KR102325621B1 - Curable resin composition, cured film, wavelength conversion film, method for forming light emitting layer, and light emitting display device - Google Patents

Abstract

(Project) To provide a curable resin composition that can easily form a highly reliable cured film containing semiconductor quantum dots and excellent in fluorescence properties, to provide a cured film, and to provide a light emitting element, a wavelength conversion film, and a method of forming a light emitting layer .
(Solutions) [A] A curable resin composition containing a compound having a molecular weight of 150 or more and 10000 or less in one molecule, [B] a semiconductor quantum dot, and [C] a hydrocarbon solvent is formed. A cured film is formed on the substrate 12 using this curable resin composition. This cured film turns into a wavelength conversion film, and uses this as the light emitting layer 13 to form the wavelength conversion board|substrate 11. As shown in FIG. In combination with the light source substrate 18 provided with the light source 17 , the light emitting display element 100 is constituted.

Description

A curable resin composition, a cured film, a wavelength conversion film, the formation method of a light emitting layer, and a light emitting display element TECHNICAL FIELD

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

The minute grains (dots) formed to confine electrons are called quantum dots, and are attracting attention in recent years. The size of one quantum dot is from several nanometers to several ten nanometers in diameter, and is composed of about 10,000 atoms.

When a quantum dot is disperse|distributed in the thin film of the semiconductor of a solar cell panel, since energy conversion efficiency can be improved significantly, application to a solar cell is examined (for example, refer patent document 1). In addition, by changing the size of the quantum dot (changing the band gap), the color (emission wavelength) of the emitted fluorescence can be changed (wavelength conversion), so a fluorescent probe in bioresearch (Non-Patent Document 1) ) and application to a display element as a wavelength conversion material (refer to patent document 2 and patent document 3) are examined.

Japanese Laid-Open Patent Publication No. 2006-216560 Japanese Laid-Open Patent Publication No. 2008-112154 Japanese Laid-Open Patent Publication No. 2009-251129

Kamitaka, "Semiconductor Quantum Dots, Their Synthesis Method and Application to Life Sciences", Production and Technology, Vol. 63, No. 2, 2011, p58-p65

As shown in the Examples of Non-Patent Document 1 and Patent Document 1, a typical quantum dot is a semiconductor quantum dot made of CdSe (cadmium selenide), CdTe (cadmium telluride), PbS, or the like of group II-V semiconductors. .

However, for example, lead (Pb), which is a main component, is a material with a well-known risk of toxicity. Moreover, cadmium (Cd) and its compound show very strong toxicity even at a low concentration, and are a material with concern about renal dysfunction and carcinogenicity. Therefore, formation of the semiconductor quantum dot which consists of a safer material is calculated|required.

In addition, when a semiconductor quantum dot is to be applied to a display of a solar cell panel or a display element, the formation of a film or a layer made of semiconductor quantum dots in particle form may be required because the fluorescence emission is used. That is, formation of a wavelength conversion film (wavelength conversion film) or a light emitting layer which shows fluorescence emission is calculated|required in some cases.

As a method of forming a light emitting layer using particle-form semiconductor quantum dots, for example, as shown in Examples of Patent Document 1 and Patent Document 2, a method of directly forming a layer made of semiconductor quantum dots on a suitable substrate is is known However, with such a formation method, the stability of the light emitting layer obtained is insufficient. In particular, there is a concern in binding properties between the layer made of semiconductor quantum dots and the substrate.

Therefore, a method of forming a layer or a film by mixing or embedding semiconductor quantum dots in the form of particles in a resin material has been proposed. However, a method for forming a layer or a film with a resin using semiconductor quantum dots while realizing high dispersibility and maintaining fluorescence properties as semiconductor quantum dots has not been sufficiently studied.

Therefore, a semiconductor quantum dot is used together with a resin material, high dispersibility is realized, and a layer or film of the semiconductor quantum dot is formed without lowering the fluorescence emission characteristic of the semiconductor quantum dot, and a highly reliable light emitting layer or wavelength conversion is performed. A technique for forming a film is required. In particular, there is a demand for a resin material that is used together with semiconductor quantum dots and is suitable for forming a light emitting layer or wavelength conversion film made of semiconductor quantum dots or resin.

In that case, it is preferable that a resin material is used especially with the semiconductor quantum dot which consists of a safe material, and a thing suitable for formation of a light emitting layer and a wavelength conversion film.

Moreover, it is preferable that the light emitting layer and wavelength conversion film which consist of a semiconductor quantum dot and a resin material can form simply and have high productivity. Therefore, it is preferable that a simple formation method, such as application|coating, can be used for formation of the light emitting layer or wavelength conversion film which consists of the semiconductor quantum dot and a resin material, for example. And it is preferable that the light emitting layer and wavelength conversion film can be formed using methods, such as application|coating, from the liquid resin composition containing a semiconductor quantum dot and a resin component, for example.

Therefore, it is prepared including a semiconductor quantum dot and a resin component, and the resin composition which can form a light emitting layer and a wavelength conversion film by use of methods, such as application|coating, is calculated|required.

Moreover, it is preferable that this resin composition has the outstanding patterning property. That is, it is preferable that patterning is possible so that the resin composition which forms a light emitting layer or a wavelength conversion film may use suitably for structures of light emitting elements, such as a light emitting display element, for example. In that case, it is preferable that the formation of the patterned light emitting layer or wavelength conversion film can be utilized, for example, a photolithographic method, etc. and can implement|achieve simply.

Therefore, the radiation-sensitive curable resin composition which can easily form the patterned light emitting layer and wavelength conversion film using well-known patterning methods, such as a photolithographic method, is calculated|required.

The present invention has been made in view of the above problems. That is, the objective of this invention is providing the curable resin composition which can form easily the highly reliable cured film excellent in a fluorescence characteristic including a semiconductor quantum dot.

Moreover, the objective of this invention is providing the cured film which is formed using the curable resin composition containing a semiconductor quantum dot, is excellent in a fluorescence characteristic, and has high reliability.

Moreover, the objective of this invention is providing the light emitting element which has a light emitting layer formed using the curable resin composition containing a semiconductor quantum dot.

Moreover, the objective of this invention is providing the wavelength conversion film which is formed using the curable resin composition containing a semiconductor quantum dot, is excellent in a fluorescence characteristic, and has high reliability.

Moreover, the objective of this invention is providing the formation method of the light emitting layer using the curable resin composition containing a semiconductor quantum dot.

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

A first aspect of the present invention is

[A] a compound having a molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule;

[B] semiconductor quantum dots and;

[C] Hydrocarbon solvent

It relates to a curable resin composition characterized in that it contains.

In the first aspect of the present invention, it is preferable to further contain an oxygen atom-containing organic solvent.

In the first aspect of the present invention, it is preferable to further contain [D] a polymerization initiator.

In the first aspect of the present invention, the [D] polymerization initiator is preferably a polymerization initiator containing a hydrocarbon group having 1 to 20 carbon atoms.

1st aspect of this invention WHEREIN: [E] It is preferable to contain the polymer whose weight average molecular weights which have a carboxyl group are 5000 or more and 40000 or less further.

In the first aspect of the present invention, [B] the semiconductor quantum dot is at least 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. It is preferable to consist of a compound containing two types of elements.

In the first aspect of the present invention, the [B] semiconductor quantum dot is preferably made of a compound containing In as a constituent component.

In the first aspect of the present invention, [B] a semiconductor quantum dot, InP/ZnS compound, CuInS ₂ /ZnS compound, AgInS ₂ compound, (ZnS/AgInS ₂ ) solid solution/ZnS compound, Zn doped It is preferable that it is at least 1 _sort(s ) chosen from the group which consists of an AgInS2 compound and a Si compound.

In the first aspect of the present invention, the compound [A] is at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) It is preferably a compound of:

(In formula (1), X represents a divalent group represented by formula (5) or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, and in formula (5), n represents an integer of 2 to 20; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group;

In formula (2), R<^2> represents a hydrogen atom or a C1-C12 alkyl group; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, m represents the integer of 0-4;

In formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, and m represents the integer of 0-4).

A 2nd aspect of this invention relates to the cured film formed using the curable resin composition of the 1st aspect of this invention, The cured film characterized by the above-mentioned.

A third aspect of the present invention relates to a light emitting element having a light emitting layer formed using the curable resin composition of the first aspect of the present invention.

A fourth aspect of the present invention relates to a wavelength conversion film formed using the curable resin composition of the first aspect of the present invention.

A fifth aspect of the present invention is a method for forming a light emitting layer of a light emitting element,

(1) A step of forming a coating film of the curable resin composition of the first aspect of the present invention on a substrate;

(2) a step of irradiating at least a part of the coating film formed in step (1) with radiation;

(3) a step of developing the coating film irradiated with radiation in step (2);

(4) It has a process of exposing the coating film developed in the process (3), It relates to the formation method of the light emitting layer characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to the 1st aspect of this invention, the curable resin composition which can form easily the highly reliable cured film excellent in a fluorescence characteristic including a semiconductor quantum dot is provided.

Moreover, according to the 2nd aspect of this invention, it is formed using the curable resin composition containing a semiconductor quantum dot, it is excellent in a fluorescence characteristic, and the cured film which has high reliability is provided.

Moreover, according to the 3rd aspect of this invention, the light emitting element which has a light emitting layer formed using the curable resin composition containing a semiconductor quantum dot is provided.

