TWI671368B - Curable resin composition, cured film, wavelength conversion film, light emitting element, and method for forming light emitting layer - Google Patents

Abstract

The present invention provides a hardenable resin composition containing quantum dots, which can easily form a highly reliable hardened film with excellent fluorescent characteristics, a hardened film, and a method for forming a wavelength conversion film, a light emitting element, and a light emitting layer. . A curable resin composition containing [A] a polymer having a structural site represented by the following formula (1) and [B] a quantum dot was prepared. A cured film is formed on the substrate 12 using a curable resin composition. The cured film constitutes a wavelength conversion film, and becomes a light emitting layer 13 to form a wavelength conversion substrate 11. The light emitting display element 100 is configured in combination with a light source substrate 18 including a light source 17.

Description

Method for forming curable resin composition, cured film, light-emitting element, wavelength conversion film, and light-emitting layer

The present invention relates to a method for forming a curable resin composition, a cured film, a wavelength conversion film, a light emitting element, and a light emitting layer.

The extremely small particles (dots) formed to block electrons are called "quantum dots" and have attracted much attention in recent years. The size of a quantum dot is several nanometers to tens of nanometers in diameter and contains about 10,000 atoms.

When quantum dots are dispersed in a thin film of a semiconductor of a solar cell panel, energy conversion efficiency can be greatly improved. Therefore, applications to solar cells are being studied (for example, refer to Patent Document 1). Furthermore, by changing the size of the quantum dots (changing the band gap), the color (luminous wavelength) (wavelength conversion) of the fluorescent light emitted can be changed. Therefore, fluorescent probes are being investigated in biological research (see Non-Patent Literature 1), or an application to a display element as a wavelength conversion material (see Patent Literature 2 and Patent Literature 3).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-216560

[Patent Document 2] Japanese Patent Laid-Open No. 2008-112154

[Patent Document 3] Japanese Patent Laid-Open No. 2009-251129

[Non-patent literature]

[Non-Patent Document 1] Shenlong, "Semiconductor Quantum Dots, Their Synthesis, and Applications in Life Science", Production and Technology, Volume 63, Number 2, 2011, Pages 58 to 65

As shown in the examples of Non-Patent Document 1 or Patent Document 1, representative quantum dots are semiconductor quantum dots such as CdSe (cadmium selenide), CdTe (cadmium telluride), and PbS including semiconductors of the II-V group.

However, for example, lead (Pb) as a main component is a widely known material that is worried about its toxicity. In addition, cadmium (Cd) and its compounds exhibit extremely strong toxicity even at low concentrations, and are materials that are feared to cause kidney disease or have carcinogenic properties. Therefore, it is required to form a quantum dot containing a more secure material.

Furthermore, when quantum dots are to be applied to a solar cell panel, a display of a display element, or the like, in order to utilize the fluorescent light emission, there are cases where it is required to form a film or layer including quantum dots in a particle form. That is, it is sometimes required to form a wavelength conversion film or a light emitting layer that displays fluorescent light emission.

As a method for forming a light-emitting layer using quantum dots in a particle form, for example, it is known to use an appropriate base as shown in Examples of Patent Document 1 or Patent Document 2. A method of forming a layer containing quantum dots directly on a board. However, in such a forming method, the stability of the obtained light emitting layer is poor. In particular, there are concerns about the adhesion between the layer containing the quantum dots and the substrate.

Therefore, a method of forming a layer or a film by mixing or embedding quantum dots in the form of particles in a resin material has been proposed. However, the method of using quantum dots to achieve high dispersibility, maintain fluorescence characteristics as quantum dots, and form a layer or film with a resin has not been sufficiently studied.

Therefore, a technique of using quantum dots together with a resin material to achieve high dispersibility, thereby forming a layer or film of the quantum dots without reducing the fluorescence emission characteristics of the quantum dots is required. In addition, a technology for forming a light emitting layer or a wavelength conversion film including a quantum dot, light resistance, and the like, which is excellent, is required. In particular, a resin material that can be used with quantum dots and is suitable for forming a light-emitting layer or a wavelength conversion film containing a quantum dot and a resin is required.

In this case, it is desirable that the resin material can be used together with a quantum dot including a security material, and is suitable for forming a light-emitting layer or a wavelength conversion film having excellent fluorescence characteristics or reliability.

In addition, it is preferable that the light emitting layer or the wavelength conversion film including the quantum dot and the resin material can be easily formed, and has high productivity. Therefore, in the formation of the light emitting layer or the wavelength conversion film including the quantum dot and the resin material, it is preferable to use a simple formation method such as coating. The light emitting layer or the wavelength conversion film is preferably formed from a liquid resin composition containing a quantum dot and a resin component by a method such as coating.

Therefore, a resin composition is required. The resin composition is prepared by including a quantum dot and a resin component, and a light emitting layer or a wavelength conversion film can be formed by a method such as coating.

Furthermore, it is further preferred that the resin composition has excellent patternability. That is, it is preferable that the resin composition forming the light emitting layer or the wavelength conversion film can be patterned, and can be used, for example, in the configuration of a light emitting element such as a light emitting display element. In this case, it is preferable that, for example, a photolithography method can be used in the formation of the patterned light-emitting layer or the wavelength conversion film, and it can be easily implemented.

Therefore, there is a need for a radiation-sensitive curable resin composition that can easily form a patterned light-emitting layer or a wavelength conversion film by a known patterning method such as a photolithography method.

The present invention has been made in view of the problems described above. That is, an object of the present invention is to provide a curable resin composition containing a quantum dot, which can easily form a highly reliable cured film exhibiting excellent fluorescent characteristics.

Furthermore, an object of the present invention is to provide a highly reliable cured film having excellent fluorescent characteristics formed using a curable resin composition containing quantum dots.

Furthermore, an object of the present invention is to provide a highly reliable wavelength conversion film having excellent fluorescence characteristics formed using a curable resin composition containing quantum dots.

An object of the present invention is to provide a light-emitting element including a light-emitting layer formed using a curable resin composition containing a quantum dot.

Another object of the present invention is to provide a method for forming a light-emitting layer using a curable resin composition containing quantum dots.

Other objects and advantages of the present invention will become clear from the following description.

A first aspect of the present invention relates to a curable resin composition comprising: [A] a polymer having a structural site represented by the following formula (1), and [B] a quantum dot;

(In the formula (1), X ¹ represents an organic group having 2 to 30 carbon atoms; X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms; X ² represents a hydrogen atom 1, monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, or divalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms A group in which one or more hydrogen atoms are substituted by a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent; * represents a bonding position).

Preferably, in the first aspect of the present invention, the [B] quantum dot contains a material selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element A group of compounds of at least two elements.

In the first aspect of the present invention, it is preferable that the [B] quantum dot contains A compound in which In is a constituent.

Preferably, in the first aspect of the present invention, the [B] quantum dot is selected from the group consisting of an InP / ZnS compound, a CuInS ₂ / ZnS compound, an AgInS ₂ compound, a (ZnS / AgInS ₂ ) solid solution / ZnS compound, and Zn. At least one of a group consisting of an AgInS ₂ compound and a Si compound.

It is preferable that the first aspect of the present invention further contains a [C] polymerization initiator.

In the first aspect of the present invention, it is preferable that the polymerizer further contains [C] a polymerization initiator, and the [C] polymerization initiator is a polymerization initiator having no nitrogen atom in the molecule.

It is preferable that the first aspect of the present invention further contains a [D] polymerizable unsaturated compound.

It is preferable that the first aspect of the present invention further contains [E] an antioxidant.

In the first aspect of the present invention, it is preferable that [E] antioxidant is further contained, and [E] antioxidant is a phosphite-based antioxidant.

A second aspect of the present invention relates to a cured film, which is formed using the curable resin composition of the first aspect of the present invention.

A third aspect of the present invention relates to a wavelength conversion film, which is formed using the curable resin composition of the first aspect of the present invention.

A fourth aspect of the present invention relates to a light-emitting device, which includes a light-emitting element formed using the curable resin composition of the first aspect of the present invention. Light layer.

A fifth aspect of the present invention relates to a method for forming a light-emitting layer, which is a method for forming a light-emitting layer of a light-emitting element, which is characterized by including the following steps: (1) forming a hardenability of the first aspect of the present invention on a substrate A step of coating a resin composition; (2) a step of irradiating at least a part of the coating film formed in step (1) with radiation; (3) a step of developing a radiation-coated film in step (2) ; And (4) a step of exposing the developed coating film in step (3).

According to the first aspect of the present invention, there is provided a curable resin composition containing a quantum dot, which can easily form a highly reliable cured film exhibiting excellent fluorescent characteristics.

In addition, according to the second aspect of the present invention, a highly reliable cured film having excellent fluorescent characteristics and formed using a curable resin composition containing quantum dots is provided.

In addition, according to a third aspect of the present invention, a highly reliable wavelength conversion film having excellent fluorescent characteristics and formed using a curable resin composition containing quantum dots is provided.

A fourth aspect of the present invention provides a light-emitting element including a light-emitting layer formed using a curable resin composition containing a quantum dot.

In addition, the fifth aspect of the present invention provides the use of a quantum dot-containing A method for forming a light-emitting layer of a curable resin composition.

1.1a‧‧‧coating film

2, 12, 16‧‧‧ substrate

3‧‧‧Mask

4, 4a‧‧‧ radiation

5‧‧‧hardened film

11‧‧‧ Wavelength Conversion Substrate

13, 13a, 13b, 13c‧‧‧ luminescent layer

14‧‧‧ Black Matrix

15‧‧‧ Adhesive layer

17, 17a, 17b, 17c

18‧‧‧ light source substrate

100‧‧‧light-emitting display element

FIG. 1 is a cross-sectional view of a substrate illustrating an example of a coating film forming step in forming a cured film according to a second embodiment of the present invention.

2 is a cross-sectional view schematically illustrating an example of a radiation irradiation step in the formation of a cured film according to a second embodiment of the present invention.

3 is a cross-sectional view of a substrate illustrating an example of a development step in the formation of a cured film according to the second embodiment of the present invention.

4 is a cross-sectional view of a cured film and a substrate illustrating an example of a curing step in the formation of a cured film according to a second embodiment of the present invention.

5 is a cross-sectional view schematically showing an example of a light-emitting display element as a light-emitting element according to a fourth embodiment of the present invention.

The curable resin composition according to the first embodiment of the present invention contains [A] the structural portion represented by the following formula (1), and further, the structural portion represented by the formula (1) is represented by the formula (2) Polymer (hereinafter also referred to as "[A] polymer" or simply "[A] component"), and [B] quantum dots (hereinafter also referred to as "[B] component") A curable resin composition.

A curable resin composition containing [A] a polymer having a structural site represented by the following formula (1), and [B] Quantum dot.

