voltage application and the drive "oil" at the time of no voltage application are judged to be weak anchoring property "○". The other cases were rated as &quot; poor &quot; with anchoring properties.

[Method of producing substrate for patterning property 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 캜 for 2 minutes to obtain a substrate having a coated film. Next, a proximity photoresist TME-150PRC (trade name, Topcon Co., Ltd.) was used in a nitrogen mask having a width of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, . The amount of exposure was determined to be 50 mJ / cm ² by measuring with a cumulative photometer UIT-102 (trade name, manufactured by Ushio Inc.) and a photoreceptor UVD-365PD (trade name, manufactured by Ushio Inc.). The substrate with the coated film after exposure was paddled with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then the substrate with the coated film was rinsed with pure water for 20 seconds and then dried with a hot plate at 100 캜 for 2 minutes. Post baking was carried out with a hot plate at 150 캜 for 30 minutes to obtain a substrate having a film thickness of about 30 nm and attached with a cured body for patterning evaluation.

[Method of observing the minimum line width]

The substrate with the obtained cured product for patterning evaluation attached was observed with an optical microscope and the minimum line width was observed.

[Evaluation method of patterning property]

When the observed minimum line width is 10 μm or less is referred to as patterning property ◯, when the minimum line width is larger than 10 μm, or when line patterns of all widths can not be resolved (marked as "non-resolution"), I appreciated.

[Examples 2 to 11 and Comparative Examples 1 to 3]

According to the method of Example 1, the respective components were mixed and dissolved at the ratios (unit: g) described in Tables 2-1 and 2-2 to obtain a curable composition. The evaluation of weak anchoring property and patternability was carried out according to the method of Example 1 by determining the presence or absence of voltage unattended visibility and whether or not to drive when voltage was applied and observing the minimum line width. -2. However, there was a case where "post-baking for 30 minutes on a hot plate at 150 ° C" of the method of manufacturing the substrate for roughly anchoring property evaluation 1 and the method of producing a substrate for patterning evaluation was changed to "post-baking for 30 minutes in an oven at 230 ° C" , And Table 2-1 and Table 2-2 show post-baking apparatuses and post-baking temperatures. In the post-baking apparatuses shown in Tables 2-1 and 2-2, the case of hot plate is denoted by "H" and the case of oven is denoted by "O".

[Refractive index controllability test (Examples 1 and 7)]

The curable compositions described in Example 1 and Example 7 were formed on a glass substrate in the same manner as in the method for manufacturing a weakly anchoring property evaluation substrate 1 to obtain a substrate having a cured body. The reflectance of the cured product on the substrate to which the cured product was attached was measured by using a reflection spectroscopic film thickness meter FE-3000 (Otsuka Electronics Co., Ltd.). The measurement wavelength range is 400 to 780 nm, and the value of the refractive index was obtained from the interference spectrum of the reflectance by fitting to the theoretical formula of nk-Cauchy. When the refractive index of the cured product was confirmed to be 589 nm, the refractive index of the cured product of Example 1 was 1.49 and the refractive index of the cured product of Example 7 was 1.54. From this, it was judged that the refractive index could be controlled by incorporating benzyl alcohol, which is aryl methacrylate, into the raw material of the copolymer (A) having fluorine and carboxyl groups and adjusting the addition amount thereof.

[Chemical resistance test (Examples 2, 4, 6, 8, and 11)]

The curable compositions described in Examples 2, 4, 6, 8, and 11 were formed on a glass substrate in the same manner as in the method for manufacturing a weakly anchoring property evaluation substrate 1 to obtain a substrate having a cured body. 0.1 mL of PGMEA was dropped on the substrate with the cured product obtained thereon, and the substrate was allowed to stand at 23 DEG C for 1 minute, followed by drying the PGMEA with an air blower. Thereafter, it was visually observed under a fluorescent lamp to determine that the chemical resistance of the cured product obtained from the curable composition was good because no mark remained on the substrate to which the cured product was attached.

[Adhesion test (Examples 2, 6, 8 and 9)]

The curable compositions described in Examples 2, 6, 8, and 9 were formed on a glass substrate in the same manner as in the method for manufacturing a weakly anchoring property evaluation substrate 1 to obtain a substrate having a cured body. A cross-cut test (JIS-K5600, ISO2409) by tape peeling of a cured product was performed on the substrate having the cured product obtained thereon, and the number of the remaining cured products was counted. Since all the test results were classified 0, it was judged that the adhesion of the cured product obtained from the curable composition to the substrate was good.