Moreover, according to the 4th aspect of this invention, it is formed using the curable resin composition containing a semiconductor quantum dot, is excellent in a fluorescence characteristic, and provides the wavelength conversion film which has high reliability.

Moreover, according to the 5th aspect of this invention, the formation method of the light emitting layer of a light emitting element using the curable resin composition containing a semiconductor quantum dot is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the board|substrate explaining the coating-film formation process in formation of the cured film of 2nd Embodiment of this invention.
It is sectional drawing explaining schematically the radiation irradiation process in formation of the cured film of 2nd Embodiment of this invention.
It is sectional drawing of the board|substrate explaining the image development process in formation of the cured film of 2nd Embodiment of this invention.
It is sectional drawing of the cured film explaining the hardening process in formation of the cured film of 2nd Embodiment of this invention, and a board|substrate.
5 is a cross-sectional view schematically showing a light emitting display device according to a third embodiment of the present invention.

(Form for implementing the invention)

The curable resin composition of the present invention is [A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule, that is, [A] a weight average molecular weight having two or more polymerizable groups in one molecule. A compound of 150 to 10000 (hereinafter simply referred to as [A] component), [B] semiconductor quantum dots (hereinafter simply referred to as [B] component), and [C] hydrocarbon-based solvent (hereinafter simply referred to as [C] component) Also called) is a curable resin composition comprising.

The curable resin composition of the present invention contains [C] a hydrocarbon-based solvent, and is a liquid resin composition suitable for a simple film or layer formation method such as application.

Although the curable resin composition of this invention contains [B] semiconductor quantum dot with component [A], the favorable dispersion state of [B] semiconductor quantum dot can be implement|achieved by containing [C] hydrocarbon type solvent.

[B] Semiconductor quantum dots tend to aggregate in a solvent of high polarity, and it is difficult to achieve a good dispersion state. [B] In a semiconductor quantum dot, aggregation impairs the characteristic as a quantum dot. On the other hand, [B] semiconductor quantum dots have a tendency to easily realize a good dispersion state in a solvent of low polarity. Therefore, in the curable resin composition of this invention, the hydrocarbon type solvent which can implement|achieve low polarity as component [C] is contained. In addition, as a resin component, the thing suitable for making it melt|dissolve or disperse|distribute in the [C] hydrocarbon solvent is selected. More specifically, [C] component [A] suitable for dissolving or dispersing in a hydrocarbon solvent is selected and contained.

As a result, the curable resin composition of this invention can form the liquid resin composition by which the favorable dispersion state of [B] semiconductor quantum dot was implement|achieved. And the curable resin composition of this invention can form the disperse|distributed layer and film|membrane of [B] semiconductor quantum dot using simple formation methods, such as application|coating.

In addition, the curable resin composition of the present invention may have radiation sensitivity. Therefore, the curable resin composition of the present invention is a polymer having a [D] polymerization initiator (hereinafter also simply referred to as [D] component) and [E] a polymer having a carboxyl group having a weight average molecular weight of 5000 or more and 40,000 or less (hereinafter simply referred to as [E] ] component). And the curable resin composition of this invention can be patterned using the photolithography method etc. based on the radiation sensitivity, for example.

In addition, in this invention, visible light, an ultraviolet-ray, a deep ultraviolet-ray, X-ray, a charged particle beam, etc. are contained in the "radiation" irradiated at the time of exposure.

In the photolithography method, a so-called resist composition is applied to the surface of a substrate to be processed or treated to form a resist film, and a resist pattern latent image is formed by irradiating light or electron beams to expose a predetermined resist pattern. , a step of heat-treating if necessary, a developing step of developing this to form a desired micropattern, and a step of performing processing such as etching on the substrate using the micropattern as a mask.

And the curable resin composition of this invention is patterned, if necessary, and forms the cured film of this invention. [B] Semiconductor quantum dot is contained in resin, and the cured film of this invention is comprised.

And the cured film of this invention has a fluorescence emission (wavelength conversion) function based on the [B] semiconductor quantum dot. Therefore, it can be used as a wavelength conversion film or a light emitting layer that emits fluorescence having a wavelength different from that of excitation light.

In particular, the cured film of this invention is suitable for use as a light emitting layer of a light emitting element, and can be used for the structure of the light emitting element of this invention mentioned later.

EMBODIMENT OF THE INVENTION Hereinafter, the formation method of curable resin composition of this invention, a cured film, a light emitting element, a wavelength conversion film, and a light emitting layer is demonstrated.

Embodiment 1.

<Curable resin composition>

As described above, the curable resin composition of the first embodiment of the present invention contains component [A], [B] semiconductor quantum dots, and [C] hydrocarbon-based solvent as essential components.

[C] By containing the hydrocarbon solvent, the curable resin composition of the present invention can form a liquid resin composition in which a good dispersion state of [B] semiconductor quantum dots is realized. And, as component [A], which is the resin component, it is used together with the [C] hydrocarbon solvent and is selected from compounds having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule capable of dissolving or dispersing.

The curable resin composition of the present invention contains a semiconductor quantum dot [B] using a method such as coating, and has an excellent fluorescence emission (wavelength conversion) function (hereinafter simply referred to as fluorescence or fluorescence characteristics). The cured film of embodiment of invention can be formed.

In addition, the curable resin composition of the present invention may have radiation sensitivity. Therefore, it is preferable that the curable resin composition of this invention contains a [D] polymerization initiator further, Furthermore, [E] It is preferable to contain the polymer whose weight average molecular weights which have a carboxyl group are 5000 or more and 40000 or less. do.

And the curable resin composition of this invention can contain the other arbitrary components mentioned later unless the effect of this invention is impaired.

EMBODIMENT OF THE INVENTION Below, the component contained in curable resin composition of 1st Embodiment of this invention is demonstrated.

[[A] A compound having a molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule]

Curable resin composition of 1st Embodiment of this invention contains the compound whose molecular weight which has two or more polymeric groups in [A] 1 molecule is 150 or more and 10000 or less.

[A] Examples of the polymerizable group of the component include a (meth)acryloyl group, a vinyl group, an oxiranyl group, and an oxetanyl group. Among these, a (meth)acryloyl group is especially preferable.

[A] Although the weight average molecular weight of component is 150 or more, when it is less than 150, there exists a tendency for the cured film physical property as a cured film not to be acquired. Moreover, when molecular weight is larger than 10000, there exists a tendency for it to become difficult to melt|dissolve in a hydrocarbon type solvent.

And it is preferable that [A] component has a 2 or more (meth)acryloyl group, and is a compound whose molecular weights are 150 or more and 10000 or less.

In addition, in this invention, the molecular weight of [A] component shows the weight average molecular weight measured by the gel permeation chromatography.

Curable resin composition of 1st Embodiment of this invention WHEREIN: Polyfunctional acrylate can be used as [A] component. Among them, [C] a polyfunctional acrylate which is used together with a hydrocarbon solvent and can be dissolved or dispersed is preferable.

[A] Examples of the polyfunctional acrylate used in the component include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acryl rate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol fluorenedi(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2-hydroxy- 3-(meth)acryloyloxypropyl methacrylate, trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyl Oxyethyl) phosphate, ethylene oxide-modified dipentaerythritol hexaacrylate, succinic acid-modified pentaerythritol triacrylate, a compound having a straight-chain alkylene group and an alicyclic structure, and having two or more isocyanate groups, and at least one in a molecule Polyfunctional (meth)acrylate compounds, such as a urethane (meth)acrylate compound obtained by making the compound which has a hydroxyl group and has 3-5 pieces (meth)acryloyloxy group react, etc. are mentioned.

As a commercial item of polyfunctional acrylate, for example,

Aronix (registered trademark) M-210, M-220, M-240, M-270, M-305, M-309, M-310, M-315 , M-321, M-400, M-402, M-405, M-408, M-450, M-1310, M-1600, M-1960, M-7100 , M-8030, M-8060, M-8100, M-8530, M-8560, M-9050, TO-1450, TO-1382 (above, manufactured by Toagose Corporation);

KAYARAD (registered trademark) DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.);

Viscoat (registered trademark) 260, Dong 295, Dong 300, Dong 310HP, Dong 335HP, Dong 360 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.);

As a urethane acrylate-based compound,

NEW FRONTIER (registered trademark) R-1150 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.);

KAYARAD (registered trademark) DPHA-40H, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, East UX-3204, East UX-3301, East UX-4101, East UX-5000, East UX-6101, East UX-7101, East UX-8101, East UX-0937, East MU-2100, East MU-4001 (or above) , manufactured by Nippon Kayaku Co., Ltd.);

Art-Resin (registered trademark) UN-333, UN-1255, UN-6060PTM, UN-7600, UN-7700, UN-9000PEP, UN-9200A (above, Negami Industries) Co., Ltd.), etc. are mentioned.

Moreover, it is preferable that it is at least 1 compound selected from the group which consists of a compound especially represented by a compound represented by a following formula (1), a compound represented by a following formula (2), and a following formula (3) as [A] component as a component especially :

(In formula (1), X represents a divalent group represented by formula (5) or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, and in formula (5), n represents an integer of 2 to 20; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group;

In formula (2), R<^2> represents a hydrogen atom or a C1-C12 alkyl group; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, m represents the integer of 0-4;

In formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, and m represents the integer of 0-4).