(In the formula (1), X ¹ represents an organic group having 2 to 30 carbon atoms. X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents a hydrogen atom 1, monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, or divalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms A group in which one or more hydrogen atoms are substituted by a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent. * Indicates a bonding position)

The curable resin composition described above contains a polymer having a structural site represented by the formula (1), which is a structural site represented by the following formula (2).

(In the formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 12 One or more hydrogen atoms of a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, an alkyl group, an aralkyl group which may have a substituent, or An alkoxy substituted group. Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom, a monovalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group or carbon having 1 to 12 carbon atoms. Divalent linear or branched or cyclic saturated or unsaturated hydrocarbon groups of 1 to 12 having one or more hydrogen atoms via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl or aromatic group which may have a substituent An alkyl or alkoxy substituted group. N represents 0 or 1)

The curable resin composition according to the first embodiment of the present invention contains a [A] polymer, and is a resin composition suitable for easily forming a film or a layer by coating or the like.

Furthermore, the curable resin composition according to the first embodiment of the present invention can achieve a good dispersion state of the [B] quantum dots by containing the quantum dots of the [B] component together with the [A] component.

When the quantum dots are used together with a resin component, a solvent, or the like to form a composition, the quantum dots tend to aggregate in the composition, and it is difficult to achieve a good dispersion state. In quantum dots, aggregation becomes detrimental to their fluorescent properties. Therefore, in the curable resin composition according to the first embodiment of the present invention, the [A] component is selectively contained as a resin component so that the [B] quantum dots show a good dispersion state.

As a result, the curable resin composition according to the first embodiment of the present invention can form a resin composition that achieves a good dispersed state of [B] quantum dots. In addition, the curable resin composition according to the first embodiment of the present invention can be easily formed by coating or the like. This method forms a layer or film in which [B] quantum dots are dispersed.

The curable resin composition according to the first embodiment of the present invention may have radiation sensitivity. Therefore, it is preferred that the curable resin composition according to the first embodiment of the present invention contains a [C] polymerization initiator (hereinafter also simply referred to as "[C] component"), and further preferably contains [D] polymerization Sexually unsaturated compounds (hereinafter also referred to as "[D] component"). In addition, the curable resin composition according to the first embodiment of the invention can be patterned by, for example, a photolithography method or the like based on its radiation sensitivity.

In addition, in the present invention, the "radiation" irradiated during exposure includes visible light rays, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

The photolithography method includes the steps of: forming a resist film by applying a so-called resist composition on the surface of a substrate to be processed or processed; irradiating light or an electron beam to expose a predetermined resist pattern; An exposure step for forming a latent image of the resist pattern; a step for performing a heat treatment as necessary; a developing step for developing it to form a desired fine pattern; and using the fine pattern as a mask to etch the substrate And other processing steps.

The curable resin composition of the present invention is patterned when necessary to form a cured film of the second embodiment of the present invention. The cured film of the second embodiment of the present invention is configured by including [B] quantum dots in a resin.

The cured film according to the second embodiment of the present invention may have a fluorescent light emission (wavelength conversion) function based on the [B] quantum dot. Therefore, a wavelength conversion film or a light emitting layer that emits fluorescent light having a wavelength different from that of the excitation light can be used.

In particular, the cured film according to the second embodiment of the present invention In addition to the wavelength conversion film of the third embodiment, it is also suitable for use as a light-emitting layer, and can be used in the configuration of the light-emitting element of the fourth embodiment of the present invention described later.

Hereinafter, the curable resin composition of the first embodiment of the present invention, the cured film of the second embodiment of the present invention, the wavelength conversion film of the third embodiment of the present invention, the light-emitting element of the fourth embodiment of the present invention, A method for forming a light emitting layer according to a fifth embodiment of the present invention will be described.

Embodiment 1.

<Curable resin composition>

As described above, the curable resin composition according to the first embodiment of the present invention contains the [A] component and [B] quantum dots as essential components.

The curable resin composition according to the first embodiment of the present invention contains the [A] component and [B] quantum dots, and can form a resin composition that achieves a good dispersion state of [B] quantum dots.

The curable resin composition according to the first embodiment of the present invention can have an excellent fluorescent light emission (wavelength conversion) function by forming a [B] quantum dot by using a method such as coating (hereinafter also referred to as "fluorescent property" ", Or" fluorescent properties ", etc.) according to the second embodiment of the present invention.

The curable resin composition according to the first embodiment of the present invention may have radiation sensitivity. Therefore, as described above, the curable resin composition according to the first embodiment of the present invention preferably further contains a [C] polymerization initiator, and further preferably further contains a [D] polymerizable unsaturated compound.

The curable resin composition according to the first embodiment of the present invention can be applied to The hardened film according to the second embodiment of the present invention having stable fluorescent properties is formed by including the [A] component, the [B] quantum dot, and the like together with the [E] antioxidant.

Further, the curable resin composition according to the first embodiment of the present invention may contain the other optional components as long as the effects of the present invention are not impaired.

Hereinafter, each content component of the curable resin composition according to the first embodiment of the present invention will be described in more detail.

[[A] Polymer]

The curable resin composition according to the first embodiment of the present invention includes [A] having a structural portion represented by the following formula (1) (hereinafter also simply referred to as "structural portion (1)"), and further, formula (1) The structural site shown is a polymer of a structural site represented by the following formula (2) (hereinafter also simply referred to as "structural site (2)").

(In the formula (1), X ¹ represents an organic group having 2 to 30 carbon atoms. X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents a hydrogen atom 1, monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, or divalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms A group in which one or more hydrogen atoms are substituted by a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent. * Indicates a bonding position)

The curable resin composition described above contains a polymer having a structural site represented by the formula (1) as a structural site represented by the following formula (2).

(In formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 12 One or more hydrogen atoms of a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, an alkyl group, an aralkyl group which may have a substituent, or An alkoxy substituted group. Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom, a monovalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group or carbon having 1 to 12 carbon atoms. Divalent linear or branched or cyclic saturated or unsaturated hydrocarbon groups of 1 to 12 having one or more hydrogen atoms via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl or aromatic group which may have a substituent An alkyl or alkoxy substituted group. N represents 0 or 1)

X ^{1 in} the formula (1) represents an organic group having 2 to 30 carbon atoms, and examples thereof include an alkylene group, a phenylene group, a naphthyl group, an epoxy alkyl group, and the like.

X ^{2 in} the formula (1) represents a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbons or a monovalent linear or branched one having 1 to 12 carbons. A group in which one or more hydrogen atoms of a cyclic saturated or unsaturated hydrocarbon group are substituted with a substituent.

Examples of monovalent linear or branched saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and 2-methylpropyl groups. Carbons such as methyl, 1-methylpropyl, third butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl Monovalent hydrocarbon groups such as linear or branched alkyl groups of 1 to 12 and the like.

Examples of the monovalent cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the formula (2) include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, bicyclo [1.1.0] butane, Bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tri Cycloalkanes such as cyclo [3.3.1.1 ^3,7 ] decane, etc.

Examples of the aromatic hydrocarbon include benzene and naphthalene.

Moreover, as described above, the monovalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in X ² in the formula (1) may be monovalent. One or more hydrogen atoms of a linear, branched or cyclic saturated or unsaturated hydrocarbon group are substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent From the base.

The structural site represented by the formula (1) can be obtained by, for example, using vinylbenzene It is provided by polymerizing monomers such as formic acid.

Y ¹ in the formula (2) represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms, and a monovalent linear or branched chain having 1 to 3 carbon atoms Examples of the saturated hydrocarbon group include methyl, ethyl, 1-propyl, and 2-propyl. Examples of preferable Y ¹ in the formula (2) include a hydrogen atom and a methyl group.

Y ^{2 in} the formula (2) represents a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, or a divalent linear or branched chain having 1 to 12 carbon atoms. A group in which one or more hydrogen atoms of a cyclic saturated or unsaturated hydrocarbon group are substituted with a substituent.

Examples of the divalent linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ² in the formula (2) include methyl, ethyl, n-propyl, and isopropyl groups. Base, n-butyl, 2-methylpropyl, 1-methylpropyl, third butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, Divalent hydrocarbon groups, such as undecyl and dodecyl, linear or branched alkyl groups having 1 to 12 carbon atoms, and the like.

Examples of the divalent cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ² in the formula (2) include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, bicyclo [1.1.0] butane, Bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tri Cycloalkanes such as cyclo [3.3.1.1 ^3,7 ] decane, etc.

Examples of the aromatic hydrocarbon include benzene and naphthalene.

Moreover, as described above, the divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ² in the formula (2) may be divalent. One or more hydrogen atoms of a linear, branched or cyclic saturated or unsaturated hydrocarbon group are substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent From the base.

Examples of the divalent organic group in Y ³ in the formula (2) include a divalent aliphatic group and a divalent aromatic group. The divalent organic group may also be a "non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually connected through a linking group". Examples of the linking group in this case include -O-, -CO-, -S-, -SO _2- , alkylene, and -C (CF ₃ ) _2- .

Examples of the divalent aliphatic group include a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group. In this case, in addition to hydrogen, a linear, branched, or cyclic saturated or unsaturated hydrocarbon group may be bonded to a carbon chain such as oxygen or nitrogen, sulfur, and chlorine. Therefore, a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group may be a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group. A halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent may be substituted.

Examples of the divalent linear or branched saturated or unsaturated hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, and 1 -Methylpropyl, third butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other carbon numbers 1 ~ 12 is a divalent hydrocarbon group such as a linear or branched alkyl group.

Furthermore, the divalent cyclic saturated or Examples of the unsaturated hydrocarbon group include groups derived from an alicyclic hydrocarbon.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, and bicyclo [1.1.0] butane. Alkane, bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane , Tricyclic [3.3.1.1 ^3,7 ] decane and other cycloalkanes.

Examples of the divalent aromatic group include an aromatic hydrocarbon group and a heteroaromatic group containing an element other than carbon in the ring structure. The divalent aromatic group may be a monocyclic aromatic group or a condensed polycyclic aromatic group.

Examples of the divalent aromatic group include groups derived from benzene, naphthalene, and anthracene.

The divalent aromatic group may be one or more hydrogen atoms of the divalent aromatic group via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent. Substituted groups.

Examples of the "non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or through a linking group" include biphenyl, phenyl ether, benzophenone, diphenylfluorene, and diphenyl. Sulfide and other groups.

In addition, when n in the formula (2) is 1, the structure portion represented by the formula (2) includes a structure in which two carboxyl groups are bonded to Y ³ . That is, when n in the formula (2) is 1, two carboxyl groups respectively bonded to Y ³ and Y ³ form a dicarboxylic acid structure.

In this case, the two carboxyl groups respectively bonded to Y ³ and Y ³ can form, for example, an aliphatic dicarboxylic acid structure and an aromatic dicarboxylic acid structure as described above. Moreover, the two carboxyl groups respectively bonded to Y ³ and Y ³ may also form a two containing "non-condensed polycyclic aromatic group bonded directly to each other or by, for example, the linking group" Carboxylic acid structure.