[Liquid repellency test (Example 10)]

A cured product was formed on a glass substrate in the same manner as in the method for manufacturing a weakly anchoring property evaluation substrate 1 according to Example 10 to obtain a substrate having a cured product. To the cured product of the substrate on which the obtained cured product was adhered, 5 占 의 of water was dropped using a portable contact angle PCA-1 (Kyowa Interface Science Co., Ltd.), 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)]

A cured body was formed on a glass substrate in the same manner as in the method for manufacturing a weakly anchoring property evaluation substrate 1 according to Example 11 to obtain a substrate having a cured body. The substrate having the obtained cured body was reheated in an oven at 230 캜 for 60 minutes to obtain a substrate having the cured body attached thereto after reheating. A liquid crystal display device was produced in the same manner as in the method for manufacturing a weakly anchored liquid crystal display element except that a substrate having a cured body after reheating was used instead of the substrate 1 for weak anchoring property evaluation, And evaluation of weak anchoring property by judging the presence or absence of driving at the time of voltage application. As a result, it was judged that the cured product obtained from the cured composition had 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 are excellent in patterning property, and the cured product obtained from the curable composition has excellent anchorability. On the other hand, the cured product obtained in Comparative Example 1, which is a curable composition containing no polymerizable compound (a1) having fluorine in the raw material, has poor poor anchoring property. Comparative Example 3, which is a curable composition that does not contain a polymerizable compound (a2) having a carboxyl group in a raw material, and Comparative Example 2, which does not contain a multifunctional polymerizable compound (B) and a photopolymerization initiator (C) , It can be seen that the patterning property is poor.

The cured product obtained from the curable composition of the present invention can be used as a weak anchoring film used in a liquid crystal display element because of its excellent anchorability. Further, since the curable composition of the present invention has a high patterning property, it is possible to form a patterned cured body in accordance with the shape of the mask pattern, and no cured body is formed at an unnecessary portion such as the outer peripheral portion of the substrate. It is possible to manufacture a liquid crystal display device.

10 Liquid crystal display element 11 Backlight unit
12A, 12B Polarizer LCP-1 First substrate
LCP-2 Second substrate LCP-3 liquid crystal layer
LCP-4 driving electrode layer 13 weak anchoring film
14 Anchoring membrane 15A Electrode line
Lp liquid crystal compound
X, Y A coordinate axis that is imaginary on a plane parallel to the first substrate and the second substrate

Claims (18)

A curable composition comprising a copolymer (A) having a fluorine and a carboxyl group, a multifunctional polymerizable compound (B), and a photopolymerization initiator (C). The method according to claim 1,
Wherein the copolymer (A) having a fluorine and carboxyl group is a copolymer from a raw material comprising a polymerizable compound (a1) having fluorine and a polymerizable compound (a2) having a carboxyl group. The method of claim 2,
Wherein the fluorine-containing polymerizable compound (a1) is contained in an amount of not less than 50% by weight and not more than 98% by weight, based on 100% by weight of the raw material of the fluorine- and carboxyl-containing copolymer (A). The method of claim 2,
Wherein the fluorine-containing polymerizable compound (a1) is present in an amount of not less than 80% by weight and not more than 95% by weight, based on 100% by weight of the raw material of the fluorine- and carboxyl-containing copolymer (A). The method of claim 2,
Wherein the raw material of the fluorine- and carboxyl-group-containing copolymer (A) comprises the fluorine-containing polymerizable compound (a1) and the carboxyl group-containing polymerizable compound (a2). The method according to any one of claims 2 to 5,
Wherein the fluorine-containing polymerizable compound (a1) is a fluorine-containing (meth) acrylate compound. The method of claim 6,
Wherein the fluorine-containing (meth) acrylate compound is a compound represented by the following formula (1).

(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, and n ² and n ⁴ Are independently an integer of 0 to 6, and at least one of R ² , R ³ , R ⁴ , R ⁵ and R ⁸ is fluorine. The method of claim 7,
Wherein the compound represented by the formula (1) is at least one compound selected from the group consisting of 2,2,2-trifluoroethyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) (Meth) acrylate, and 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate. The method of claim 7,
A curable composition wherein the compound represented by the formula (1) is 2,2,2-trifluoroethyl methacrylate. The method according to any one of claims 2 to 9,
Wherein the polymerizable compound (a2) having a carboxyl group is at least one selected from the group consisting of (meth) acrylic acid and a (meth) acrylate compound having a carboxyl group. The method according to any one of claims 2 to 9,
Wherein the polymerizable compound (a2) having a carboxyl group is methacrylic acid. The method 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 method of claim 12,
Wherein the compound having three or more polymerizable double bonds per molecule is selected from the group consisting of isocyanuric acid ethyleneoxide modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol (Meth) acrylate, pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl group-containing polyfunctional (meth) acrylate. The method according to any one of claims 1 to 13,
A curable composition for forming a weak anchoring film of a liquid crystal display element. A cured product obtained by curing the curable composition according to any one of claims 1 to 14. A liquid crystal display element having the weakened anchoring film according to claim 15. A first substrate (LCP-1) formed with the weak anchoring film according to claim 15,
A second substrate (LCP-2) having a strong anchoring film disposed opposite to the weak anchoring film with an interval therebetween,
A liquid crystal layer (LCP-3) disposed between the weak anchoring film and the strong anchoring film,
(LCP-1) and a second substrate (LCP-2) are provided on one of the first and second substrates (LCP-1 and LCP-2) And a driving electrode layer (LCP-4) for applying an electric field in a direction along the direction of the liquid crystal layer;
And the liquid crystal molecules are driven by the electric field applied to the driving electrode layer (LCP-4), whereby the transmittance of light changes. 18. The method of claim 17,
The driving electrode layer LCP-4 is composed of a plurality of electrode lines arranged on a substrate surface of the first substrate LCP-1 or the second substrate LCP-2, and when the electric field is not applied , The alignment direction of the liquid crystal molecules on the side of the second substrate (LCP-2) is parallel or orthogonal to the direction in which the electrode lines continue.

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