Among the compounds represented by Formula (1), Formula (2), and Formula (3) used as the component [A], those used particularly preferably are polyfunctional acryl having 2 to 4 functional groups excellent in solubility in hydrocarbon solvents. rate, for example, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, tricyclodecanedimethanol diacrylate, propylene oxide modified trimethylol A propane triacrylate, a ditrimethylol propane tetraacrylate, a propylene oxide modified|denatured ditrimethylol propane tetraacrylate, etc. are mentioned.

As a commercial item of the said polyfunctional acrylate, for example,

Aronix (registered trademark) M-310, Dong M-321, Dong M-408 (above, manufactured by Toagose Co., Ltd.);

NK Ester (registered trademark)　A-NOD-N, Copper A-DOD-N, Copper A-DCP, Copper A-TMPT-3PO, Copper A-TMPT-6PO, Copper AD-TMP-L, Copper AD-TMP- 4P (above, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.);

New Frontier (registered trademark) L-C9A, Dong TMP-3P (above, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.);

Viscote (trademark) 260, (above, the Osaka Organic Chemical Industry Co., Ltd. make) etc. are mentioned.

The above component [A] is contained in the curable resin composition of the first embodiment of the present invention, dissolved or dispersed, and a liquid resin composition for forming a layer or a film is formed using a simple forming method such as application. can

[[B] Semiconductor quantum dots]

[B] The semiconductor quantum dot, which is an essential component of the curable resin composition of the first embodiment of the present invention, does not contain Cd or Pb as a constituent component, but comprises In (indium), Si (silicon), etc., for example. It is a semiconductor quantum dot which consists of components and consists of a safe material.

[B] The semiconductor quantum dot contains at least two or more elements selected from the group of elements represented by 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 It is preferable that it is a semiconductor quantum dot which consists of the compound which says.

And, more specifically, elements with high concern for safety for humans, such as Pb and Cd, are excluded, and Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium) , Ba (barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium) , C (carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen) It is preferable that it is a semiconductor quantum dot which consists of a compound containing at least 2 or more types of elements selected from , S (sulfur), Se (selenium), Te (tellurium), and Po (polonium) group.

At this time, it is preferable that the [B] semiconductor quantum dot consists of 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. do.

[B] A semiconductor quantum dot is composed of a compound (a) and/or a compound (b) having such a fluorescence emission characteristic, and thus a wavelength region of 500 nm to 600 nm and/or a wavelength region of 600 nm to 700 nm may have a fluorescence maxima. As a result, the curable resin composition of this embodiment containing [B] semiconductor quantum dot can form a cured film suitable for the structure of the light emitting layer of the light emitting element which displays an image using the light of a visible region. .

Moreover, it is more preferable that the [B] semiconductor quantum dot contained in the curable resin composition of this embodiment is a semiconductor quantum dot which consists of a compound containing In as a structural component. Moreover, Si or a Si compound is mentioned as another [B] semiconductor quantum dot.

[B] As a semiconductor quantum dot, Si is especially preferable among Si or Si compounds.

[B] By making the component configuration of the semiconductor quantum dot as described above, the curable resin composition of the present embodiment is safe and can form a cured film having excellent fluorescence properties, and furthermore, safe and excellent fluorescence properties A wavelength conversion film or a light emitting layer of a light emitting element can be formed.

In addition, the [B] semiconductor quantum dot contained in the curable resin composition of this embodiment is a semiconductor quantum dot of at least one structural type selected from the homogeneous structure type which consists of 1 type of compound, and the core-shell structure type which consists of 2 or more types of compounds. It is preferable to be

The [B] semiconductor quantum dot of the core-shell structure type is constituted by forming a core structure with one type of compound and covering the periphery of the core structure with another compound. For example, by covering the semiconductor of the core with a semiconductor having a larger band gap, excitons (electron-hole bands) generated by photoexcitation are trapped in the core. As a result, the probability of the radiation-free transition on the surface of the quantum dot is reduced, and the quantum yield of light emission and the stability of the fluorescence property of the [B] semiconductor quantum dot are improved.

[B] The semiconductor quantum dots contained in the curable resin composition of the present embodiment are core-shell structured semiconductor quantum dots InP/ZnS, CuInS ₂ /ZnS and (ZnS/AgInS ₂ ) solid solution/ ZnS, and is preferably at least one member selected from the homogeneous-structure semiconductor quantum dot of AgInS ₂ and the group consisting of Zn-doped AgInS _2.

From the above, [B] semiconductor quantum dots contained in the curable resin composition of this embodiment are InP/ZnS compound, CuInS ₂ /ZnS compound, AgInS ₂ compound, (ZnS/AgInS ₂ ) solid solution/ZnS compound, Zn doped It is preferable that it is at least 1 selected from the group of AgInS _{2 compound and Si compound.}

By the [B] semiconductor quantum dot exemplified above, the curable resin composition of the present embodiment containing the same is safe and forms a cured film having more excellent fluorescence properties, and furthermore, a wavelength conversion film of more excellent fluorescence properties Alternatively, the light emitting layer of the light emitting device can be formed.

Moreover, it is preferable that average particle diameters are 0.5 nm - 20 nm, and, as for [B] semiconductor quantum dot contained in curable resin composition of this embodiment, it is more preferable that they are 1.0 nm - 10 nm. When the average particle diameter is less than 0.5 nm, it is difficult to prepare the [B] semiconductor quantum dot, and even if it can be prepared, the fluorescence characteristic of the [B] semiconductor quantum dot may become unstable. [B] When the average particle diameter of the semiconductor quantum dots exceeds 20 nm, the quantum confinement effect due to the size of the semiconductor quantum dots may not be obtained, and the desired fluorescence characteristics cannot be obtained, which is not preferable.

In addition, [B] The shape of a semiconductor quantum dot is not specifically limited, For example, a spherical shape, a rod shape, a disk shape, and other shapes may be sufficient. Information such as the particle size, shape, and dispersion state of the quantum dots can be obtained by a transmission electron microscope (TEM).

As a method of obtaining the [B] semiconductor quantum dot contained in the curable resin composition of the first embodiment of the present invention, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent can be used. In addition, the semiconductor quantum dots of the core-shell structure type, after forming a homogeneous core structure by reaction, add a precursor for forming a shell on the surface of the core in the reaction system, and after shell formation, the reaction is stopped, and the reaction is removed from the solvent. It can be obtained by separating. Moreover, it is also possible to use a commercially available thing.

As content of [B] semiconductor quantum dot in curable resin composition of this embodiment, with respect to 100 mass parts of [A] component mentioned above, Preferably it is 0.1 mass part - 100 mass parts, More preferably, 0.2 mass parts to 50 parts by mass. [B] By making content of a semiconductor quantum dot into the above-mentioned range, the cured film which has the outstanding fluorescence characteristic can be formed, As a result, the wavelength conversion film of the outstanding fluorescence characteristic, or the light emitting layer of a light emitting element can be formed. [B] When content of a semiconductor quantum dot is less than 0.1 mass part with respect to 100 mass parts of [A] component, the fluorescence characteristic made desired in the cured film formed cannot be acquired, but a wavelength conversion film or a light emitting element A light emitting layer cannot be formed. Moreover, when there are more than 100 mass parts with respect to 100 mass parts of [A] component, stability of the cured film formed will be impaired, and the light emitting layer of a stable wavelength conversion film or a light emitting element cannot be formed.

[[C] Hydrocarbon solvent]

The curable resin composition of the first embodiment of the present invention contains [C] a hydrocarbon-based solvent. Curable resin composition of this embodiment can form a liquid resin composition by containing [C] hydrocarbon-type solvent, On the other hand, [B] suppresses aggregation of semiconductor quantum dots, [B] semiconductor quantum A dotted dispersed curable resin composition can be formed.

The hydrocarbon-based solvent refers to a solvent composed of only carbon atoms and hydrogen atoms. Examples of the hydrocarbon solvent include an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent include toluene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cymene, tetralin, biphenyl, and mesitylene. Examples of the aliphatic hydrocarbon solvent include hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-mentane, decalin, isooctane, isododecane, cyclohexene, and cyclopentane. , Dipentene, Isopar E, Isopar G, Isopar H, Isofar L, Isopar M (manufactured by Kokura Kosan Co., Ltd.), turpentine oil, decahydronaphthaline, finan, α -Pinene, β-pinene, limonene, benzine, Kyowasol C-800, shellsol, isosol, and ligroin (manufactured by God Industrial Co., Ltd.), and the like.

Moreover, in the curable resin composition of 1st Embodiment of this invention, an oxygen atom containing organic solvent can be contained with the [C] hydrocarbon-type solvent mentioned above. An oxygen-containing organic solvent is a solvent containing an oxygen atom in a molecule|numerator. By containing this oxygen atom containing organic solvent, the curable resin composition of this embodiment can improve the solubility or dispersibility of [A] component more.

Examples of the oxygen atom-containing organic solvent include ester solvents such as ethyl acetate, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ether solvents such as tetrahydrofuran, dioxane, and dialkyl ether, dimethyl sulfoxide and amide solvents such as solvents such as dimethylformamide, N-methylpyrrolidone, and N,N-dimethylacetamide.

[C] When using an oxygen atom-containing organic solvent by mixing with a hydrocarbon-based solvent, [C] When the use ratio of the hydrocarbon-based solvent is 100, the oxygen atom-containing organic solvent is used in the range of 1% by mass to 50% by mass. it is preferable When the said usage-amount of the oxygen atom containing organic solvent is less than 1 mass %, the addition effect of an oxygen atom containing organic solvent may not fully be acquired. Moreover, when the above-mentioned usage-amount of an oxygen atom containing organic solvent is more than 50 mass %, fear of aggregation of [B] semiconductor quantum dot may arise.