More specifically, the aliphatic dicarboxylic acid structure can form a malonic acid structure, a succinic acid structure, a glutaric acid structure, an adipic acid structure, a pimelic acid structure, a suberic acid structure, an azelaic acid structure, decane Aliphatic saturated dicarboxylic acid structures such as diacid structure; maleic acid structure, fumaric acid structure, itaconic acid structure, mesaconic acid structure, citraconic acid structure and other aliphatic unsaturated dicarboxylic acid structures; hexahydro o-benzene Alicyclic dicarboxylic acid structures such as dicarboxylic acid structure, hexahydroisophthalic acid structure, hexahydroterephthalic acid structure, and 4-methylcyclohexanedicarboxylic acid structure.

In addition, an aromatic dicarboxylic acid structure or a dicarboxylic acid structure containing "a non-condensed polycyclic aromatic group in which aromatic groups are directly or indirectly connected to each other by, for example, the linking group" can form phthalic acid, for example. Structure, 2,3-benzophenone dicarboxylic acid structure, 3,4-benzophenone dicarboxylic acid structure, 2,3-dicarboxyphenylphenyl ether structure, 3,4-dicarboxyphenylbenzene Ether structure, 2,3-biphenyldicarboxylic acid structure, 3,4-biphenyldicarboxylic acid structure, 2,3-dicarboxyphenylphenylfluorene structure, 3,4-dicarboxyphenylphenylfluorene Structure, 2,3-dicarboxyphenylphenylsulfide structure, 3,4-dicarboxyphenylphenylsulfide structure, 1,2-naphthalenedicarboxylic acid structure, 2,3-naphthalenedicarboxylic acid structure, Dicarboxylic acid structures such as 1,8-naphthalenedicarboxylic acid structure, 1,2-anthracene dicarboxylic acid structure, 2,3-anthracene dicarboxylic acid structure, and 1,9-anthracene dicarboxylic acid structure.

Y ^{4 in} the formula (2) represents a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms, or a monovalent linear or branched chain having 1 to 12 carbon atoms. A group in which one or more hydrogen atoms of a cyclic saturated or unsaturated hydrocarbon group are substituted with a substituent.

Examples of the monovalent linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the formula (2) include methyl, ethyl, n-propyl, and isopropyl groups. Base, n-butyl, 2-methylpropyl, 1-methylpropyl, third butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, Monovalent hydrocarbon groups, such as undecyl and dodecyl, linear or branched alkyl groups having 1 to 12 carbon atoms.

Examples of the monovalent cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the formula (2) include groups derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, bicyclo [1.1.0] butane, Bicyclo [2.1.0] pentane, bicyclo [2.2.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, tri Cycloalkanes such as cyclo [3.3.1.1 ^3,7 ] decane, etc.

Examples of the aromatic hydrocarbon include benzene and naphthalene.

In addition, as described above, the monovalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the formula (2) may be monovalent. One or more hydrogen atoms of a linear, branched or cyclic saturated or unsaturated hydrocarbon group are substituted with a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent From the base.

Specific examples of the structural part represented by the following formula (2) include those represented by the following formulas (2-1) to (2-2).

[Chemical 4]

Preferred monomers that provide the structural site represented by the formula (2) include (meth) acrylic acid, 2- (meth) acryloxyethylsuccinic acid, and ω-carboxy-polycaprolactone. (Meth) acrylate compounds such as monoacrylate, 2-methacryloxyethylhexahydrophthalic acid, and the like.

Commercially available products that provide preferred monomers of the structural site represented by the formula (2) include: Light ester (registered trademark) HO-MS, Light ester HO-HH (above manufactured by Kyoeisha Chemical Co., Ltd.) ; Light acrylate (registered trademark) HOA-MS, Light acrylate HOA-HH, Light acrylate HOA-MPL (above manufactured by Kyoeisha Chemical Co., Ltd.); etc.

[A] Molar ratio of the structural site represented by the formula (1) and the structural site represented by the formula (2) in the polymer ((structural site (1) / (structural site (2)) The range of) is preferably (structural part (1) / (structural part (2)) = 1/3 ~ 5/1, and more preferably (structural part (1) / (structural part (2)) = 3 / 5 ~ 3/1. In addition, as the total content of the structural site (1) and the structural site (2) in the [A] polymer, the total of all structural sites in the [A] polymer is set to 100. In the case of Molar%, 5 Molar% to 100 Molar% is preferred, 5 Molar% to 95 Molar% is more preferred, and 10 Molar% to 90 Molar% is even more preferred.

When the content of the structural part (1) and the structural part (2) is 5 mol% or more of the total of all the structural parts based on the molar ratio contained, the [A] polymer can achieve [B] ] Resin component with good dispersion of quantum dots.

The [A] polymer described above is contained, dissolved, or dispersed in the curable resin composition according to the first embodiment of the present invention. Further, a resin composition for obtaining a layer or film containing [B] quantum dots by a simple formation method such as coating can be formed.

[[B] Quantum dot]

[B] quantum dots, which are an essential component of the curable resin composition according to the first embodiment of the present invention, are preferably semiconductor quantum dots formed using a semiconductor material. In addition, the [B] quantum dot is preferably a quantum dot including a security material, which is not constituted by Cd or Pb, but is constituted by, for example, In (indium) or Si (silicon).

Therefore, the [B] quantum dot is preferably a quantum dot including a compound selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, and a group 13 element. A group of at least two or more elements of the group represented by a prime, a group 14 element, a group 15 element, and a group 16 element.

Furthermore, more specifically, it is preferable to include a quantum dot including a compound selected from the group consisting of Be (beryllium) and Mg (magnesium), excluding elements such as Pb and Cd, which are of great concern for human safety. ), Ca (calcium), Sr (strontium), Ba (barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium ), In (indium), Tl (rhenium), C (carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony ), Bi (bismuth), O (oxygen), S (sulfur), Se (selenium), Te (tellurium), and at least two elements of the group of Po (rhenium).

At this time, it is preferable that the [B] quantum dot includes a compound (a) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a compound (b) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm. ).

[B] The quantum dot includes the compound (a) and / or the compound (b) having such a fluorescence emission characteristic, and therefore can have a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a wavelength region of 600 nm to 700 nm. . As a result, the curable resin composition according to the first embodiment of the present invention containing [B] quantum dots can form a cured film suitable for the structure of the light-emitting layer of a light-emitting element that displays images using light in the visible region.

Furthermore, [B] quantum dots contained in the curable resin composition according to the first embodiment of the present invention are more preferably quantum dots containing a compound containing In as a constituent component. In addition, the [B] quantum dot may be Si or a Si compound.

[B] The quantum dot is particularly preferably Si or Si compound.

By setting the component composition of [B] quantum dots as described above, the curable resin composition according to the first embodiment of the present invention can form a cured film having a safe and excellent fluorescent property, and it can also form a safe and excellent film. A wavelength conversion film of a fluorescent property or a light emitting layer of a light emitting element.

In addition, the [B] quantum dot contained in the curable resin composition according to the first embodiment of the present invention is preferably selected from a homogeneous structure type containing one compound and a core-shell structure type containing two or more compounds. At least one structural quantum dot.

[B] Quantum dots of core-shell structure type are composed of a compound that forms a core structure, and other compounds that surround the core structure. For example, an exciton (electron-hole pair) generated by light excitation is enclosed in the core by a semiconductor having a core covered with a semiconductor having a larger band gap. As a result, the probability of non-radiation migration on the surface of the quantum dot is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of the [B] quantum dot are improved.

[B] quantum dots contained in the curable resin composition according to the first embodiment of the present invention are preferably selected from quantum dots consisting of core-shell structure type InP / ZnS, in consideration of the composition and structure of the core, At least one of the group consisting of CuInS ₂ / ZnS and (ZnS / AgInS ₂ ) solid solution / ZnS, and homogeneous structure type quantum dots AgInS ₂ and Zn-doped AgInS ₂ .

As described above, the [B] quantum dot contained in the curable resin composition according to the first embodiment of the present invention is preferably selected from the group consisting of InP / ZnS compound, CuInS ₂ / ZnS compound, AgInS ₂ compound, and (ZnS / AgInS ₂ ) at least one of the group of a solid solution / ZnS compound, a Zn-doped AgInS ₂ compound, and a Si compound.

Since the [B] quantum dots exemplified above, the curable resin composition according to the first embodiment of the present invention containing the same can form a cured film having a safer and more excellent fluorescent characteristic, and can further form a more excellent fluorescent light. A characteristic wavelength conversion film or a light emitting layer of a light emitting element.

The [B] quantum dots contained in the curable resin composition according to the first embodiment of the present invention preferably have an average particle diameter of 0.5 to 20 nm, and more preferably 1.0 to 10 nm. When the average particle diameter is less than 0.5 nm, it is difficult to prepare [B] quantum dots, and even if they can be prepared, the fluorescent characteristics of [B] quantum dots may become unstable. In the case where the average particle diameter of the [B] quantum dot exceeds 20 nm, there may be cases where the quantum confinement effect cannot be obtained due to the size of the quantum dot, and desired fluorescent characteristics cannot be obtained, which is not ideal.

The shape of the [B] quantum dot is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disc shape, or other shapes. Information about the particle size, shape, and dispersion state of the quantum dots can be obtained by a transmission electron microscope (TEM).

As a method for obtaining the [B] quantum dot contained in the curable resin composition according to the first embodiment of the present invention, a known method for thermally decomposing an organometallic compound in a complex organic solvent can be used. Moreover, a core-shell structure type quantum dot can be obtained by forming a homogeneous core structure by reaction, adding a precursor to form a shell on the core surface in the reaction system, and stopping the reaction after the shell is formed , Separated from the solvent. Alternatively, a commercially available product may be used.

[B] in the curable resin composition as the first embodiment of the present invention The content of the quantum dots is preferably 0.1 to 100 parts by mass, and more preferably 0.2 to 50 parts by mass, with respect to 100 parts by mass of the [A] component. When the content of the [B] quantum dot is within the above range, a cured film having excellent fluorescent characteristics can be formed, and as a result, a wavelength conversion film or a light emitting layer of a light emitting element having excellent fluorescent characteristics can be formed. [B] If the content of the quantum dots is less than 0.1 parts by mass relative to 100 parts by mass of the [A] component, desired fluorescent characteristics cannot be obtained in the formed cured film, and a wavelength conversion film or a light emitting element cannot be formed. Light-emitting layer. In addition, if the amount of the component [A] is more than 100 parts by mass, the stability of the formed cured film is impaired, and a stable wavelength conversion film or a light emitting layer of a light emitting element cannot be formed.

[[C] Polymerization initiator]

The curable resin composition according to the first embodiment of the present invention may further contain a [C] polymerization initiator. [C] The polymerization initiator of the present embodiment is preferably one that generates active species that can induce radiation to initiate polymerization of a compound having a polymerizable group. Therefore, the [C] polymerization initiator of this embodiment is preferably a radiation-sensitive polymerization initiator, that is, a radiation-sensitive polymerization initiator.