[[D] Polymerization Initiator]

The curable resin composition of 1st Embodiment of this invention can contain [D] a polymerization initiator further. [D] The polymerization initiator is a component that generates active species capable of initiating polymerization of a compound having the same polymerizable group as component [A] in response to radiation. Curable resin composition of this embodiment can improve radiation sensitivity and patternability by containing [D] a polymerization initiator. And the curable resin composition of this embodiment can form the light emitting layer and wavelength conversion film which were patterned simply using well-known patterning methods, such as a photolithography method.

Curable resin composition of this embodiment WHEREIN: As a [D] polymerization initiator, an oxime ester compound, an acetophenone compound, a biimidazole compound, etc. are mentioned, for example. In addition, [D] You may use a polymerization initiator individually or in combination of 2 or more type.

Examples of the oxime ester compound include ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1, 2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octane-1- Onoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-oneoxime-O-benzoate, 1-[9- n-Butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-oneoxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-) Methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetra) Hydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-) O-acyloxime compounds, such as dioxolanyl) methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyl oxime), etc. are mentioned.

In the above, examples of the oxime ester compound include ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1,2 -Octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-) Preference is given to dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime).

Examples of the acetophenone compound include α-aminoketone and α-hydroxyketone compounds.

Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl). )-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, etc. can

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-i-propylphenyl)-2-hydroxy-2-methyl. Propan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, etc. are mentioned.

The acetophenone compound is preferably an α-aminoketone compound, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one is more preferable.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' -Biimidazole, 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, etc. are mentioned. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5, 5'-tetraphenyl-1,2'-biimidazole is preferred, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole is more preferable.

[D] As content of a polymerization initiator, 0.1 mass part - 40 mass parts are preferable with respect to 100 mass parts of [A] component, and 0.5 mass part - 20 mass parts are more preferable. [D] By making content of a polymerization initiator into the said range, curable resin composition of this embodiment can show favorable patterning property even in the case of a low exposure amount, and can form the cured film which has sufficient surface hardness and adhesiveness.

Moreover, it is preferable that the [D] polymerization initiator is a polymerization initiator containing a C1-C20 hydrocarbon group. By setting it as the [D] polymerization initiator having such a structure, in the curable resin composition of the present embodiment, the solubility of the [D] polymerization initiator in the [C] hydrocarbon-based solvent can be improved.

Examples of the polymerization initiator containing a hydrocarbon group having 1 to 20 carbon atoms include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane- 1-one (IRUGACURE (registered trademark) 379), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (IRUGACURE (registered trademark) ) OXE01), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure® OXE02 ) (above, manufactured by BASF) and the like.

[[E] Polymer having a carboxyl group and having a weight average molecular weight of 5000 or more and 40000 or less]

The polymer having a weight average molecular weight of 5000 or more and 40,000 or less having a [E] carboxyl group as the [E] component in the curable resin composition of the present invention contains the compound (e1) and the compound (e2) described later in a solvent, the presence of a polymerization initiator A copolymer (hereinafter, also referred to as a [E1] component) and a carboxyl group-containing elastomer (hereinafter also referred to as a [E2] component) which can be produced by radical polymerization under the following conditions are mentioned.

[E1] Among the components, (e1) ethylenically unsaturated carboxylic acid and/or ethylenically unsaturated carboxylic acid anhydride (hereinafter, these are collectively referred to as unsaturated carboxylic acid monomer (e1)) include, for example, acrylic acid and methacrylic acid. monocarboxylic acids such as acid, crotonic acid, 2-methacryloyloxyethylsuccinic acid, and 2-methacryloyloxyethylhexahydrophthalic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, metaconic acid, and itaconic acid; The anhydrides of the said dicarboxylic acid etc. are mentioned.

Among these unsaturated carboxylic acid monomers (e1), acrylic acid, methacrylic acid, maleic anhydride, 2-methacryloyloxyethylhexahydrophthalic acid, from the viewpoint of copolymerization reactivity, solubility of the polymer obtained in aqueous alkali solution, and easy availability. etc. are preferable.

[E1] Component WHEREIN: The unsaturated carboxylic acid-type monomer (e1) can be used individually or in mixture of 2 or more types.

[E1] In the component, the content of the repeating unit derived from the unsaturated carboxylic acid monomer (e1) is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, particularly preferably 15 mass % - 30 mass %. In this case, when the content rate of the repeating unit derived from the unsaturated carboxylic acid monomer (e1) is less than 5% by mass, the solubility in aqueous alkali solution tends to decrease, whereas when it exceeds 40% by mass, the solubility in aqueous alkali solution is poor. There is a risk of becoming too large.

Further, as (e2) other ethylenically unsaturated compounds (hereinafter simply referred to as (e2) other monomers), (meth)acrylic acid alkyl esters, (meth)acrylic acid alicyclic esters, (meth)acrylic acid aryl esters, dicarboxylic acid dialkyl esters, (meth)acrylic acid epoxyalkyl esters; dicarbonylimide derivatives; A conjugated diene type compound, a vinyl aromatic compound, etc. are mentioned.

Among these (e2) other monomers, 2-methylcyclohexyl acrylate, hydroxyethyl methacrylate, tricyclo[5.2.1.0 ^{2,6 methacrylate from the viewpoint of copolymerization reactivity and solubility of the polymer obtained in aqueous alkali solution.} ]Decan-8-yl, styrene, glycidyl methacrylate, 3-(methacryloxymethyl)-3-ethyloxetane, tetrahydrofurfuryl methacrylate, 1,3-butadiene, phenylmaleimide, cyclo Hexylmaleimide and the like are preferable. (e2) Other monomers can be used individually or in mixture of 2 or more types.

[E1] component, (e2) the repeating unit derived from other monomers, preferably 50 mass% to 95 mass%, more preferably 60 mass% to 90 mass%, particularly preferably 70 mass% to 85 mass% % by mass. In this case, when the repeating unit is less than 10% by mass, the storage stability of the component [E1] tends to decrease, while when it exceeds 70% by mass, the component [E1] becomes difficult to dissolve in the aqueous alkali solution.

As described above, the [E1] component used in the present invention has a carboxyl group and/or a carboxylic acid anhydride group and other ethylenically unsaturated compounds, has appropriate solubility in aqueous alkali solution, and does not use a special curing agent in combination. It can be easily hardened by heating.

[E1] As a solvent used for manufacture of a component, For example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene A glycol alkyl ether propionate, an aromatic hydrocarbon, a ketone, ester, etc. are mentioned.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and dipropylene Glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate and 3-methoxybutyl acetate are particularly preferable.

The said solvent can be used individually or in mixture of 2 or more types.

Moreover, it does not specifically limit as a radical polymerization initiator used for the said superposition|polymerization, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis-(2, 4- dimethylvalero nitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azo azo compounds such as bis(2-methylpropionate) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1-bis(t-butylperoxy)cyclohexane; Hydrogen peroxide etc. are mentioned. In addition, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator by using it and a reducing agent together.

These radical polymerization initiators can be used individually or in mixture of 2 or more types.

Moreover, (meth)acrylic acid ester which has an epoxy group can be made to react with the carboxyl group in [E1] component, and a (meth)acryloyloxy group can be introduce|transduced in a polymer.

In the reaction with an unsaturated compound such as (meth)acrylic acid ester having a carboxyl group in a polymer and an epoxy group, in the presence of a suitable catalyst as needed, preferably in a solution of a polymer containing a polymerization inhibitor, an unsaturated compound having an epoxy group The compound is added and stirred under heating for a predetermined time. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxyphenol etc. are mentioned, for example. As for reaction temperature, 70 degreeC - 100 degreeC are preferable. As for reaction time, 8 hours - 12 hours are preferable.

It is preferable that they are 10 mol% - 70 mol% in [E1] component whole component, and, as for content of the structural unit which has a (meth)acryloyloxy group, it is more preferable that they are 20 mol% - 50 mol%.

When content of the structural unit which has a (meth)acryloyloxy group is less than 10 mol%, there exists a tendency for the sensitivity to the radiation of curable resin composition to fall, and the heat resistance of the cured film obtained is also not enough. Moreover, when it contains more than 70 mol%, it becomes a cause at the time of image development at the time of image development, and it becomes easy to generate|occur|produce image development residue.

A carboxyl group containing elastomer is mentioned as [E2] component in curable resin composition of this invention.

[E2] As the carboxyl group-containing elastomer used as the component, for example, carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade names "LIR-410" "UC-102" "UC-203"), maleic anhydride-modified EEA resin (manufactured by Nippon Paper Co., Ltd., trade name "AUROREN 350S"), maleic anhydride-modified SEBS resin (manufactured by Asahi Kasei Chemicals, trade name "TUFTEC M-1943"), ethylene-methacrylic Acid copolymer resin (The Mitsui DuPont Polychemical Co., Ltd. make, brand name "Nucrel") etc. are mentioned.

Among the carboxyl group-containing elastomers used as the component [E2], in particular, carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade names "LIR-410" "UC-102" "UC-203") is a quantum dot dispersion stability It is preferable from a viewpoint, and especially, "UC-102" is especially preferable from a viewpoint of patterning.

The above component [E] WHEREIN: The polystyrene conversion weight average molecular weight (henceforth "Mw") by gel permeation chromatography (GPC) is 5000-40000 normally, Preferably it is 5000-20000. In this case, when Mw is less than 5000, there is a possibility that the developability, the remaining film ratio, etc. of the obtained film may fall, or a pattern shape, heat resistance, etc. may be impaired. On the other hand, when Mw exceeds 20000, there exists a possibility that a resolution may fall or a pattern shape may be impaired.