The curable resin composition according to the first embodiment of the present invention contains a [C] polymerization initiator, thereby improving radiation sensitivity and improving patternability. In addition, the curable resin composition according to the first embodiment of the present invention can easily form a patterned light-emitting layer or a wavelength conversion film by a known patterning method such as a photolithography method. The [C] polymerization initiator is preferably used together with the [D] polymerizable unsaturated compound described later and contained in the curable resin composition according to the first embodiment of the present invention. Thereby, the curable resin composition according to the first embodiment of the present invention can further improve the crosslinking reaction. It can further improve the film strength of the cured film of the second embodiment of the present invention formed from the curable resin composition and the adhesion to the substrate.

Examples of the [C] polymerization initiator in the curable resin composition according to the first embodiment of the present invention include an oxime ester compound, an acetophenone compound, and a biimidazole compound. The [C] polymerization initiator may be used alone or in combination of two or more.

Examples of the oxime ester compound include ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamoxime ), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzylideneoxime)], 1- [9-ethyl-6-benzylidene-9H- Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3- Yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzyl) -9H-carbazol-3-yl]- Ethane-1-one oxime-O-benzoate, ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylbenzyl) -9H-carbazole-3 -Yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzyl) -9H-carbazole -3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofurylbenzyl) -9H-carbazole- 3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-di O-fluorenyl oxime compounds such as oxetanyl) methoxybenzyl} -9H-carbazol-3-yl] -1- (O-acetamoxime) and the like.

Among the above, the oxime ester compound is preferably ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O -Ethyl oxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzyl oxime)], ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -1- (O-acetamoxime), ethyl ketone-1- [9-ethyl- 6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzyl} -9H-carb Azol-3-yl] -1- (O-acetamoxime).

Examples of the acetophenone compound include α-aminoketone compounds.

Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino 2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropane-1-one and the like.

The acetophenone compound is preferably an α-amino ketone compound, and more preferably 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4- -Phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-bi Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-bis (Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4' , 5,5'-tetraphenyl-1,2-biimidazole and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

[C] A commercially available polymerization initiator may be used, and examples thereof include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure (registered trademark)) 907), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butane-1-one (Irgacure 379), 1,2 -Octanedione-1- [4- (phenylthio) -2- (O-benzidine oxime)] (Irgacure (registered trademark) OXE01), ethyl ketone-1- [9-ethyl-6- ( 2-methylbenzidine Group) -9H-carbazol-3-yl] -1- (O-acetamoxime) (Irgacure (registered trademark) OXE02) (the above is manufactured by BASF Japan) and the like.

Further, the [C] polymerization initiator is preferably a polymerization initiator having no nitrogen atom in the molecule. With the [C] polymerization initiator having such a structure, the curable resin composition according to the first embodiment of the present invention can form a cured film according to the second embodiment of the present invention which has more excellent fluorescent characteristics.

Specific examples of such a polymerization initiator having no nitrogen atom in the molecule include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651), 1-hydroxycyclohexylphenyl ketone (Irgacure (registered trademark) 184), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Irgacure (registered trademark) 1173), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (Irgacure (registered trademark) 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] phenyl} -2-methyl-propane-1-one (Irgacure (registered trademark) 127), phenylglyoxylate Esters (Darocur (registered trademark) MBF), 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (LUCIRIN (registered trademark) TPO), bis (2,4,6-trimethyl Benzamidine) -phenylphosphine oxide (Irgacure (registered trademark) 819) and the like.

The content of the [C] polymerization initiator is preferably from 0.1 to 40 parts by mass, and more preferably from 0.5 to 20 parts by mass, relative to 100 parts by mass of the [A] component. By setting the content of the [C] polymerization initiator to the above-mentioned range, the curable resin composition according to the first embodiment of the present invention exhibits good patternability even at a low exposure amount, and furthermore, Forms a cured film with sufficient surface hardness and adhesion.

[[D] Polymerizable unsaturated compound]

The curable resin composition according to the first embodiment of the present invention may further contain a [D] polymerizable unsaturated compound. The [D] polymerizable unsaturated compound contained in the curable resin composition according to the first embodiment of the present invention is a compound having a polymerizable unsaturated structure. The curable resin composition according to the first embodiment of the present invention can improve the crosslinking reactivity by containing a [D] polymerizable unsaturated compound. Further, the cured film of the second embodiment of the present invention formed from the curable resin composition can improve the film strength and adhesion to the substrate. In this case, the [D] polymerizable unsaturated compound is preferably used together with the [C] polymerization initiator and contained in the curable resin composition according to the first embodiment of the present invention.

Such a [D] polymerizable unsaturated compound is preferably a monofunctional, difunctional, or trifunctional (meth) acrylate from the viewpoints of good self-polymerizability and improved strength of the resulting cured film.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, and diethylene glycol monoethyl ether methyl. Acrylate, (2-propenyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloxyethyl) (2-hydroxypropyl) phthalate , Ω-carboxy polycaprolactone monoacrylate and the like. Examples of commercially available products include ARONIX M-101, ARONIX M-111, ARONIX M-114, and ARONIX M-5300 (above manufactured by Toa Kosei); KAYARAD TC-110S and KAYARAD TC-120S (above manufactured by Nippon Kayaku Co., Ltd.) (Manufactured); Viscoat 158, Viscoat 2311 (above manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and dicarboxylic acid. Ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate , 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, and the like. Examples of commercially available products include ARONIX (registered trademark) M-210, ARONIX M-240, and ARONIX M-6200 (above manufactured by Toa Kosei); KAYARAD (registered trademark) HDDA, KAYARAD HX-220, KAYARAD R-604 ( The above are manufactured by Nippon Kayaku Co., Ltd.); Viscoat 260, Viscoat 312, Viscoat 335HP (above manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate (registered trademark) 1,9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetraacrylic acid. Ester, pentaerythritol tetramethacrylate, di-trimethylolpropane tetraacrylate, di-trimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexa Acrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tris (2-propenyloxyethyl) phosphate , Tris (2-methacryloxyethyl) phosphate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, and linear elongation Group and alicyclic structure, and has two or more isocyanates A polyfunctional acrylic urethane-based compound obtained by reacting a compound having a group with one or more hydroxyl groups in the molecule and having three, four, or five (meth) acryloxy groups. Examples of commercially available products include ARONIX (registered trademark) M-309, ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, and ARONIX TO-1450 ( The above are manufactured by Toa Kosei Corporation); KAYARAD (registered trademark) TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA-12 (above manufactured by Nippon Kayaku Co., Ltd.) ); Viscoat (registered trademark) 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above manufactured by Osaka Organic Chemical Industry Co., Ltd.); As a commercially available product containing a polyfunctional urethane-based compound New frontier (registered trademark) R-1150 (manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD (registered trademark) DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Among these [D] polymerizable unsaturated compounds, ω-carboxy polycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, and pentaerythritoltriene are preferable. Acrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, di-trimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or dipentaerythritol hexaacrylate Mixture with dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, polyfunctional acrylic amino acid Commercially available ester compounds Goods and so on.

The [D] polymerizable unsaturated compound may be used alone or as a mixture of two or more. The use ratio of the [D] polymerizable unsaturated compound in the curable resin composition according to the first embodiment of the present invention is preferably 30 to 250 parts by mass relative to 100 parts by mass of the [A] component. , More preferably 50 parts by mass to 200 parts by mass. When the use amount of the [D] polymerizable unsaturated compound is 30 parts by mass to 250 parts by mass, the sensitivity of the curable resin composition according to the first embodiment of the present invention and the heat resistance of the obtained cured film are further increased. good.

[[E] Antioxidant]

The curable resin composition according to the first embodiment of the present invention may further contain [E] an antioxidant. The curable resin composition according to the first embodiment of the present invention can further improve the properties of the present invention obtained by using [E] antioxidant in addition to essential components such as the [A] component and the [B] component, and the present invention. The transmittance and heat-resistant transparency of the cured film of the second embodiment.

Examples of the [E] antioxidant that is preferable as a component of the curable resin composition according to the first embodiment of the present invention include a phosphite-based antioxidant. The phosphite-based antioxidant includes a compound having a phosphite structure. In addition, the [E] antioxidant may include a phenol compound, a compound having a hindered phenol structure, a compound having a hindered amine structure, and a compound having a thioether structure.

Examples of the phosphite-based antioxidant include tris (2,4-di-third-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6- Methylphenyl] ethyl phosphite, bis (2,4-di-third-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl Phenyl) pentaerythritol diphosphite, bis (2,6-di-third-butyl-4-methylphenyl) pentaerythritol-diphosphite, tris (nonylphenyl) phosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, tris (o-tolyl) phosphine, tris (p-tolyl) phosphine, cyclohexyldiphenylphosphine, ethyldiphenylphosphine, and the like. Examples of commercially available products include Adekastab (registered trademark) PEP-36, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8F, Adekastab PEP-8W, Adekastab PEP-11C, Adekastab PEP-24G, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab (registered trademark) P, Adekastab (registered trademark) QL, Adekastab 522A, Adekastab 329K, Adekastab 1178, Adekastab 1500, Adekastab (registered trademark) C, Adekastab 135A, Adekastab 3010, Adekastab (registered trademark) TPP (above manufactured by ADEKA), Irgafos (registered trademark) 38, Irgafos (registered trademark) 168, Irgafos (registered trademark) P-EPQ (all of which are manufactured by BASF Japan) and the like.

Among these, a phosphite-based antioxidant having an aromatic group represented by the following formula is particularly preferred.

In the formula, R _A represents a single bond or an oxygen atom. R _B represents an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group. R _C represents a hydrocarbon group having 1 to 30 carbon atoms. n represents an integer from 1 to 3, and m represents an integer from 0 to 5.

Examples of R _B include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, third butyl, pentyl, isopentyl, and neopentyl. Base, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, and the like.

Examples of R _C include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, third butyl, pentyl, isopentyl, Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, 17 Alkyl, octadecyl, undecyl, eicosyl, eicosyl, twenty one, twenty one, twenty two alkyl, twenty three alkyl, twenty four alkyl, Carbon numbers such as pentacosyl, hexacosyl, icosyl, octacosyl, icosyl, icosyl, phenyl, tolyl, xylyl, naphthyl, etc. 1 to 30 linear or branched alkyl hydrocarbon group.

Examples of the phenol compound include 4-methoxyphenol and 4-ethoxyphenol.