As content of [E] component, 20 mass parts - 200 mass parts are preferable with respect to 100 mass parts of [A] component, and 40 mass parts - 150 mass parts are more preferable. By making content of a polymer into the said range, curable resin composition of this embodiment can form the cured film which is excellent in adhesiveness and has sufficient surface hardness also in a low exposure amount.

[Other optional ingredients]

The curable resin composition of the first embodiment of the present invention contains [A] a compound having a molecular weight of 150 to 10000 having two or more polymerizable groups in one molecule, [B] a semiconductor quantum dot, and [C] a hydrocarbon solvent. As long as the effects of the present invention are not impaired, other optional components may be contained. As another optional component, a hardening accelerator, a thermal acid generator, etc. are mentioned, for example.

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

A thermal acid generator is a compound capable of releasing an acidic active substance that acts as a catalyst when curing a resin by applying heat.

Moreover, the curable resin composition of this embodiment can contain other arbitrary components, such as surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improving agent, as needed within the range which does not impair the effect of this invention. Each of these optional components may be used independently, and 2 or more types may be mixed and used for them.

[Method for preparing curable resin composition]

The curable resin composition of the first embodiment of the present invention includes [A] a compound having a molecular weight (weight average molecular weight) of 150 to 10000 having two or more polymerizable groups in one molecule, [B] a semiconductor quantum dot, and [C] It is prepared by uniformly mixing a hydrocarbon solvent. In addition, when the component [D] or the component [E] is contained, it is prepared by uniformly mixing the component [D] and the component [E] together with the component [A], the component [B] and the component [C].

Moreover, when selecting other arbitrary components as needed, and making them contain, it prepares by mixing uniformly [A] component, [B] component, and [C] component, and other arbitrary components. And the curable resin composition of this embodiment contains the [C] hydrocarbon type solvent, and also contains an oxygen atom containing organic solvent if necessary, other components melt|dissolve, Preferably it is used in a solution state.

[C] The content of the hydrocarbon-based solvent and the oxygen atom-containing organic solvent (hereinafter simply referred to as a solvent component) used when necessary is not particularly limited. However, from the viewpoint of solubility of other components of the obtained curable resin composition, applicability and stability of the curable resin composition, the total concentration of each component excluding the solvent component of the curable resin composition is 2% by mass to 50% by mass The quantity is preferable, and the quantity used as 5 mass % - 40 mass % is more preferable. When preparing the solution of curable resin composition, in fact, in the above-mentioned density|concentration range, the solid content concentration (components other than the solvent component which occupies in curable resin composition solution) according to the value of a desired film thickness etc. is set.

After filtering the curable resin composition of this embodiment of the solution state prepared in this way using the Millipore filter etc. with a pore diameter of about 0.5 micrometer, it is preferable to use for formation of the cured film of this embodiment.

Embodiment 2.

<Cured film>

The cured film of 2nd Embodiment of this invention apply|coats the curable resin composition of 1st Embodiment of this invention mentioned above on a board|substrate, after patterning if necessary, it heat-hardens and forms. Below, the cured film of this embodiment and its formation method are demonstrated.

In the formation method of the cured film of this embodiment, it is preferable to include the following process (1) - a process (4) in the following order at least so that a cured film may be formed on a board|substrate.

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

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

(3) A developing step of developing the coating film irradiated with radiation in step (2).

(4) A curing step of exposing the coating film developed in step (3).

And FIGS. 1-4 are figures explaining the formation method of the cured film of 2nd Embodiment of this invention.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the board|substrate explaining the coating-film formation process in formation of the cured film of 2nd Embodiment of this invention.

2 : is sectional drawing explaining schematically the radiation irradiation process in formation of the cured film of 2nd Embodiment of this invention.

It is sectional drawing of the board|substrate explaining the image development process in formation of the cured film of 2nd Embodiment of this invention.

It is sectional drawing of the cured film explaining the hardening process in formation of the cured film of 2nd Embodiment of this invention, and a board|substrate.

Hereinafter, the above-mentioned process (1) (coating-film formation process) - process (4) (hardening process) are demonstrated, respectively.

[Process (1)]

In the coating film formation process which is process (1) of the formation method of the cured film of this embodiment, as shown in FIG. 1, the coating film 1 of curable resin composition of 1st Embodiment of this invention is formed on the board|substrate 2 do.

To the substrate 2 forming the coating film 1, glass, quartz, silicon, or resin (for example, polyimide, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate) , polyester, a ring-opened polymer of a cyclic olefin, a hydrogenated substance thereof, etc.) can be used. Further, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method or vacuum deposition, if desired.

In the board|substrate 2, after the curable resin composition of this embodiment is apply|coated to one surface, prebaking is performed, components, such as a solvent contained in curable resin composition, evaporate, and the formation of the coating film 1 is is done

As a coating method of the curable resin composition in this process, for example, a spray method, a roll coating method, a spin coating method (the spin coating method or a spinner method may be called), a slit coating method (slit die coating method) ), a bar coating method, and an appropriate method such as an inkjet coating method can be employed. Among these, the spin coating method or the slit coating method is preferable at the point which can form the film|membrane of uniform thickness.

Although the conditions of the above-mentioned pre-baking differ depending on the kind, blending ratio, etc. of each component which comprises curable resin composition, it is preferable to carry out at the temperature of 70 degreeC - 120 degreeC, and time is a heating apparatus, such as a hotplate and oven, Although it varies depending on the time, it is about 1 minute to 15 minutes.

[Process (2)]

Next, in the radiation irradiation process which is the process (2) of the formation method of the cured film of this embodiment, as shown in FIG. 2, at least a part of the coating film 1 formed on the board|substrate 2 in the process (1) is radiated ( 4) is investigated. At this time, in order to irradiate only a part of the coating film 1 with the radiation 4a, it carries out via the photomask 3 of the pattern corresponding to formation of a desired shape, for example. By using the photomask 3 , a part of the irradiated radiation 4 passes through the photomask, and the part of the radiation 4a is irradiated to the coating film 1 .

As the radiation 4 used for irradiation, a visible ray, an ultraviolet-ray, a deep ultraviolet ray, etc. are mentioned. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The dose (exposure dose) of the radiation 4 is a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation 4 with an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), and is 10 J/m 2 to 10000 J/m 2 and 100 J/m 2 to 5000 J/m 2 are preferable, and 200 J/m 2 to 3000 J/m 2 are more preferable.

[Process (3)]

Next, in the developing process which is process (3) of the formation method of the cured film of this embodiment, as shown in FIG. 3, the coating film 1 of FIG. 2 after irradiation is developed, an unnecessary part is removed, and a predetermined shape to obtain a patterned coating film 1a.

As a developing solution used for image development, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. An aqueous solution of an alkaline compound such as quaternary ammonium salt or choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene may be used. can An appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added to the aqueous solution of the above-mentioned alkaline compound and used. Moreover, surfactant can also be used by itself or by adding an appropriate amount together with addition of the above-mentioned water-soluble organic solvent.

The developing method may be any of a puddle method, a dipping method, a shower method, a spray method, and the like, and the developing time can be 5 seconds to 300 seconds at room temperature, and preferably about 10 seconds to 180 seconds at room temperature. . Following the developing treatment, for example, washing under running water is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen to obtain a desired pattern.

[Process (4)]

Next, in the hardening process which is process (4) of the formation method of the cured film of this embodiment, the patterned coating film 1a shown in FIG. 3 is hardened by exposure using the exposure apparatus (it is also called post exposure). Thereby, as shown in FIG. 4, the cured film 5 of this embodiment formed on the board|substrate 2 is obtained. As mentioned above, the cured film 5 is patterned so that it may become a desired shape.

The curable resin composition of 1st Embodiment mentioned above is used for formation of the cured film 5 of this embodiment, At this process, a part of the coating film is irradiated with a radiation. Specifically, the coating film formed in the step (1) and patterned in the steps (2) and (3) is irradiated with a predetermined radiation. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of the above-mentioned ultraviolet rays include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). As far ultraviolet rays, KrF excimer laser beam etc. are mentioned, for example. Examples of X-rays include synchrotron radiation. As a charged particle beam, an electron beam etc. are mentioned, for example. Among these radiations, the use of ultraviolet rays is preferable, and among the ultraviolet rays, the radiation containing at least one of g-rays, h-rays and i-rays is more preferable. As an exposure amount of a radiation, 0.1 J/m<2> - 30000 J/m<2> is preferable.

The cured film of this embodiment formed by the method for forming a cured film including the above steps (1) to (4) is constituted by including [B] semiconductor quantum dots in resin, and based on [B] semiconductor quantum dots It has a fluorescence emission (wavelength conversion) function. Therefore, it can be used as a wavelength conversion film which emits fluorescence of a wavelength different from excitation light. Therefore, the wavelength conversion film of embodiment of this invention can be formed according to the formation method of the cured film of 2nd Embodiment mentioned above using the curable resin composition of 1st Embodiment of this invention. And the wavelength conversion film of this embodiment has the function of fluorescence emission (wavelength conversion) based on [B] semiconductor quantum dot.