Examples of the compound having a hindered phenol structure include 2,6-di-third-butyl-4-cresol and pentaerythritol tetrakis [3- (3,5-di-third-butyl-4-hydroxyphenyl) Propionate], thiodiethyl bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di -Third-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tri (3,5-di-third-butyl-4-hydroxybenzyl) ) Benzene, N, N'-hexane-1,6-diylbis [3- (3,5- Di-third butyl-4-hydroxyphenylpropanamine), 3,3 ', 3 ", 5,5', 5" -hexa-third butyl-a, a ', a "-(all Xylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl)- O-cresol, ethylidenebis (oxyethylene) bis [3- (5-thirdbutyl-4-hydroxy-m-tolyl) propionate, hexamethylenebis [3- (3,5 -Di-third-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [(4-tert-butyl-3-hydroxy-2,6-stubyl) methyl ] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-third-butyl-4- (4,6-bis (octylthio) ) -1,3,5-triazin-2-ylamine) phenol, tri- (3,5-di-third-butyl-4-hydroxybenzyl) -isotricyanate, and the like.

Examples of commercially available products of the compound having a hindered phenol structure include Adekastab (registered trademark) AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, and Adekastab. AO-80, Adekastab AO-330 (above manufactured by Aidico), sumilizer (registered trademark) GM, sumilizer GS, sumilizer MDP-S, sumilizer BBM-S, sumilizer WX-R, sumilizer GA-80 (above by (Made by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, IRGANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD (Registered trademark) 295 (above manufactured by BASF, Japan), Yoshinox (registered trademark) BHT, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Yoshinox SS, Yoshinox TT, Yoshinox 917, Yoshinox 314 (above manufactured by API Corporation) and the like.

Examples of commercially available compounds having a hindered amine structure include Adekastab (registered trademark) LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Adekastab LA-63P, Adekastab LA-68LD, and Adekastab LA- 77. Adekastab LA-82, Adekastab LA-87 (above manufactured by Adic), sumilizer (registered trademark) 9A (made by Sumitomo Chemical Co., Ltd.), CHIMASSORB (registered trademark) 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN (registered (Trademark) 622LD, TINUVIN 144, TINUVIN 765, TINUVIN 770DF (above manufactured by BASF Japan).

Commercially available products of the compound having a sulfide structure include, for example, Adekastab (registered trademark) AO-412S, Adekastab AO-503 (manufactured by Adiko), sumilizer (registered trademark) TPL-R, sumilizer TPM, and sumilizer TPS. , Sumilizer TP-D, sumilizer MB (above manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) PS800FD, IRGANOX PS802FD (above manufactured by BASF Japan), DLTP, DSTP, DMTP, DTTP (above manufactured by API company), etc. .

[E] The antioxidant may be used alone or in combination of two or more. The content of the [E] antioxidant in the curable resin composition according to the first embodiment of the present invention is preferably from 0.1 to 10 parts by mass relative to 100 parts by mass of the [A] component, and more preferably It is 0.2 to 5 parts by mass. By setting the content of the [E] antioxidant to the above range, the curable resin composition according to the first embodiment of the present invention can be used. The obtained cured film of the second embodiment of the present invention has further improved transmittance and heat-resistant transparency.

[Other optional ingredients]

The curable resin composition according to the first embodiment of the present invention contains the [A] component and [B] quantum dots as essential components, and may contain other optional components as long as the effects of the present invention are not impaired. Examples of other optional components include solvents, hardening accelerators, and thermal acid generators.

A hardening accelerator is a compound which functions to accelerate hardening of the film formed from the curable resin composition of this embodiment.

The thermal acid generator is a compound that can release an acidic active material that functions as a catalyst when the resin is cured by applying heat.

In addition, the curable resin composition of the present embodiment may contain other optional components such as a surfactant, a storage stabilizer, an adhesive, a heat resistance accelerator, and the like, as long as the effect of the present invention is not impaired. Each of these arbitrary components may be used alone or in combination of two or more.

[Preparation method of curable resin composition]

The curable resin composition according to the first embodiment of the present invention is prepared by uniformly mixing the [A] polymer and the [B] quantum dot. In addition, when it contains any [C] component, [D] component, or [E] component, the [C] component or [ D] component or [E] component is prepared by mixing uniformly.

Further, if necessary, the other optional components are selected, and when these components are contained, the other optional components can be added together with the [A] component and the [B] component and the like. It is prepared by mixing uniformly.

When the curable resin composition according to the first embodiment of the present invention is prepared, an organic solvent may be used in order to prepare a curable resin composition in a dispersion state.

Examples of the function of the organic solvent include adjusting the viscosity and the like of the curable resin composition according to the first embodiment of the present invention, for example, improving the coatability on a substrate and the like, and improving the workability and moldability.

Examples of the organic solvent that can be used in the curable resin composition of the present embodiment include organic solvents that dissolve or disperse other contained components and do not react with other contained components. Examples of such organic solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoethers. Alkyl ether propionates, hydrocarbons, ketones, esters, etc.

Examples of the organic solvents include benzyl alcohol and diacetone alcohol. Examples of the ether include tetrahydrofuran or diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, and diisopentyl ether. And dialkyl ethers such as di-n-hexyl ether; examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol Diethyl ether, diethylene glycol ethyl methyl ether, and the like; examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, and ethylene glycol monobutyl ether. Acetate, ethylene glycol monoethyl ether acetate, etc .; Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like; examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether Diethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and the like; examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol Monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like; examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, and 2-hydroxy-2-methyl Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 -Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-formyl Methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy Propyl acetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, butoxyacetate Ethyl ester, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methyl Butyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

From the viewpoint of dispersibility of quantum dots, a hydrocarbon solvent is preferred. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents. Examples of the aromatic hydrocarbon solvent include toluene, ethylbenzene, pentylbenzene, cumene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cumene, tetrahydronaphthalene, biphenyl, mesitylene Wait. Examples of the aliphatic hydrocarbon-based solvent include hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, Decalin, isooctane, isododecane, cyclohexene, cyclopentane, dipentene, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M (manufactured by Kokura Kosan Co., Ltd.), pine Fuel-saving, decalin, limonene, phenylyne, KYOWASOL C-800, ShellSol, ISOSOL, petroleum ether (manufactured by Godo Industrial Co., Ltd.), etc.

Among these organic solvents, from the viewpoints of excellent solubility, non-reactivity with each component, and ease of coating film formation, ethers such as dialkyl ethers and diethylene glycol alkyl ethers are preferred. , Ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, particularly diethylene glycol diethyl ether, diethylene glycol ethyl Methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate , Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate. These organic solvents can be used alone or in combination.

In addition to the organic solvent, benzyl ethyl may be further used in combination as necessary. Ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1 -Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve ester , Carbitol acetate and other high boiling point solvents.

The content of the organic solvent in the curable resin composition according to the first embodiment of the present invention can be appropriately determined in consideration of viscosity and the like. That is, the solid content concentration (components other than the solvent component in the curable resin composition solution) of the curable resin composition of the present embodiment can be arbitrarily set according to the purpose of use, a desired film thickness, and the like, It is preferably 5 mass% to 50 mass%, more preferably 10 mass% to 40 mass%, and still more preferably 15 mass% to 35 mass%.

The curable resin composition of the present embodiment prepared as described above is preferably used in the present embodiment after being filtered using a microporous filter or the like having a pore size of about 0.5 μm when the liquid is in a liquid state. Formation of hardened film.

Embodiment 2.

<Hardened film>

The cured film of the second embodiment of the present invention is formed by applying the curable resin composition of the first embodiment of the present invention to a substrate, patterning it if necessary, and then heating and curing it. Hereinafter, the cured film and its formation method according to the second embodiment of the present invention will be described.

In the method for forming a cured film according to the second embodiment of the present invention, in order to form a cured film on a substrate, it is preferable to include at least the following in the following order: The steps (1) to (4) are described.

(1) A coating film forming step of forming a coating film of the curable resin composition according to the first embodiment of the present invention on a substrate.

(2) A radiation irradiation step, which irradiates at least a part of the coating film formed in the step (1) with radiation.

(3) Development step, which develops the coating film irradiated with radiation in step (2).

(4) A hardening step, which exposes the coating film developed in step (3).

1 to 4 are diagrams illustrating an example of a method for forming a cured film according to a second embodiment of the present invention.

FIG. 1 is a cross-sectional view of a substrate illustrating an example of a coating film forming step in forming a cured film according to a second embodiment of the present invention.

2 is a cross-sectional view schematically illustrating an example of a radiation irradiation step in the formation of a cured film according to a second embodiment of the present invention.

3 is a cross-sectional view of a substrate illustrating an example of a development step in the formation of a cured film according to the second embodiment of the present invention.

4 is a cross-sectional view of a cured film and a substrate illustrating an example of a curing step in the formation of a cured film according to a second embodiment of the present invention.

The steps (1) (coating film forming step) to step (4) (hardening step) will be described below.

[step 1)]

Step (1) in the method for forming a cured film according to the second embodiment of the present invention, That is, in the coating film forming step, as illustrated in FIG. 1, the coating film 1 of the curable resin composition according to the first embodiment of the present invention is formed on the substrate 2.

The substrate 2 forming the coating film 1 can be made of glass, quartz, silicon, or a resin (e.g., polyimide, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate). Esters, polyethers, polycarbonates, polyesters, ring-opening polymers of cyclic olefins and their hydrides, etc.). In addition, pretreatments such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation may be performed on these substrates in advance as necessary.

After the curable resin composition according to the first embodiment of the present invention is applied to one surface of the substrate 2, pre-baking is performed, and components such as an organic solvent contained in the curable resin composition are evaporated and applied. Formation of the film 1.

As a method for applying the curable resin composition according to the first embodiment of the present invention in this step, for example, a spray method, a roll coating method, or a spin coating method (also sometimes referred to as a spin coating method or a spinner method) can be used. ), A slit coating method (slot die coating method), a bar coating method, or an inkjet coating method. Among these, a spin coating method or a slit coating method is preferable from the viewpoint that a film having a uniform thickness can be formed.

The conditions for the pre-baking vary depending on the type and blending ratio of each component constituting the curable resin composition, and it is preferably performed at a temperature of 70 ° C to 120 ° C, and the time depends on a heating device such as a hot plate or an oven. The difference is about 1 minute to 15 minutes.

[Step (2)]

Next, the steps in the method for forming a cured film according to the second embodiment of the present invention (2) That is, in the radiation irradiation step, as illustrated in FIG. 2, at least a part of the coating film 1 formed on the substrate 2 in step (1) is irradiated with radiation 4. At this time, in order to irradiate only a part of the coating film 1 with the radiation 4a, it is performed through, for example, a photomask 3 having a pattern corresponding to the formation of a desired shape. By using this mask 3, a part of the irradiated radiation 4 is transmitted through the mask, and the radiation 4 a at this portion is irradiated on the coating film 1.

Examples of the radiation 4 used in the irradiation include visible rays, ultraviolet rays, and extreme ultraviolet rays. Among them, radiation having a wavelength in a range of 200 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The irradiation amount (exposure amount) of the radiation 4 can be set to a value that measures the intensity of the wavelength of the radiation 4 at a wavelength of 365 nm with an illuminance meter (OAI model 356, manufactured by Optical Associates Inc.), and can be set to 10 J / m. ² ~ 10000J / m ^2, preferably is ^{100J / m 2 ~ 5000J / m} 2, more preferably is ^{200J / m 2 ~ 3000J / m} 2.

[Step (3)]

Next, in step (3) of the method for forming a cured film according to the second embodiment of the present invention, that is, the development step, as illustrated in FIG. 3, the coating film 1 of FIG. 2 after radiation irradiation is developed to The unnecessary portion is removed, and a coating film 1a patterned into a predetermined shape is obtained.

The developing solution used in the development can be, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, or the like. Quaternary ammonium salt, or choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, etc. Basic compounds Aqueous solution. The aqueous solution of the basic compound may be used by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol. Furthermore, it is also possible to add only an appropriate amount of a surfactant or to add an appropriate amount together with the addition of the water-soluble organic solvent.

The development method may be any of a liquid coating method, a dipping method, a shower method, and a spray method. The development time may be set at 5 to 300 seconds at room temperature, and preferably 10 to 180 seconds at room temperature. about. After the development process, for example, running water cleaning for 30 seconds to 90 seconds, and then air drying with compressed air or compressed nitrogen to obtain a desired pattern.

[Step (4)]

Next, in step (4) of the method for forming a cured film according to the second embodiment of the present invention, that is, the curing step, the patterned coating film 1a illustrated in FIG. 3 is cured by exposure using an exposure device. (Also known as post-exposure). Thereby, as illustrated in FIG. 4, a cured film 5 formed on the substrate 2 as an example of the second embodiment of the present invention is obtained. The cured film 5 is patterned so that it may become a desired shape as mentioned above.

In the formation of the cured film 5 as an example of the second embodiment of the present invention, the curable resin composition of the first embodiment of the present invention is used, and in this step, a part of the coating film is irradiated with radiation. Specifically, a predetermined radiation is irradiated to the coating film formed in step (1) and patterned in steps (2) and (3). Examples of the radiation used in this case include ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser light. Examples of the X-ray include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiation rays, it is preferable to use ultraviolet rays, and more preferable is ultraviolet rays to include at least one of g rays, h rays, and i rays. The radiation exposure is preferably from 0.1 J / m ² to 30000 J / m ² .

The cured film of the second embodiment of the present invention, which is formed by the method for forming a cured film including the above steps (1) to (4), is constituted by including [B] quantum dots in a resin, and has a basis based on [B] Quantum dot fluorescent emission (wavelength conversion) function. Therefore, it can be used as a wavelength conversion film of the third embodiment of the present invention that emits fluorescent light having a wavelength different from that of the excitation light.

The light-emitting element of the fourth embodiment of the present invention can also be provided by using the cured film of the second embodiment of the present invention as a light-emitting layer. In this case, the light-emitting layer included in the light-emitting element according to the fourth embodiment of the present invention can use the curable resin composition of the first embodiment of the present invention to form a hardened resin according to the second embodiment of the present invention as described above. The film is formed in the same manner. The light-emitting layer of the light-emitting element according to the fourth embodiment of the present invention has a function of fluorescent light emission (wavelength conversion) based on [B] quantum dots.

In particular, the cured film of the second embodiment of the present invention is suitably used as a light-emitting layer of a light-emitting display element as an example of a light-emitting element as described later, and can be used in the structure of a light-emitting display element.

Therefore, in order to improve the light utilization efficiency, the cured film of the second embodiment of the present invention has a total light transmittance of 0.1 mm in the resin constituting the cured film. (JIS K7105) is preferably 75% to 95%, more preferably 78% to 95%, and even more preferably 80% to 95%. When the total light transmittance is within this range, the obtained cured film can constitute a wavelength conversion film or a light emitting layer of a light emitting element having excellent light utilization efficiency.

Embodiment 3.

<Wavelength conversion film>

As described above, the cured film according to the second embodiment of the present invention is constituted by containing [B] quantum dots in a resin based on the [A] polymer of the curable resin composition according to the first embodiment of the present invention. The cured film according to the second embodiment of the present invention has a fluorescent light emission (wavelength conversion) function based on the contained [B] quantum dot. Therefore, the cured film of the second embodiment of the present invention can be used as a wavelength conversion film of the third embodiment of the present invention that emits fluorescent light having a wavelength different from that of the excitation light.

Therefore, the wavelength conversion film according to the third embodiment of the present invention can be formed using the curable resin composition according to the first embodiment of the present invention in accordance with the method for forming a cured film according to the second embodiment of the present invention. In addition, the wavelength conversion film according to the third embodiment of the present invention has a fluorescent light emission (wavelength conversion) function based on [B] quantum dots.

The wavelength conversion film according to the third embodiment of the present invention can be used with, for example, a color liquid crystal display panel to provide a color liquid crystal display element. In this case, for example, by disposing the wavelength conversion film of the third embodiment of the present invention on a known color liquid crystal display panel or the like, a color liquid crystal display element capable of performing color display with high color purity can be provided. That is, the wavelength conversion film according to the third embodiment of the present invention can be used to improve the color purity of the display originally possessed by a color liquid crystal display panel, and can provide a display A color liquid crystal display element having further improved color purity.

Embodiment 4.

<Formation of light emitting element and light emitting layer>

In the present invention, by using the cured film according to the second embodiment of the present invention as a wavelength conversion film or a light-emitting layer, a light-emitting element such as a lighting device or a light-emitting display element can be provided.

That is, the light-emitting element according to the fourth embodiment of the present invention is a light-emitting element that uses a cured film according to the second embodiment of the present invention as a wavelength conversion film or a light-emitting layer, and can constitute, for example, a light-emitting display element. Further, as a light-emitting display element as an example of the fourth embodiment of the present invention, for example, a wavelength conversion substrate including a cured film of the second embodiment of the present invention as a light-emitting layer can be used. In the light-emitting element according to the fourth embodiment of the present invention, the light-emitting layer can be formed in accordance with the method for forming the light-emitting layer according to the fifth embodiment of the present invention.

5 is a cross-sectional view schematically showing an example of a light-emitting display element as a light-emitting element according to a fourth embodiment of the present invention.

A light-emitting display element 100 as an example of the fourth embodiment of the present invention includes a wavelength conversion substrate 11 including a light-emitting layer 13 (13a, 13b, 13c) and a black matrix 14 on a substrate 12, and an adhesive layer 15 via The light source substrate 18 is bonded to the wavelength conversion substrate 11.

The substrate 12 includes glass, quartz, or a transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, and the like).

The light emitting layer 13 of the wavelength conversion substrate 11 is a cured film using the second embodiment of the present invention. That is, the light emitting layer 13 is formed by patterning using the curable resin composition according to the first embodiment of the present invention.

Regarding the method for forming the light-emitting layer according to the fifth embodiment of the present invention, the light-emitting layer uses the cured film according to the second embodiment of the present invention, and thus is different from the method for forming the cured film according to the second embodiment of the present invention. Got the same. That is, the cured film of the second embodiment of the present invention is formed on the substrate 12, and these become the light-emitting layer 13 and constitute the wavelength conversion substrate 11 of the light-emitting display element 100. Therefore, the method for forming the light emitting layer 13 preferably includes the following steps (1) to (4) in the same order as described above.

(1) A coating film forming step of forming a coating film of the curable resin composition according to the first embodiment of the present invention on a substrate.

(2) A radiation irradiation step, which irradiates at least a part of the coating film formed in the step (1) with radiation.

(3) Development step, which develops the coating film irradiated with radiation in step (2).

(4) A hardening step, which exposes the coating film developed in step (3).

The formation of the cured film in steps (1) to (4) of the light-emitting layer 13 according to the second embodiment of the present invention has been described using FIGS. 1 to 4. Therefore, the detailed description is omitted, but the cured film 5 patterned so as to have a desired shape shown in FIG. 4 becomes the light emitting layer 13 of the wavelength conversion substrate 11 of FIG. 5.

The wavelength conversion substrate 11 uses the quantum dots contained in each of the light emitting layers 13 to perform wavelength conversion on the excitation light from the excitation light source 17 of the light source substrate 18 to emit fluorescent light of a desired wavelength.

Further, in the wavelength conversion substrate 11, the light-emitting layer 13 a, the light-emitting layer 13 b, and the light-emitting layer 13 c of the light-emitting layer 13 are each composed of different quantum dots, and can emit different fluorescent light.

For example, the wavelength conversion substrate 11 may be configured as follows: the light emitting layer 13a converts excitation light into red light, the light emitting layer 13b converts excitation light into green light, and the light emitting layer 13c converts excitation light into blue light.

In this case, the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c are selected so that the quantum dots contained therein have a desired fluorescent characteristic. Therefore, for the formation of the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c of the wavelength conversion substrate 11, for example, three types of curable resin compositions according to the first embodiment including quantum dots having different light-emitting characteristics are prepared.

Then, using the three types of curable resin compositions according to the first embodiment, the method for forming the light-emitting layer 13 including steps (1) to (4) is repeatedly performed to sequentially form the light-emitting layer 13a and the light-emitting layer 13b. And light-emitting layer 13c. Then, a light emitting layer 13 is formed on the substrate 12 to obtain a wavelength conversion substrate 11.

The thickness of the light emitting layer 13 of the wavelength conversion substrate 11 is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. If the thickness is less than 100 nm, there is a problem that the excitation light cannot be sufficiently absorbed and the light conversion efficiency is lowered, so that the brightness of the light-emitting display element cannot be sufficiently ensured. To further increase the absorption of excitation light It is sufficient to ensure the brightness of the light-emitting display element, and the film thickness is preferably set to 1 μm or more.

A black matrix 14 is arranged between the light emitting layers 13 on the substrate 12. The black matrix 14 can be formed by patterning according to a known method using a known light-shielding material. In addition, the black matrix 14 is not an essential constituent element in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may have a configuration in which the black matrix 14 is not provided.

The adhesive layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light having a wavelength described later. In addition, the adhesive layer 15 does not need to be provided on the substrate 12 so as to cover the entire surface of the light-emitting layer 13 a, the light-emitting layer 13 b, and the light-emitting layer 13 c as shown in FIG. 5, and may be provided only around the wavelength conversion substrate 11. .

The light source substrate 18 includes a substrate 16 and a light source 17 disposed on the wavelength conversion substrate 11 side of the substrate 16. Ultraviolet light or blue light is emitted from the light source 17 as excitation light.

The light source 17 may be a UV light-emitting organic EL element, a blue light-emitting organic EL element, or the like with a known structure, and is not particularly limited. Here, the ultraviolet light is preferably light emission having a main emission peak of 360 nm to 435 nm, and the blue light is preferably light emission having a main emission peak of 435 nm to 480 nm. The light source 17 preferably has directivity such that each emitted light is irradiated to the opposite light-emitting layer 13.