Moreover, it is also possible to provide a light emitting element using the cured film of this embodiment as a light emitting layer. In that case, the light emitting layer of the light emitting element of embodiment of this invention can be formed similarly using the curable resin composition of 1st Embodiment of this invention according to the formation method of the cured film of this embodiment mentioned above. And the light emitting layer of the light emitting element of this embodiment has a fluorescent light emission (wavelength conversion) function based on [B] semiconductor quantum dot.

In particular, the cured film of this embodiment is suitable for use as a light emitting layer of the light emitting display element which is an example of a light emitting element so that it may mention later, and can be used for the structure of a light emitting display element.

Therefore, the cured film has a total light transmittance (JIS K7105) in a thickness of 0.1 mm in the resin constituting the cured film so as to increase light utilization efficiency, preferably 75% to 95%, more preferably 78 % to 95%, more preferably 80% to 95%. The cured film obtained as a total light transmittance being such a range can comprise the light emitting layer of the wavelength conversion film of the outstanding light utilization efficiency, or a light emitting element.

Embodiment 3.

<Light emitting display element and its light emitting layer>

In this invention, light emitting elements, such as a lighting device and a light emitting display element, can be provided by using the cured film of 2nd Embodiment of this invention mentioned above as a wavelength conversion film or a light emitting layer.

The light emitting display element which is a 3rd Embodiment of this invention is an example of the light emitting element of this invention. The light emitting display element which is 3rd Embodiment of this invention is comprised using the wavelength conversion board|substrate which uses the cured film of 2nd Embodiment of this invention mentioned above as a light emitting layer.

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

The light emitting display device 100 of the first embodiment of the present invention includes a wavelength conversion substrate 11 configured by forming light emitting layers 13 ( 13a , 13b , 13c ) and a black matrix 14 on a substrate 12 ; , has a light source substrate 18 bonded to a wavelength conversion substrate 11 via an adhesive layer 15 .

The substrate 12 is made of glass, quartz, or a transparent resin (eg, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).

The light emitting layer 13 of the wavelength conversion substrate 11 is formed using the cured film of 2nd Embodiment of this invention mentioned above. That is, the light emitting layer 13 is formed by patterning using the curable resin composition of 1st Embodiment of this invention mentioned above.

About the formation method of a light emitting layer, since they are formed using the cured film of 2nd Embodiment of this invention, it becomes the same as the formation method of the cured film of 2nd Embodiment of this invention mentioned above.

That is, the cured film of 2nd Embodiment of this invention is formed on the board|substrate 12, and they become the light emitting layer 13 and comprise the wavelength conversion board|substrate 11 of the light emitting display element 100. As shown in FIG. Accordingly, the method for forming the light emitting layer 13 preferably includes the following steps (1) to (4), which are the same as those described above, in this order.

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

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

(3) A developing step of developing the coating film irradiated with radiation in step (2).

(4) A curing step of exposing the coating film developed in step (3).

And each of the (1) process - (4) process for forming the light emitting layer 13 is as having demonstrated using FIGS. 1-4 in formation of the cured film of 2nd Embodiment of this invention. Therefore, although the detail is abbreviate|omitted, the cured film 5 patterned so that it may become the desired shape shown with respect to FIG. 4 turns into the light emitting layer 13 of the wavelength conversion board|substrate 11 of FIG.

The wavelength conversion substrate 11 converts the excitation light from the excitation light source 17 of the light source substrate 18 to wavelength using the semiconductor quantum dots contained in each of the light emitting layers 13 to obtain a desired wavelength. emit fluorescence.

And, in the wavelength conversion substrate 11, the light emitting layer 13a, the light emitting layer 13b, and the light emitting layer 13c of the light emitting layer 13 are each configured to include different semiconductor quantum dots, so that different fluorescence can be emitted. .

For example, in the wavelength conversion substrate 11 , the light emitting layer 13a converts the excitation light into red light, the light emitting layer 13b converts the excitation light into green light, and the light emitting layer 13c converts the excitation light into green light. It can be configured to convert to blue light.

In that case, the semiconductor quantum dots to contain are selected so that each of the light emitting layers 13a, 13b, and 13c has a desired fluorescence characteristic. Therefore, in the formation of the light-emitting layers 13a, 13b, and 13c of the wavelength conversion substrate 11, for example, the curable resin composition of the first embodiment of three types containing semiconductor quantum dots having different light-emitting properties is used. Ready.

And the formation method of the light emitting layer 13 containing the above-mentioned process (1) - process (4) is repeated using the curable resin composition of 3 types of 1st Embodiment, respectively, and the light emitting layer 13a and the light emitting layer (13b) and the light emitting layer 13c are sequentially formed. And the light emitting layer 13 is formed on the board|substrate 12, and the wavelength conversion board|substrate 11 is obtained.

About 100 nm - 100 micrometers are preferable, and, as for the thickness of the light emitting layer 13 of the wavelength conversion board|substrate 11, 1 micrometer - 100 micrometers are more preferable. If the thickness is less than 100 nm, the excitation light cannot be sufficiently absorbed and the light conversion efficiency is lowered, so that the luminance of the light emitting display element cannot be sufficiently secured. Moreover, in order to increase absorption of excitation light and to ensure sufficient brightness|luminance of a light emitting display element, as a film thickness, it is preferable to set it as 1 micrometer or more.

A black matrix 14 is disposed between each light emitting layer 13 on the substrate 12 . The black matrix 14 can be formed by using a known light-shielding material and patterning according to a known method. In addition, the black matrix 14 is not an essential component in the wavelength conversion board|substrate 11, The wavelength conversion board|substrate 11 can also be set as the structure which does not form the black matrix 14. As shown in FIG.

The adhesive layer 15 is formed using a well-known adhesive agent which transmits the ultraviolet light or blue light of the wavelength mentioned later. In addition, as shown in FIG. 5, it is not necessary to form the adhesive bond layer 15 so that the whole surface of the light emitting layers 13a, 13b, 13c may be covered on the board|substrate 12, and it is periphery of the wavelength conversion board|substrate 11. It is also possible to form only on

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, respectively.

As the light source 17, an ultraviolet light emitting organic EL element having a known structure, a blue light emitting organic EL element, or the like can be used, and it is not particularly limited, and it can be produced by a known material or a known manufacturing method. Here, as ultraviolet light, light emission having a main emission peak of 360 nm to 435 nm is preferable, and as blue light, light emission having a main emission peak of 435 nm to 480 nm is preferable. It is preferable that the light source 17 has directivity so that each emitted light irradiates the opposing light emitting layer 13 .

The light emitting display element 100 of this embodiment converts the excitation light from the light source 17a which is one of the light sources 17 into wavelength by the semiconductor quantum dot of the light emitting layer 13a of the wavelength conversion board|substrate 11 which opposes. do. Similarly, the excitation light from the light source 17b is wavelength-converted by the semiconductor quantum dots of the light emitting layer 13b of the wavelength conversion substrate 11 that are opposed to each other, and the excitation light from the light source 17c is converted to an opposing wavelength. The wavelength is converted by the semiconductor quantum dots of the light emitting layer 13c of the conversion substrate 11 . In this way, the excitation light from the light source 17 is converted into visible light having a desired wavelength, and is used for display.

In addition, in the wavelength conversion substrate 11, the excitation light is converted into blue light in the light emitting layer 13c as will be described later. In this case, the wavelength conversion substrate 11 may use a light scattering layer configured by dispersing light scattering particles in a resin instead of the light emitting layer 13c. In this way, when the excitation light is blue light, the excitation light can be used with the wavelength characteristics as it is without wavelength conversion.

As described above, the wavelength conversion substrate 11 of the light emitting display device 100 has a light emitting layer 13a, a light emitting layer 13b, and a light emitting layer 13c made of a semiconductor quantum dot and a resin, respectively, patterned on the substrate 12 . has been formed The light-emitting layers 13a, 13b, and 13c are each formed from the curable resin composition of 1st Embodiment containing a semiconductor quantum dot.

In the light-emitting display element 100, the portion where the light-emitting layer 13a is formed constitutes a sub-pixel that displays red. That is, the light emitting layer 13a of the wavelength conversion substrate 11 converts the excitation light from the opposing light source 17a of the light source substrate 18 into red. Further, the portion where the light emitting layer 13b is formed constitutes a sub-pixel that displays green. That is, the light emitting layer 13b converts the excitation light from the light source 17b opposite to the light source substrate 18 into green. Further, the portion where the light-emitting layer 13c is formed constitutes a sub-pixel for performing blue display. That is, the light emitting layer 13c converts the excitation light from the light source 17c opposite to the light source substrate 18 into blue.

In addition, the light emitting display element 100 has the minimum of three types of sub-pixels including the light-emitting layer 13a, the sub-pixel with the light-emitting layer 13b, and the sub-pixel with the light-emitting layer 13c. One pixel serving as a unit is constituted.

The light emitting display device 100 of the present embodiment having the above configuration has red and green sub-pixels with the light-emitting layer 13a, sub-pixels with the light-emitting layer 13b, and sub-pixels with the light-emitting layer 13c, respectively. Alternatively, the emission of blue light is controlled. Then, light emission of red, green, and blue light is controlled for each pixel composed of three types of sub-pixels, and full-color display is performed.

In addition, in the light emitting display element 100 of the embodiment of the present invention, it is possible to form a color filter between the light emitting layer 13 and the substrate 12 . That is, a red color filter is formed between the light emitting layer 13a and the substrate 12 , a green color filter is formed between the light emitting layer 13b and the substrate 12 , and the light emitting layer 13c and the substrate 12 are formed. A red color filter can be formed between (12).