As a light-emitting display element 100 as an example of the fourth embodiment of the present invention, the excitation light from the light source 17a as one of the light sources 17 is wavelength-converted by the quantum dots of the light-emitting layer 13a of the opposite wavelength conversion substrate 11. Similarly, the quantum dot pair of the light emitting layer 13b of the opposite wavelength conversion substrate 11 comes from light. The excitation light from the source 17b is wavelength-converted; further, the excitation light from the light source 17c is wavelength-converted by the quantum dots of the light-emitting layer 13c of the opposite wavelength-conversion substrate 11. As described above, the excitation light from the light source 17 is converted into visible light of a desired wavelength and used for display.

The wavelength conversion substrate 11 converts excitation light into blue light in the light emitting layer 13 c as described later. In this case, the wavelength conversion substrate 11 may be used instead of the light-emitting layer 13c in a light-scattering layer formed by dispersing light-scattering particles in a resin. As described above, when the excitation light is blue light, the excitation light can be used without its wavelength conversion.

The wavelength conversion substrate 11 of the light-emitting display element 100 is formed by patterning the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c including the quantum dots and the resin on the substrate 12 as described above. The light emitting layer 13a, the light emitting layer 13b, and the light emitting layer 13c are each formed of a curable resin composition according to the first embodiment of the present invention including quantum dots.

In the light-emitting display element 100, a portion provided with the light-emitting layer 13a constitutes a sub-pixel that performs red display. That is, the light emitting layer 13 a of the wavelength conversion substrate 11 converts the excitation light from the light source 17 a opposite to the light source substrate 18 into red. The portion provided with the light-emitting layer 13b constitutes a sub-pixel that performs green display. That is, the light emitting layer 13 b converts the excitation light from the light source 17 b facing the light source substrate 18 to green. The portion provided with the light-emitting layer 13c constitutes a sub-pixel that performs blue display. That is, the light emitting layer 13 c converts the excitation light from the light source 17 c facing the light source substrate 18 into blue.

The light-emitting display element 100 is composed of three types of sub-pixels including the light-emitting layer 13a, sub-pixels including the light-emitting layer 13b, and sub-pixels including the light-emitting layer 13c, and constitutes one pixel that is the smallest unit constituting an image.

As an example of the light emitting display element 100 according to the fourth embodiment of the present invention having the above configuration, in each of the sub-pixels including the light-emitting layer 13a, the sub-pixels including the light-emitting layer 13b, and the sub-pixels including the light-emitting layer 13c Controls the glow of red, green, or blue light. In addition, in each pixel including three seed pixels, the light emission of red, green, and blue light is controlled to perform full-color display.

In the light emitting display element 100 as an example of the fourth embodiment of the present invention, a color filter may be provided between the light emitting layer 13 and the substrate 12. That is, a red color filter may be provided between the light emitting layer 13 a and the substrate 12, a green color filter may be provided between the light emitting layer 13 b and the substrate 12, and a blue color may be provided between the light emitting layer 13 c and the substrate 12. Color filters.

The light-emitting display element 100 as an example of the fourth embodiment of the present invention can improve the purity of display colors by providing a color filter. Here, a color filter can be formed by a well-known method, and can be used as a color filter which is well-known as a liquid crystal display element.

[Example]

Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples.

<[A] polymer ([A] component)>

In this embodiment, as an example of the [A] polymer, a polymer may be used (A-1), polymer (A-2), polymer (A-3), polymer (A-4), and polymer (A-5). Synthesis examples of polymer (A-1) to polymer (A-5) are shown below.

Synthesis Example 1

[Synthesis of Polymer (A-1)]

A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and replaced with nitrogen. Heat to 80 ° C, and dropwise add 50 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of 2-methacryloxyethyl succinic acid, and 10 parts by mass of benzyl methacrylate at the same temperature over 2 hours. , 60 parts by mass of a mixed solution of 2-ethylhexyl methacrylate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), and the polymerization was carried out for 1 hour while maintaining the temperature. . Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour, thereby obtaining a polymer (A-1). The polymer (A-1) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11000, Mn = 6100, and Mw / Mn = 1.80. Let this be a polymer (A-1) solution.

Synthesis Example 2

[Synthesis of Polymer (A-2)]

A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and replaced with nitrogen. Heat to 80 ° C, and dropwise add 50 parts by mass of propylene glycol monomethyl ether acetate, 35 parts by mass of 2-methacryloxyethyl succinic acid, and 65 parts by mass of methacrylic acid-2 at the same temperature dropwise over 2 hours. A mixed solution of -ethylhexyl ester and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was polymerized for 1 hour while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and the temperature was further increased for 1 hour. Polymerization was performed to obtain a polymer (A-2). The polymer (A-2) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11300, Mn = 6000, and Mw / Mn = 1.88. Let this be a polymer (A-2) solution.

Synthesis Example 3

[Synthesis of Polymer (A-3)]

A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and replaced with nitrogen. Heat to 80 ° C, and dropwise add 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of vinyl benzoic acid, 10 parts by mass of styrene, 10 parts by weight of benzyl methacrylate, and 40 parts by mass at the same temperature over 2 hours. A mixed solution of parts of lauryl methacrylate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was polymerized for 1 hour while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour, thereby obtaining a polymer (A-3). The polymer (A-3) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11100, Mn = 6000, and Mw / Mn = 1.85. Let this be a polymer (A-3) solution.

Synthesis Example 4

[Synthesis of Polymer (A-4)]

A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and replaced with nitrogen. Heat to 80 ° C, and dropwise add 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of 2-methacryloxyethylhexahydrophthalic acid, and 60 parts by mass of methyl at the same temperature over 2 hours. A mixed solution of stearyl acrylate and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), and maintained at this temperature for 1 hour. Time of aggregation. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour, thereby obtaining a polymer (A-4). The polymer (A-4) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), Mw = 12100, Mn = 6500, and Mw / Mn = 1.86. Let this be a polymer (A-4) solution.

Synthesis Example 5

[Synthesis of Polymer (A-5)]

A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and replaced with nitrogen. Heat to 80 ° C, and dropwise add 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of 2-methacryloxyethyl succinic acid, and 30 parts by weight of methacrylic acid-2 at the same temperature dropwise over 2 hours. -A mixed solution of ethylhexyl ester, 30 parts by mass of isobornyl methacrylate, and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), and the temperature was maintained for 1 hour. polymerization. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and polymerization was further performed for 1 hour, thereby obtaining a polymer (A-5). The polymer (A-5) was obtained in the state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11100, Mn = 6100, and Mw / Mn = 1.82. Let this be a polymer (A-5) solution.

<[B] quantum dot ([B] component)>

The quantum dots used in this embodiment are shown below.

Quantum dot A: InP / ZnS core-shell quantum dot

Quantum dot B: InCuS ₂ / ZnS core-shell quantum dot

Quantum dot C: Si quantum dot

Moreover, the quantum dots A: InP / ZnS core-shell quantum dots, quantum dots B: InCuS ₂ / ZnS core-shell quantum dots, and quantum dots C: Si quantum dots used in the following examples can be generally known. Method of synthesis.

For example, the quantum dot A: InP / ZnS core-shell quantum dot can be synthesized by referring to a method described in a technical document "Journal of American Chemical Society. 2007, 129, 15432-15433". For quantum dot B: InCuS ₂ / ZnS core-shell quantum dots, refer to the technical literature "Journal of American Chemical Society. 2009, 131, 5691-5697" and the technical literature "Materials Chemistry ( Chemistry of Materials.) 2009, 21, 2422-2429 ", and the quantum dots C: Si quantum dots can be referred to the technical document" Journal of American Chemical Society. 2010 " , 132, 248-253 ".

Using the above [A] polymer ([A] component) and [B] quantum dots, further use [C] polymerization initiator ([C] component), [D] polymerizable unsaturated compound ([D] component ) And the curable resin composition of the example was prepared. Next, the cured films of Examples were formed using these, and the cured films were evaluated.

Example 1

[Preparation of curable resin composition (β-I)]

After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-1) solution to dissolve them, 10 parts by mass of the quantum dot A was mixed to prepare a uniform solution, and 10 parts by mass of 1,2- Octanedione-1- [4- (phenylthio) -2- (O-benzidine oxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF Japan), 70 parts by mass of 1,9-nonane Alcohol diacrylate to prepare a curable resin composition (β-I).

Example 2

[Preparation of curable resin composition (β-II)]

After adding 40 parts by mass of ethylcyclohexane to 90 parts by mass of the polymer (A-2) solution to dissolve them, 10 parts by mass of the quantum dots B were mixed to prepare a uniform solution, and 10 parts by mass of 1,2- Octanedione-1- [4- (phenylthio) -2- (O-benzidine oxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF Japan), 60 parts by mass of 1,10-decanedi Alcohol diacrylate to prepare a curable resin composition (β-II).

Example 3

[Preparation of curable resin composition (β-III)]

After adding 40 parts by mass of paramente to 90 parts by mass of the polymer (A-3) solution to dissolve them, 10 parts by mass of the quantum dots C were mixed to prepare a uniform solution, and 10 parts by mass of 2-dimethylamine was mixed. 2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one (Irgacure (registered trademark) 379 manufactured by BASF Japan), 30 Part by mass of di-trimethylolpropane tetraacrylate to prepare a curable resin composition (β-III).

Example 4

[Preparation of curable resin composition (β-IV)]

After adding 40 parts by mass of pinane to 90 parts by mass of the polymer (A-4) solution to dissolve them, 10 parts by mass of the quantum dot A was mixed to make a uniform solution, and 10 parts by mass of the bis (2,4,6) was mixed. -Trimethylbenzyl) -phenylphosphine oxide (Irgacure (registered trademark) 819 manufactured by BASF Japan), 5 parts by mass of tris (2,4-di-third-butylphenyl) A phosphite and 30 parts by mass of di-trimethylolpropane tetraacrylate were used to prepare a curable resin composition (β-IV).

Example 5

[Preparation of curable resin composition (β-V)]

After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-5) solution to dissolve them, 10 parts by mass of the quantum dot A was mixed to prepare a uniform solution, and 25 parts by mass of 2,2- Dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651 manufactured by BASF, Japan), 2 parts by mass of tri (nonylphenyl) phosphite, 30 parts by mass of -Trimethylolpropane tetraacrylate to prepare a curable resin composition (β-V).

Example 6

[Preparation of curable resin composition (β-VI)]

After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-5) solution to dissolve them, 10 parts by mass of the quantum dot A was mixed to prepare a uniform solution, and 25 parts by mass of the 1-hydroxy ring was mixed. Hexyl phenyl ketone (Irgacure (registered trademark) 184 manufactured by BASF, Japan), 30 parts by mass of di-trimethylolpropane tetraacrylate, 2 parts by mass of pentaerythritol tetrakis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propionate] to prepare a curable resin composition (β-VI).