In the light emitting display element 100 of the third embodiment of the present invention, the color purity of display can be improved by forming a color filter. Here, as a color filter, a well-known thing for liquid crystal display elements etc. can be formed by a well-known method, and can be used.

(Example)

Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples at all.

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

The semiconductor quantum dots used in this embodiment are shown below.

Semiconductor quantum dot A: InP/ZnS core-shell type quantum dot

Semiconductor quantum dot B: InCuS ₂ /ZnS core-shell type quantum dot

Semiconductor quantum dot C: Si quantum dot

And, semiconductor quantum dot A: InP/ZnS core-shell type quantum dot, semiconductor quantum dot B: InCuS ₂ /ZnS core-shell type quantum dot, semiconductor quantum dot C: Si quantum dot used in the following examples are generally known methods. can be synthesized.

For example, regarding the semiconductor quantum dot A: InP/ZnS core-shell type quantum dot, the technical document "Journal of American Chemical Society. 2007, 129, 15432-15433 on the "semiconductor quantum dots B: InCuS ₂ / ZnS core-shell quantum dots are technical literature as to" Journal of American Chemical Society. 2009, 131, 5691-5697” and the technical literature “Chemistry of Materials. 2009, 21, 2422-2429," regarding the semiconductor quantum dot C: Si quantum dot, the technical document "Journal of American Chemical Society. 2010, 132, 248-253", and can synthesize|combine it with reference to the method described in.

Together with the above [B] semiconductor quantum dots, [A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule (component [A]) and [C] a hydrocarbon-based solvent (component [C]) ), and further, [D] a polymerization initiator (component [D]), [E] the above-mentioned [E1] component, which is a polymer having a weight average molecular weight of 5000 or more and 40,000 or less (component [E]) having a carboxyl group, [E2] Curable resin composition of an Example was prepared using the component. Next, the cured film of an Example was formed using it, and the evaluation was performed.

<Synthesis example of [E1] component>

Into a flask provided with a cooling tube and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate was introduced and nitrogen-substituted. It is heated to 80 degreeC, and at the same temperature, 50 mass parts of propylene glycol monomethyl ether acetate, 20 mass parts of methacrylic acid, 5 mass parts of benzyl methacrylate, 10 mass parts of styrene, 13 mass of 2-hydroxyethyl methacrylate A mixed solution of 40 parts by mass of part, 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is added dropwise over 2 hours. Then, the temperature was maintained and polymerization was carried out for 1 hour. Then, the temperature of the reaction solution was raised to 90 degreeC, and the resin solution (solid content concentration = 33 mass %) was obtained by superposing|polymerizing for 1 hour further. The obtained resin was Mw=11100, Mn=6000, and Mw/Mn=1.85. Let this be a carboxyl group containing resin solution (E-1).

Example 1

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

[E2] A solution containing carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade name "UC-102") as a component, in an amount equivalent to 30 parts by mass (solid content) of the polymer, and [D] 1,2 as component -Octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) 10 parts by mass, 1,9-no as component [A] 70 parts by mass of nandiol diacrylate (NK ester (registered trademark) A-NOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) was mixed, dissolved in p-mentane as component [C], and semiconductor quantum dot A as component [B]. 10 parts by mass of was mixed to prepare a curable resin composition (β-I).

Example 2

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

[E2] 20 parts by mass of carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade name "UC-203") as a component and 1,2-octanedione-1-[4-(phenylthio)- as a component [D] 2-(O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) 10 parts by mass, [A] 1,10-decanediol diacrylate (NK ester manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (registered trademark) A-DOD-N) 80 parts by mass, dissolved in evacuation as component [C], and 10 parts by mass of semiconductor quantum dot A as component [B] to obtain a curable resin composition (β-II) prepared

Example 3

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

[E2] 30 parts by mass of carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade name "UC-102") as a component, and 2-dimethylamino-2-(4-methylbenzyl)-1-( 10 parts by mass of 4-morpholin-4-yl-phenyl)-butan-1-one (Irgacure (registered trademark) 379 manufactured by BASF) 1,9-nonanediol diacrylate (Shin 50 parts by mass of Nakamura Chemical Industry Co., Ltd. NK ester (registered trademark) A-NOD-N) and 20 parts by mass of propylene oxide-modified trimethylolpropane triacrylate (Aronix (registered trademark) M-321, manufactured by Toagose Corporation) are mixed. Then, it was made to melt|dissolve in decane as [C] component, 10 mass parts of semiconductor quantum dots C were mixed as [B] component, and curable resin composition ((beta)-III) was prepared.

Example 4

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

[E2] 40 parts by mass of carboxyl group-containing polyisoprene (manufactured by Kuraray Co., Ltd., trade name "UC-102") as a component and 1,2-octanedione-1-[4-(phenylthio)- as a [D] component 2-(O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) 10 parts by mass, ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-1-(O-acetyloxime) (Irgacure (registered trademark) OXE02 manufactured by BASF) 5 parts by mass, [A] 1,9-nonanediol diacrylate (Shin-Nakamura Chemical Industry Co., Ltd.) 60 parts by mass of manufactured NK ester (registered trademark) A-NOD-N) was mixed, dissolved in evacuation as component [C], and 10 parts by mass of semiconductor quantum dots B were mixed as component [B], and a curable resin composition (β -IV) was prepared.

Example 5

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

[E1] After adding and dissolving 40 parts by mass of p-mentane as component [C] to 90 parts by mass of the carboxyl group-containing resin solution (E-1) as component [B], 10 parts by mass of semiconductor quantum dot A is mixed as component [B] to prepare a uniform solution, and as [D] component 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure (registered trademark) manufactured by BASF) 907) 5 parts by mass, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) 5 parts by mass, [ A] 20 parts by mass of tricyclodecane dimethanol diacrylate (NK ester (registered trademark) A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as a component, ditrimethylolpropane tetraacrylate (Aronix (registered trademark) manufactured by Toagose Corporation) ) M-408) 10 parts by mass was mixed to prepare a curable resin composition (β-V).

Example 6

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

After apply|coating the curable resin composition ((beta)-I) prepared in Example 1 with a spinner on an alkali free glass substrate, the coating film was formed by prebaking on an 80 degreeC hotplate for 2 minutes.

Next, through a photomask having a predetermined pattern, the obtained coating film was irradiated with radiation at an exposure amount of 700 J/m 2 using a high-pressure mercury lamp. Then, development was performed for 23 degreeC and 80 second in 0.04 mass % potassium hydroxide aqueous solution.

Next, the obtained pattern was irradiated with an exposure amount of 10000 J/m<2> using a high-pressure mercury-vapor lamp, and the cured film patterned in the predetermined shape was formed.

Next, the edge part of the patterned cured film was observed with the optical microscope, when there is no image development residue and the linear part of a pattern is formed in linear shape, it judged that patterning property is favorable.

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

Example 7

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

On an alkali free glass substrate, after apply|coating curable resin composition ((beta)-II) prepared in Example 2 with a spinner, the coating film was formed by prebaking on an 80 degreeC hotplate for 2 minutes.

Next, through a photomask having a predetermined pattern, the obtained coating film is irradiated with a high-pressure mercury lamp at an exposure amount of 1000 J/m 2 , and development is performed at 23° C. for 80 seconds with a 0.04 mass% potassium hydroxide aqueous solution. did

Next, the obtained pattern was irradiated with an exposure amount of 10000 J/m<2> using a high-pressure mercury-vapor lamp, and the cured film patterned in the predetermined shape was formed.

Next, the edge part of the patterned cured film was observed with the optical microscope, when there is no image development residue and the linear part of a pattern is formed in linear shape, it judged that patterning property is favorable.

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

Example 8

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

After apply|coating the curable resin composition ((beta)-III) prepared in Example 3 with a spinner on an alkali-free-glass board|substrate, the coating film was formed by prebaking on an 80 degreeC hotplate for 2 minutes.

Next, through a photomask having a predetermined pattern, the obtained coating film is irradiated with an exposure amount of 800 J/m 2 using a high-pressure mercury lamp, and development is performed at 23° C. for 80 seconds with a 0.04 mass % potassium hydroxide aqueous solution. did

Next, the obtained pattern was irradiated with an exposure amount of 10000 J/m<2> using a high-pressure mercury-vapor lamp, and the cured film patterned in the predetermined shape was formed.

Next, the edge part of the patterned cured film was observed with the optical microscope, when there is no image development residue and the linear part of a pattern is formed in linear shape, it judged that patterning property is favorable.

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

Example 9

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

After apply|coating curable resin composition ((beta)-IV) prepared in Example 4 with a spinner on an alkali-free-glass board|substrate, the coating film was formed by prebaking on an 80 degreeC hotplate for 2 minutes.

Next, through a photomask having a predetermined pattern, the obtained coating film is irradiated with an exposure amount of 800 J/m 2 using a high-pressure mercury lamp, and development is performed at 23° C. for 80 seconds with a 0.04 mass % potassium hydroxide aqueous solution. did

Next, the obtained pattern was irradiated with an exposure amount of 10000 J/m<2> using a high-pressure mercury-vapor lamp, and the cured film patterned in the predetermined shape was formed.

Next, the edge part of the patterned cured film was observed with the optical microscope, when there is no image development residue and the linear part of a pattern is formed in linear shape, it judged that patterning property is favorable.

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

Example 10

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

After apply|coating curable resin composition ((beta)-V) prepared in Example 5 with a spinner on an alkali free glass substrate, the coating film was formed by prebaking on an 80 degreeC hotplate for 2 minutes.