Example 7

[Formation of a cured film using a curable resin composition (β-I)]

After applying the curable resin composition (β-I) prepared in Example 1 on an alkali-free glass substrate by a spinner, pre-baking was performed on a hot plate at 80 ° C. for 2 minutes. A coating film is formed.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp with an exposure amount of 700 J / m ² . Next, development was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was observed with an optical microscope, and when there was no development residue and the linear portion of the pattern was formed into a linear shape, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-I) was good.

Example 8

[Formation of a cured film using a curable resin composition (β-II)]

After the curable resin composition (β-II) prepared in Example 2 was coated on a non-alkali glass substrate by a spinner, pre-baking was performed on a hot plate at 80 ° C. for 2 minutes to form a coating film.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp at an exposure amount of 1000 J / m ^2, and was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds. Development.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was subjected to an optical microscope. When no development residue was observed and the linear portion of the pattern was formed into a straight line, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-II) was good.

Example 9

[Formation of a cured film using a curable resin composition (β-III)]

After the curable resin composition (β-III) prepared in Example 3 was applied on a non-alkali glass substrate by a spinner, pre-baking was performed on a hot plate at 80 ° C. for 2 minutes to form a coating film.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp at an exposure amount of 800 J / m ^2, and was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds. Development.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was observed with an optical microscope, and when there was no development residue and the linear portion of the pattern was formed into a linear shape, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-III) was good.

Example 10

[Formation of a cured film using a curable resin composition (β-IV)]

The hardening prepared in Example 4 was applied on an alkali-free glass substrate by a spinner. After the resin composition (β-IV), it was pre-baked on a hot plate at 80 ° C. for 2 minutes to form a coating film.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp at an exposure amount of 800 J / m ^2, and was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds. Development.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was observed with an optical microscope, and when there was no development residue and the linear portion of the pattern was formed into a linear shape, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-IV) was good.

Example 11

[Formation of a cured film using a curable resin composition (β-V)]

After the curable resin composition (β-V) prepared in Example 5 was applied on a non-alkali glass substrate by a spinner, pre-baking was performed on a hot plate at 80 ° C. for 2 minutes to form a coating film.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp at an exposure amount of 800 J / m ^2, and was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds. Development.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was observed with an optical microscope, and when there was no development residue and the linear portion of the pattern was formed into a linear shape, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-V) was good.

Example 12

[Formation of a cured film using a curable resin composition (β-VI)]

After the curable resin composition (β-VI) prepared in Example 6 was applied on a non-alkali glass substrate by a spinner, pre-baking was performed on a hot plate at 80 ° C. for 2 minutes to form a coating film.

Next, the obtained coating film was irradiated with radiation through a photomask having a predetermined pattern using a high-pressure mercury lamp at an exposure amount of 800 J / m ^2, and was performed in a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. for 60 seconds. Development.

Next, the obtained pattern was irradiated with a high-pressure mercury lamp at an exposure amount of 10,000 J / m ² to form a cured film patterned into a predetermined shape.

Next, the end portion of the patterned cured film was observed with an optical microscope, and when there was no development residue and the linear portion of the pattern was formed into a linear shape, it was determined that the patternability was good.

As a result, the patternability of the cured film formed by patterning using the curable resin composition (β-VI) was good.

Example 13

[Evaluation of hardening shrinkage]

The cured film obtained by the forming method of Example 7 was further exposed to 10,000 J / m ² and measured with a stylus-type film thickness measuring machine (Alpha-Step IQ, KLA-TENCOR). The film thickness before and after this exposure. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Similarly, the cured film obtained by the forming method of Example 8 was further subjected to an exposure treatment of 10,000 J / m ² , and the exposure was measured by a stylus-type film thickness measuring machine (Alpha-Step IQ, Cree). Film thickness before and after. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Similarly, the cured film obtained by the forming method of Example 9 was further subjected to an exposure treatment of 10,000 J / m ² , and the exposure was measured by a stylus-type film thickness measuring machine (Alpha-Step IQ, Cree). Film thickness before and after. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Similarly, the cured film obtained by the forming method of Example 10 was further subjected to an exposure treatment of 10,000 J / m ² , and the exposure was measured by a stylus-type film thickness measuring machine (Alpha-Step IQ, Cree Corporation). Film thickness before and after. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Similarly, the cured film obtained by the forming method of Example 11 was further subjected to an exposure treatment of 10,000 J / m ² , and the exposure was measured by a stylus-type film thickness measuring machine (Alpha-Step IQ, Cree). Film thickness before and after. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Similarly, the cured film obtained by the forming method of Example 12 was further subjected to an exposure treatment of 10,000 J / m ² , and the exposure was measured by a stylus-type film thickness measuring machine (Alpha-Step IQ, Cree Corporation). Film thickness before and after. Next, the residual film rate (film thickness after treatment / film thickness before treatment × 100) was calculated, and this residual film rate was used as the curing shrinkage. The residual film rate was 99%, and it was judged that the curing shrinkage was good.

Example 14

[Evaluation of light resistance]

Regarding the cured film obtained by the forming method of Example 7, a UV irradiation device (UVX-02516S1JS01, USHIO) was used to further irradiate 800,000 J / m ² of ultraviolet light at an illumination of 130 mW, and investigate the reduction of the film after the irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Similarly, regarding the cured film obtained by the forming method of Example 8, a UV irradiation device (UVX-02516S1JS01, Oxtail Co., Ltd.) was further used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and investigate the film reduction after irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Similarly, regarding the cured film obtained by the forming method of Example 9, a UV irradiation device (UVX-02516S1JS01, Oxtail Co., Ltd.) was further used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and investigate the film reduction after irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Similarly, regarding the cured film obtained by the forming method of Example 10, a UV irradiation device (UVX-02516S1JS01, Oxtail Co., Ltd.) was further used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and investigate the reduction in film after irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Similarly, regarding the cured film obtained by the forming method of Example 11, a UV irradiation device (UVX-02516S1JS01, Oxtail Co., Ltd.) was further used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and investigate the film reduction after irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Similarly, regarding the cured film obtained by the forming method of Example 12, a UV irradiation device (UVX-02516S1JS01, Oxtail Co., Ltd.) was further used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and investigate the reduction in film after irradiation. the amount. The film reduction was 2% or less, and it was judged that the light resistance was good.

Example 15

[Evaluation of fluorescence characteristics]

Regarding the cured film obtained by the forming method of Example 7, the absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics) was used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 38%, and it was judged that the fluorescence characteristics were good.

Similarly, regarding the cured film obtained by the forming method of Example 8, an absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics Corporation) was further used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 34%, and it was judged that the fluorescence characteristics were good.

Similarly, regarding the cured film obtained by the forming method of Example 9, an absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics Corporation) was used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 30%, and it was judged that the fluorescence characteristics were good.

Similarly, regarding the cured film obtained by the forming method of Example 10, an absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics Corporation) was used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 43%, and it was judged that the fluorescence characteristics were good.

Similarly, regarding the cured film obtained by the forming method of Example 11, an absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics Corporation) was further used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 47%, and it was judged that the fluorescence characteristics were good.

Similarly, regarding the cured film obtained by the forming method of Example 12, an absolute PL quantum yield measurement device (C11347-01, Hamamatsu Photonics Corporation) was further used to investigate the fluorescence quantum yield at 25 ° C. The fluorescence quantum yield was 45%, and it was judged that the fluorescence characteristics were good.

[Industrial availability]

The cured film formed by using the curable resin composition of the present invention has excellent reliability such as light resistance and easy patterning. It can be used as a wavelength conversion layer or a wavelength conversion film in a display element or an electronic device using the same. It can also be used in the fields of LEDs and solar cells.

Claims (13)

A curable resin composition comprising: [A] a polymer having a structural site represented by the following formula (1), [B] a quantum dot, and [D] a polymerizable unsaturated compound, (In the formula (1), X ¹ represents an organic group having 2 to 30 carbon atoms; X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms; X ² represents a hydrogen atom 1, monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms, or divalent linear, branched or cyclic saturated or unsaturated hydrocarbon groups having 1 to 12 carbon atoms A group in which one or more hydrogen atoms are substituted by a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, or an alkyl group, an aralkyl group, or an alkoxy group which may have a substituent; * represents a bonding position), where The structural site represented by the formula (1) is a polymer of the structural site represented by the following formula (2): (In formula (2), Y ¹ represents a hydrogen atom or a methyl group; Y ² represents a divalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 12 One or more hydrogen atoms of a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group via a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, an alkyl group, an aralkyl group which may have a substituent, or An alkoxy-substituted group; Y ³ represents a divalent organic group; Y ⁴ represents a hydrogen atom; n represents 0 or 1), and the content of the [B] quantum dot relative to 100 parts by mass of the [A] The ingredients are 0.1 to 100 parts by mass. According to the curable resin composition according to item 1 of the scope of patent application, the monomer of the structural site represented by the formula (2) is 2-methacryloxyethyl succinic acid, ω -carboxy-poly Caprolactone monoacrylate, 2-methacryloxyethyl hexahydrophthalic acid. The hardenable resin composition according to item 1 or item 2 of the patent application scope, wherein the [B] quantum dot contains a component selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, and a group 14 element. A compound of at least two elements of the group consisting of, 15 group elements, and 16 group elements. The curable resin composition according to claim 1 or claim 2, wherein the [B] quantum dot includes a compound containing In as a constituent. The hardenable resin composition according to item 1 or item 2 of the scope of the patent application, wherein the [B] quantum dot is selected from the group consisting of an InP / ZnS compound, a CuInS ₂ / ZnS compound, an AgInS ₂ compound, and (ZnS / AgInS ₂ ) At least one of the group consisting of a solid solution / ZnS compound, a Zn-doped AgInS ₂ compound, and a Si compound. The curable resin composition according to item 1 or 2 of the scope of patent application, further comprising a [C] polymerization initiator. The hardenable resin composition according to item 6 of the scope of patent application, wherein the [C] polymerization initiator is a polymerization initiator having no nitrogen atom in the molecule. The curable resin composition according to claim 1 or claim 2, further comprising [E] an antioxidant. The curable resin composition according to item 8 of the scope of patent application, wherein the [E] antioxidant is a phosphite-based antioxidant. A cured film formed by using the curable resin composition according to any one of claims 1 to 9 of the scope of patent application. A wavelength conversion film formed by using the curable resin composition according to any one of claims 1 to 9 of the scope of patent application. A light-emitting element comprising a light-emitting layer formed using the curable resin composition according to any one of claims 1 to 9 of the scope of patent application. A method for forming a light-emitting layer, which is a method for forming a light-emitting layer of a light-emitting element, which is characterized by including the following steps: (1) forming a substrate as described in any one of items 1 to 9 of the scope of patent application on a substrate; A step of coating the curable resin composition; (2) a step of irradiating at least a part of the coating film formed in step (1) with radiation; (3) developing a coating film irradiated with radiation in step (2) And (4) a step of exposing the developed coating film in step (3).