Next, through a photomask having a predetermined pattern, the obtained coating film is irradiated with an exposure amount of 800 J/m 2 using a high-pressure mercury lamp, and development is performed at 23° C. for 80 seconds with a 0.04 mass % potassium hydroxide aqueous solution. did

Next, the obtained pattern was irradiated with an exposure amount of 10000 J/m<2> using a high-pressure mercury-vapor lamp, and the cured film patterned in the predetermined shape was formed.

Next, the edge part of the patterned cured film was observed with the optical microscope, when there is no image development residue and the linear part of a pattern is formed in linear shape, it judged that patterning property is favorable.

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

Example 11

[Evaluation of curing shrinkage]

About the cured film by the formation method of Example 6, the exposure process of 10000 J/m<2> was further performed, and the film thickness before and behind this exposure was measured with a stylus type film thickness meter (Alpha Step IQ, KLA Tenko Corporation). And the residual film ratio ((film thickness after process/film thickness before process) x100) was computed, and this residual film ratio was made into cure shrinkage property. The residual film rate was 99 %, and it judged that cure shrinkage property was favorable.

Similarly, about the cured film by the formation method of Example 7, the exposure process of 10000 J/m<2> was further performed, and the film thickness before and behind this exposure was measured with a stylus type film thickness meter (alpha step IQ, KLA Tenko Corporation). . And the residual film ratio ((film thickness after process / film thickness before process) *100) was computed, and this residual film ratio was made into cure shrinkage property. The residual film rate was 99 %, and it judged that cure shrinkage property was favorable.

Similarly, about the cured film by the formation method of Example 8, the exposure process of 10000 J/m<2> was further performed, and the film thickness before and behind this exposure was measured with a stylus type film thickness meter (alpha step IQ, KLA Tenko Corporation). . And the residual film ratio ((film thickness after process/film thickness before process) x100) was computed, and this residual film ratio was made into cure shrinkage property. The residual film rate was 99 %, and it judged that cure shrinkage property was favorable.

Similarly, about the cured film by the formation method of Example 9, the exposure process of 10000 J/m<2> was further performed, and the film thickness before and behind this exposure was measured with a stylus type film thickness meter (Alpha Step IQ, KLA Tenko Corporation). . And the residual film ratio ((film thickness after process / film thickness before process) *100) was computed, and this residual film ratio was made into cure shrinkage property. The residual film rate was 99 %, and it judged that cure shrinkage property was favorable.

Similarly, about the cured film by the formation method of Example 10, the exposure process of 10000 J/m<2> was further performed, and the film thickness before and behind this exposure was measured with a stylus type film thickness meter (Alpha Step IQ, KLA Tenko Corporation). . And the residual film ratio ((film thickness after process/film thickness before process) x100) was computed, and this residual film ratio was made into cure shrinkage property. The residual film rate was 99 %, and it judged that cure shrinkage property was favorable.

Example 12

[Evaluation of light resistance]

About the cured film by the formation method of Example 6, using UV irradiation apparatus (UVX-02516S1JS01, Ushiosa), irradiate 800000J/m<2> ultraviolet light at 130 mW illumination intensity, and the film|membrane decrease amount after irradiation further investigated. The film reduction amount was 2% or less, and it was judged that light resistance was favorable.

Similarly, about the cured film by the formation method of Example 7, using UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), 800000 J/m<2> ultraviolet light is irradiated with 130 mW illuminance, and the film|membrane after irradiation decrease was investigated. The film reduction amount was 2% or less, and it was judged that light resistance was favorable.

Similarly, about the cured film by the formation method of Example 8, using UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), 800000 J/m<2> ultraviolet light is irradiated with 130 mW illuminance, and the film|membrane after irradiation decrease was investigated. The film reduction amount was 2% or less, and it was judged that light resistance was favorable.

Similarly, about the cured film by the formation method of Example 9, using UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), 800000 J/m<2> ultraviolet light is irradiated with 130 mW illuminance, and the film|membrane after irradiation decrease was investigated. The film reduction amount was 2% or less, and it was judged that light resistance was favorable.

Similarly, about the cured film by the formation method of Example 10, using UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), irradiating 800000 J/m<2> ultraviolet light at 130 mW illumination intensity, and irradiating the film|membrane further similarly decrease was investigated. The film reduction amount was 2% or less, and it was judged that light resistance was favorable.

Example 13

[Evaluation of fluorescence properties]

About the cured film by the formation method of Example 6, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics company). The fluorescence quantum yield was 37%, and it was judged that a fluorescence characteristic was favorable.

Similarly, about the cured film by the formation method of Example 7, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics company). The fluorescence quantum yield was 39%, and it was judged that a fluorescence characteristic was favorable.

Similarly, about the cured film by the formation method of Example 8, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics company). The fluorescence quantum yield was 38%, and it was judged that a fluorescence characteristic was favorable.

Similarly, about the cured film by the formation method of Example 9, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics company). The fluorescence quantum yield was 35 %, and it was judged that a fluorescence characteristic was favorable.

Similarly, about the cured film by the formation method of Example 10, the fluorescence quantum yield in 25 degreeC was further investigated using the absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics company). The fluorescence quantum yield was 36%, and it was judged that a fluorescence characteristic was favorable.

The cured film formed using the curable resin composition of this invention is excellent in reliability, such as light resistance, and it is also easy to pattern, and as a wavelength conversion layer or a wavelength conversion film, in addition to a display element and the electronic device using the same, LED and a solar cell. It can also be used in the field of

1, 1a: coating film
2, 12, 16: substrate
3: photo mask
4, 4a: radiation
5: cured film
11: wavelength conversion substrate
13, 13a, 13b, 13c: light emitting layer
14 : Black Matrix
15: adhesive layer
17, 17a, 17b, 17c: light source
18: light source substrate
100: light emitting display element

Claims (13)

[A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule;
[B] semiconductor quantum dots,
[C] a hydrocarbon-based solvent, and
[E] contains a polymer having a carboxyl group and having a weight average molecular weight of 5000 or more and 40000 or less,
The [A] compound is at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)
Curable resin composition:

(in formula (1), X represents a divalent group represented by formula (5), in formula (5), n represents an integer of 7 to 20; Y represents a group represented by formula (4), and R ¹ is a hydrogen atom or a methyl group;
In formula (2), R<^2> represents a hydrogen atom or a C1-C12 alkyl group; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, m represents an integer of 1-4;
In formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, and m represents the integer of 0-4). According to claim 1,
Further [D] Curable resin composition containing a polymerization initiator. 3. The method of claim 2,
[D] The curable resin composition wherein the polymerization initiator is a polymerization initiator containing a hydrocarbon group having 1 to 20 carbon atoms. According to claim 1,
[B] A compound in which the semiconductor quantum dot contains at least two elements 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 curable resin composition comprising a. According to claim 1,
[B] Curable resin composition in which the semiconductor quantum dot contains the compound which contains In as a structural component. According to claim 1,
[B] at least a semiconductor quantum dot is selected from the group consisting of InP/ZnS compound, CuInS ₂ /ZnS compound, AgInS ₂ compound, (ZnS/AgInS ₂ ) solid solution/ZnS compound, Zn-doped AgInS ₂ compound, and Si compound One type, curable resin composition. [A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule;
[B] semiconductor quantum dots and;
[C] contains a hydrocarbon solvent,
The [A] compound is at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)
Curable resin composition:

(in formula (1), X represents a divalent group represented by formula (5), in formula (5), n represents an integer of 7 to 20; Y represents a group represented by formula (4), and R ¹ is a hydrogen atom or a methyl group;
In formula (2), R<^2> represents a hydrogen atom or a C1-C12 alkyl group; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, m represents an integer of 1-4;
In formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, and m represents the integer of 0-4). The cured film formed using the curable resin composition in any one of Claims 1-7. [A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule;
[B] semiconductor quantum dots and;
[C] a wavelength conversion film formed using a curable resin composition containing a hydrocarbon solvent,
The [A] compound is at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3)
Wavelength Conversion Film:

(in formula (1), X represents a divalent group represented by formula (5), in formula (5), n represents an integer of 7 to 20; Y represents a group represented by formula (4), and R ¹ is a hydrogen atom or a methyl group;
In formula (2), R<^2> represents a hydrogen atom or a C1-C12 alkyl group; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, m represents an integer of 1-4;
In formula (3), R ³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; Y represents group represented by Formula (4), R<^1> represents a hydrogen atom or a methyl group; W represents an ethylene oxide group or a propylene oxide group, and m represents the integer of 0-4). A method of forming a light emitting layer of a light emitting device, comprising:
(1) a step of forming a coating film of the curable resin composition on a substrate;
(2) a step of irradiating at least a part of the coating film formed in step (1) with radiation;
(3) a step of developing the coating film irradiated with radiation in step (2);
(4) having a step of exposing the coating film developed in step (3);
The said curable resin composition is curable resin composition in any one of Claims 1-7
A method of forming a light emitting layer. The light emitting display element which has the cured film of Claim 8. The light emitting display element which has the wavelength conversion film of Claim 9. [A] a compound having a weight average molecular weight of 150 or more and 10000 or less having two or more polymerizable groups in one molecule;
[B] semiconductor quantum dots,
[C] a hydrocarbon-based solvent, and
[E] containing a polymer having a weight average molecular weight of 5000 or more and 40000 or less having a carboxyl group
Curable resin composition.

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